CN104211735A - Metal complex ligand, metal complex, preparation method and application of metal complex, high-molecular polymer as well as preparation method and application of high-molecular polymer - Google Patents
Metal complex ligand, metal complex, preparation method and application of metal complex, high-molecular polymer as well as preparation method and application of high-molecular polymer Download PDFInfo
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- CN104211735A CN104211735A CN201410412074.6A CN201410412074A CN104211735A CN 104211735 A CN104211735 A CN 104211735A CN 201410412074 A CN201410412074 A CN 201410412074A CN 104211735 A CN104211735 A CN 104211735A
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- Prior art keywords
- substituted
- unsubstituted
- alkyl
- carbonyl
- aryl
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 56
- 239000003446 ligand Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 315
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 18
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims description 496
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 389
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 375
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 310
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 258
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 250
- 239000001257 hydrogen Substances 0.000 claims description 194
- 229910052739 hydrogen Inorganic materials 0.000 claims description 194
- 150000002431 hydrogen Chemical group 0.000 claims description 158
- -1 imino- Chemical class 0.000 claims description 143
- 150000003254 radicals Chemical class 0.000 claims description 124
- 125000003545 alkoxy group Chemical group 0.000 claims description 105
- 125000000217 alkyl group Chemical group 0.000 claims description 97
- 125000004429 atom Chemical group 0.000 claims description 76
- 229910052736 halogen Inorganic materials 0.000 claims description 72
- 150000002367 halogens Chemical class 0.000 claims description 72
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 72
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 69
- 239000002585 base Substances 0.000 claims description 68
- 229910052760 oxygen Inorganic materials 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 63
- 239000001301 oxygen Substances 0.000 claims description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 56
- 125000003282 alkyl amino group Chemical group 0.000 claims description 54
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 49
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 125000001769 aryl amino group Chemical group 0.000 claims description 34
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 125000000266 alpha-aminoacyl group Chemical group 0.000 claims description 30
- 229910052727 yttrium Inorganic materials 0.000 claims description 30
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 29
- 238000005865 alkene metathesis reaction Methods 0.000 claims description 28
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 27
- 238000005649 metathesis reaction Methods 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 22
- 229910052707 ruthenium Inorganic materials 0.000 claims description 22
- 125000004076 pyridyl group Chemical group 0.000 claims description 20
- 125000004104 aryloxy group Chemical group 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 18
- 125000003375 sulfoxide group Chemical group 0.000 claims description 17
- 125000005844 heterocyclyloxy group Chemical group 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 9
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 3
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 1
- OBTZDIRUQWFRFZ-UHFFFAOYSA-N 2-(5-methylfuran-2-yl)-n-(4-methylphenyl)quinoline-4-carboxamide Chemical compound O1C(C)=CC=C1C1=CC(C(=O)NC=2C=CC(C)=CC=2)=C(C=CC=C2)C2=N1 OBTZDIRUQWFRFZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1015
- 229910052786 argon Inorganic materials 0.000 description 507
- 239000012327 Ruthenium complex Substances 0.000 description 409
- 239000000047 product Substances 0.000 description 141
- 230000015572 biosynthetic process Effects 0.000 description 132
- 238000003786 synthesis reaction Methods 0.000 description 132
- 239000007789 gas Substances 0.000 description 128
- 238000001914 filtration Methods 0.000 description 127
- 239000012265 solid product Substances 0.000 description 126
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 123
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 123
- USPLDBATMHXKKD-UHFFFAOYSA-N dichloromethane;pentane Chemical compound ClCCl.CCCCC USPLDBATMHXKKD-UHFFFAOYSA-N 0.000 description 123
- 238000001035 drying Methods 0.000 description 123
- 239000000706 filtrate Substances 0.000 description 123
- 239000004576 sand Substances 0.000 description 123
- 239000000741 silica gel Substances 0.000 description 123
- 229910002027 silica gel Inorganic materials 0.000 description 123
- 238000010898 silica gel chromatography Methods 0.000 description 123
- 238000005406 washing Methods 0.000 description 123
- 238000012360 testing method Methods 0.000 description 113
- 238000005481 NMR spectroscopy Methods 0.000 description 64
- 239000003054 catalyst Substances 0.000 description 16
- 238000006555 catalytic reaction Methods 0.000 description 16
- 238000003556 assay Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 125000005257 alkyl acyl group Chemical group 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000005277 alkyl imino group Chemical group 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002098 pyridazinyl group Chemical group 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000002393 azetidinyl group Chemical group 0.000 description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 125000003453 indazolyl group Chemical class N1N=C(C2=C1C=CC=C2)* 0.000 description 2
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 125000001786 isothiazolyl group Chemical group 0.000 description 2
- 125000000842 isoxazolyl group Chemical group 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 229940002612 prodrug Drugs 0.000 description 2
- 239000000651 prodrug Substances 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- VMLKTERJLVWEJJ-UHFFFAOYSA-N 1,5-naphthyridine Chemical compound C1=CC=NC2=CC=CN=C21 VMLKTERJLVWEJJ-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- FJRPOHLDJUJARI-UHFFFAOYSA-N 2,3-dihydro-1,2-oxazole Chemical compound C1NOC=C1 FJRPOHLDJUJARI-UHFFFAOYSA-N 0.000 description 1
- ZABMHLDQFJHDSC-UHFFFAOYSA-N 2,3-dihydro-1,3-oxazole Chemical compound C1NC=CO1 ZABMHLDQFJHDSC-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- WEQPBCSPRXFQQS-UHFFFAOYSA-N 4,5-dihydro-1,2-oxazole Chemical compound C1CC=NO1 WEQPBCSPRXFQQS-UHFFFAOYSA-N 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000002527 bicyclic carbocyclic group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000004623 carbolinyl group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical class N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004598 dihydrobenzofuryl group Chemical group O1C(CC2=C1C=CC=C2)* 0.000 description 1
- 125000004582 dihydrobenzothienyl group Chemical group S1C(CC2=C1C=CC=C2)* 0.000 description 1
- 125000005051 dihydropyrazinyl group Chemical group N1(CC=NC=C1)* 0.000 description 1
- 125000005056 dihydrothiazolyl group Chemical group S1C(NC=C1)* 0.000 description 1
- 125000005058 dihydrotriazolyl group Chemical group N1(NNC=C1)* 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- KJTLSVCANCCWHF-BKFZFHPZSA-N ruthenium-106 Chemical compound [106Ru] KJTLSVCANCCWHF-BKFZFHPZSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
- C07D207/48—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a metal complex ligand, a metal complex as well as a preparation method and an application of the metal complex. The structural formula of the metal complex disclosed by the invention is shown in the specification. The metal complex has the advantages of relatively high catalytic activity, diversities of structures and physical properties and the like and provides a diverse optimum selection for the catalytic application of various raw materials. The invention also discloses various novel functional high-molecular materials generated by catalytic ring opening polymerization (ROMP) reaction of various different types of small-molecular cycloolefins and application thereof and the novel functional high-molecular materials have the formulas shown in the specification.
Description
The application is application number is 2009101757906, the applying date is on September 27th, 2009, and denomination of invention is the divisional application of the patent application of " a kind of metal complex part, metal complex and its preparation method and application, high molecular polymer and its preparation method and application ".
Technical field
The present invention relates to a kind of part, complex compound and its preparation method and application, a kind of polymkeric substance and its preparation method and application, is specifically related to a kind of metal complex part, metal complex and its preparation method and application, a kind of high molecular polymer and its preparation method and application.
Background technology
The research and development of olefin metathesis metathesis ruthenium catalyst and utilize new and effective ruthenium complex catalyst to prepare the multifunctional macromolecule novel materials such as all kinds of high strength and high hardness by the method for olefin catalytic metathesis ring-opening polymerization (ROMP:Ring Opening Metathesis Polymerization) oneself causes and payes attention to widely.In this field, the seminar such as originator Grubbs of ruthenium complex catalyst has reported dissimilar ruthenium complex catalyst and has prepared all kinds of multi-functional polymer novel material by associated olefinic catalysed metathesis ring-opening polymerization and reaction and injection molding process (RIM:Reaction Injection Molding) technology, and the key wherein preparing all kinds of multifunctional macromolecule novel material is effective ROMP catalyzer.
Olefin catalytic polymerization product (ROMP-RIM) has higher resistance to impact shock and modulus in flexure, not easily temperature influence, there is fabulous erosion resistance, the very good mechanical properties such as low density, all have broad application prospects in fields such as traffic, electric installation, sports and amusement facility, civil construction material, casting, communications.Current main ROMP new material industry manufacturer is the ZEON company that Nobel laureate professor Grubbs provides the Hercules company of the U.S. Materia Inc. of ROMP patented technology and the U.S., Goodrich company and Japan.
Some current olefin catalytic polymerization products oneself obtain industrial applications, but the strength and modulus etc. that its shortcoming prepares all kinds of multi-functional polymer novel material by the method for ruthenium catalyst ring-opening polymerization is in above the average, need to be researched and developed further more effective alkene ring-opening polymerization catalyst and polymerization reaction monomer thereof and complete processing, reach the object improving mechanical property.
Summary of the invention
The present invention is in order to solve the shortcoming of existing olefin metathesis reaction catalyzer and associated olefinic catalysed metathesis ring-opening polymerization, and the performance being improved olefin metathesis reaction catalyzer by research and development improves the mechanical propertys such as the strength and modulus of olefinic polymerization product.The feature of novel metal complexes part of the present invention is that the part that formed with Sauerstoffatom and/or nitrogen-atoms can be formed with metal especially ruthenium ion and comparatively stablizes and have the metal complex catalyst of greater activity, the present invention introduces dissimilar, different physical characteristics, different catalytically active part in metal complex catalyst, thus for chemical industry, medicine and polymer novel material synthesis preparation provide metal complex catalyst that is more effectively various, different activities, the optimization for olefin metathesis reaction and products thereof provides the selection of more catalysis techniques.
Therefore, an object of the present invention is to provide the olefin metathesis metal complex part that a kind of structural formula is formula Ia, Ib, Ic:
Wherein, Z is CH
2or
M=0 or 1, n=0 or 1;
During n=1, X
1and Y
1be nitrogen, oxygen, sulphur, CH independently
2, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy, substituted or unsubstituted C
2-C
20heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
20alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; X
1the parent that each group represented connects is Y
1, the part wherein connecting Y can be each group itself, also can be the various substituting groups of group, Y
1the parent that each group represented connects is X
1, wherein connect R
2part can be group itself, also can be the various substituting groups of group;
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
6-C
20aryloxy, substituted or unsubstituted C
2-C
20heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
20alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; In formula Ia, the parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; In formula Ib, the parent that the group that Y represents connects is aromatic ring, and the parent that the group that in Ic, Y represents connects is for connecting R
3carbon;
During m=1, X is nitrogen, oxygen, sulphur, CH, CH
2, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy, substituted or unsubstituted C
2-C
20heterocyclic aryl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
20alkyl imino base, unsubstituted C
1-C
20alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is Y, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
between can be singly-bound or double bond;
R
1for hydrogen, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20alkylthio, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy or substituted or unsubstituted C
2-C
20heterocyclic radical;
R
2for hydrogen, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20alkylthio, substituted or unsubstituted C
1-C
20alkyl siloxy, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
6-C
20aryl, C
6-C
20aryloxy, aldehyde radical, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
6-C
20the carbonyl of aryl, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclic radical or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
R
3for hydrogen, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20alkylthio, C
2-C
20heterocyclic radical, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
2-C
20heterocyclic radical, C
6-C
20aryl, C
6-C
20aryloxy, connection C
1-C
20the carbonyl of alkyl, connection C
6-C
20the carbonyl of aryl, connection C
2-C
20the carbonyl of heterocyclic radical, connection C
1-C
20the carbonyl of alkoxyl group, connection C
6-C
20the carbonyl of aryloxy, connection C
6-C
20the carbonyl of heterocyclyloxy base, aminoacyl, connection C
1-C
20the carbonyl of alkylamino, connection C
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido, substituted or unsubstituted C
2-C
20heterocyclic radical urea groups, connection C
1-C
20the alkylsulfonyl of alkylamino, connection C
6-C
20the alkylsulfonyl of arylamino, connection C
2-C
20the alkylsulfonyl of heterocyclylamino group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, itrile group, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
2-C
20heterocyclic radical, substituted or unsubstituted amino, aminoacyl, connection C
1-C
20the carbonyl of alkylamino, C
6-C
20aryl, C
6-C
20aryloxy, sulfoxide group, sulfuryl, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
6-C
20the carbonyl of aryl, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclic radical, connection C
1-C
20the carbonyl of alkoxyl group, connection C
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido or substituted or unsubstituted C
2-C
20heterocyclic radical urea groups;
E
2for hydrogen, halogen, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, aminoacyl, connection C
1-C
20the carbonyl of alkylamino, connection C
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, C
6-C
20aryl, C
6-C
20aryloxy, C
2-C
20heterocyclic aryl, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, connection C
6-C
20the carbonyl of aryl, connection C
2-C
20the carbonyl of heterocyclic radical, connection C
1-C
20the carbonyl of alkoxyl group, connection C
6-C
20the carbonyl of aryloxy, connection C
2-C
20the carbonyl of heterocyclylamino group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkyl siloxy, C
6-C
20aryloxy, C
6-C
20aryl, C
2-C
20heterocyclic aryl, connection C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
4, E
5, E
6and E
7be hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted C independently
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkane siloxy, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted amino, aminoacyl, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkylamino, connect substituted or unsubstituted C
6-C
20the carbonyl of arylamino, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
6-C
20the carbonyl of aryl, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclic radical, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido or substituted or unsubstituted C
2-C
20heterocyclic radical urea groups, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring.
In the present invention, preferably, in formula Ia, Ib, Ic,
Z is CH
2or TsNHN=;
M=0 or 1, n=0 or 1;
During n=1, X
1and Y
1be nitrogen, oxygen, sulphur, CH independently
2, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
15alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; X
1the parent that each group represented connects is Y
1, the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; Y
1the parent that each group represented connects is X
1, the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
15alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; In formula Ia, the parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; In formula Ib, the parent that the group that Y represents connects is aromatic ring, and the parent that the group that in Ic, Y represents connects is for connecting R
3carbon;
During m=1, X is nitrogen, oxygen, sulphur, CH, CH
2, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
1-C
15imido grpup; Such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is Y, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
between can be singly-bound or double bond;
R
1for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy or substituted or unsubstituted C
2-C
15heterocyclic radical;
R
2for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, substituted or unsubstituted C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, aldehyde radical, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
R
3for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, connection C
1-C
15the carbonyl of alkyl, connection C
6-C
15the carbonyl of aryl, connection C
2-C
15the carbonyl of heterocyclic radical, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, connection C
6-C
15the carbonyl of arylamino, connection C
2-C
15the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
20heterocyclic radical, C
1-C
20alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, C
1-C
15alkyl sulphonyl, C
6-C
20aryl sulfonyl or C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, sulfuryl, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, aldehyde radical, connection C
1-C
15the carbonyl of alkyl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, substituted or unsubstituted C
1-C
15alkyl, connection C
1-C
15amino alkylsulfonyl or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
20heterocyclic radical, C
1-C
20alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, C
1-C
15alkyl sulphonyl, C
6-C
20aryl sulfonyl or C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
2for hydrogen, halogen, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
6-C
15aryl, C
6-C
15aryloxy, C
2-C
15heterocyclic aryl, aldehyde radical, connection C
1-C
15the carbonyl of alkyl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkylamino or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
15aryl, C
2-C
15heterocyclic radical, C
1-C
15alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane siloxy, C
6-C
15aryl, C
6-C
15aryloxy, C
2-C
15heterocyclic aryl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
15aryl, C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical; Or Rc, Rd and atom N connect into ring;
E
4, E
5, E
6and E
7be hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted C independently
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, substituted or unsubstituted C
2-C
15heterocyclic radical, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, connection C
6-C
15the carbonyl of arylamino, connection C
2-C
15the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, substituted or unsubstituted C
1-C
15alkylsulfonamido, connection C
1-C
15the sulphonyl of alkylamino, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
15alkyl sulphonyl, substituted or unsubstituted C
6-C
15aryl sulfonyl or substituted or unsubstituted C
2-C
15heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring.
In the present invention, better, in formula Ia, Ib, Ic,
Z is CH
2or
M=0 or 1, n=0 or 1;
During n=1, X
1for oxygen, CH
2, substituted or unsubstituted C
6-C
12aryl; Y
1for oxygen, nitrogen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imino-; Wherein, X
1the parent that each group represented connects is Y
1, Y
1the parent that each group represented connects is X
1;
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imido grpup or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
1-C
8aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; In formula Ia, the parent that the group that Y represents connects is X, and in formula Ib, the parent that the group that Y represents connects is aromatic ring, and the parent that the group that in Ic, Y represents connects is for connecting R
3carbon;
During m=1, X is nitrogen, oxygen, methyne, methylene radical, carbonyl; Y is nitrogen, oxygen, substituted or unsubstituted C
6-C
12aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is Y, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
between can be singly-bound or double bond;
R
1for hydrogen or substituted or unsubstituted C
6-C
12aryl;
R
2for methyl, sec.-propyl, substituted or unsubstituted C
1-C
8alkyl or substituted or unsubstituted C
6-C
12aryl;
R
3for hydrogen, substituted or unsubstituted C
1-C
8alkyl, substituted or unsubstituted C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, C
2-C
12heterocyclic aryl, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
8alkyl formyl radical, substituted or unsubstituted C
6-C
12aryl formyl radical or substituted or unsubstituted C
2-C
12heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E is hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, connection C
1-C
8the carbonyl of alkyl, connection C
1-C
8the carbonyl of alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, connection C
1-C
8the carbonyl of alkylamino, connection C
6-C
12the carbonyl of arylamino, connection C
2-C
12the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
8the alkylsulfonyl of alkyl amine group; Or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
8aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
2for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, C
2-C
12heterocyclic aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, substituted or unsubstituted C
1-C
8alkyl, formyl radical, substituted or unsubstituted C
1-C
8alkyl formyl radical, substituted or unsubstituted C
6-C
12aryl formyl radical; Or Rc, Rd and atom N connect into ring;
E
4, E
5, E
6and E
7be hydrogen, halogen, nitro, substituted or unsubstituted C independently
1-C
8alkyl, substituted or unsubstituted C
1-C
8alkoxyl group, substituted or unsubstituted C
1-C
8alkylamino, formamido-, substituted or unsubstituted C
1-C
8alkyl amido, connection C
1-C
8the carbonyl of alkylamino, connection C
6-C
12the carbonyl of arylamino, connection C
2-C
12the carbonyl of heterocyclylamino group, connection C
1-C
8the carbonyl of alkoxyl group, sulfoamido, substituted or unsubstituted C
6-C
12aryl, substituted or unsubstituted C
6-C
12aryloxy or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl, substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring.
During the best of the present invention is implemented, in formula Ia, Ib and Ic,
Z is CH
2or
N=0 or 1;
During n=1, X
1for CH
2or phenyl; Y
1for oxygen or carbonyl;
During m=0, Y is C
1-C
4alkylamino or C
1-C
3alkoxyl group;
During m=1, X is carbonyl, CH
2, CH or phenmethyl; Y be nitrogen, NH,
c
1-C
4alkoxyl group, C
5heterocyclic oxy group or C
1-C
3alkane siloxy; Singly-bound or double bond is can be between X and Y;
R
1for the phenyl that hydrogen, phenyl or nitro replace;
R
2for C
1-C
3alkyl or C
1-C
3alkoxyl group;
R
3for hydrogen or C
6aryl;
E is halogen, nitro, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, C
1-C
8alkyl amino sulfonyl, C
6-C
12n-aryl sulfonyl;
E
1and E
2for hydrogen, halogen, C independently
1-C
4alkyl or C
1-C
4alkoxyl group; E
3for hydrogen;
E
4, E
5and E
7for being hydrogen, C independently
1-C
4alkyl or C
1-C
4alkoxyl group;
E
6for hydrogen, halogen, C
1-C
4alkyl or C
1-C
6alkoxyl group;
In Ia, as n=0, R
2for hydrogen, halogen, C
1-C
4alkyl or C
1-C
4alkoxyl group.
Two of object of the present invention is to provide the metal complex that a kind of structural formula is formula IIa, IIb, IIc:
Wherein, M is metal Ru (Ru), tungsten (W) or nickel (Ni);
L
1and L
2be halogen (Cl, Br-or I), RCOO independently
-or ArO
-negatively charged ion;
L
3for a kind of complex ligands giving electronics;
L is a kind of to the complex ligands of electronics;
Wherein, Z is CH
2or
M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;
During n=1, X
1and Y
1be nitrogen, oxygen, sulphur, CH independently
2, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy, substituted or unsubstituted C
2-C
20heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
20alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; X
1the parent that each group represented connects is Y
1, the part wherein connecting Y can be each group itself, also can be the various substituting groups of group, Y
1the parent that each group represented connects is X
1, wherein connect R
2part can be group itself, also can be the various substituting groups of group;
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
6-C
20aryloxy, substituted or unsubstituted C
2-C
20heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
20alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; In formula Ia, the parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; In formula Ib, the parent that the group that Y represents connects is aromatic ring, and the parent that the group that in Ic, Y represents connects is for connecting R
3carbon;
During m=1, X is nitrogen, oxygen, sulphur, CH, CH
2, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy, substituted or unsubstituted C
2-C
20heterocyclic aryl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
20alkyl imino base, unsubstituted C
1-C
20alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is Y, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
between can be singly-bound or double bond;
R
1for hydrogen, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20alkylthio, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy or substituted or unsubstituted C
2-C
20heterocyclic radical;
R
2for hydrogen, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20alkylthio, substituted or unsubstituted C
1-C
20alkyl siloxy, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
6-C
20aryl, C
6-C
20aryloxy, aldehyde radical, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
6-C
20the carbonyl of aryl, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclic radical or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
R
3for hydrogen, substituted or unsubstituted C
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20alkylthio, C
2-C
20heterocyclic radical, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical or substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
2-C
20heterocyclic radical, C
6-C
20aryl, C
6-C
20aryloxy, connection C
1-C
20the carbonyl of alkyl, connection C
6-C
20the carbonyl of aryl, connection C
2-C
20the carbonyl of heterocyclic radical, connection C
1-C
20the carbonyl of alkoxyl group, connection C
6-C
20the carbonyl of aryloxy, connection C
6-C
20the carbonyl of heterocyclyloxy base, aminoacyl, connection C
1-C
20the carbonyl of alkylamino, connection C
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido, substituted or unsubstituted C
2-C
20heterocyclic radical urea groups, connection C
1-C
20the alkylsulfonyl of alkylamino, connection C
6-C
20the alkylsulfonyl of arylamino, connection C
2-C
20the alkylsulfonyl of heterocyclylamino group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, itrile group, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
2-C
20heterocyclic radical, substituted or unsubstituted amino, aminoacyl, connection C
1-C
20the carbonyl of alkylamino, C
6-C
20aryl, C
6-C
20aryloxy, sulfoxide group, sulfuryl, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
6-C
20the carbonyl of aryl, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclic radical, connection C
1-C
20the carbonyl of alkoxyl group, connection C
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido or substituted or unsubstituted C
2-C
20heterocyclic radical urea groups;
E
2for hydrogen, halogen, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, aminoacyl, connection C
1-C
20the carbonyl of alkylamino, connection C
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, C
6-C
20aryl, C
6-C
20aryloxy, C
2-C
20heterocyclic aryl, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, connection C
6-C
20the carbonyl of aryl, connection C
2-C
20the carbonyl of heterocyclic radical, connection C
1-C
20the carbonyl of alkoxyl group, connection C
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkyl siloxy, C
6-C
20aryloxy, C
6-C
20aryl, C
2-C
20heterocyclic aryl, connection C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
4, E
5, E
6and E
7be hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted C independently
1-C
20alkyl, substituted or unsubstituted C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkane siloxy, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted amino, aminoacyl, the substituted or unsubstituted C of connection
1-C
20the carbonyl of alkylamino, connect substituted or unsubstituted C
6-C
20the carbonyl of arylamino, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
20the carbonyl of alkyl, connect substituted or unsubstituted C
6-C
20the carbonyl of aryl, connect substituted or unsubstituted C
2-C
20the carbonyl of heterocyclic radical, connect substituted or unsubstituted C
1-C
20the carbonyl of alkoxyl group, connect substituted or unsubstituted C
6-C
20the carbonyl of aryloxy, connect substituted or unsubstituted C
6-C
20the carbonyl of heterocyclyloxy base, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido or substituted or unsubstituted C
2-C
20heterocyclic radical urea groups, substituted or unsubstituted C
6-C
20aryl, substituted or unsubstituted C
6-C
20aryloxy or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
20heterocyclic radical, substituted or unsubstituted C
1-C
20alkyl, formyl radical, substituted or unsubstituted C
1-C
20alkyl formyl radical, substituted or unsubstituted C
6-C
20aryl formyl radical, substituted or unsubstituted C
2-C
20heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
20alkyl sulphonyl, substituted or unsubstituted C
6-C
20aryl sulfonyl or substituted or unsubstituted C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring.
In the present invention, in described IIa, IIb and IIc, L is preferably following structural III a, III b, III c or III d:
Wherein, R
4and R
5be C independently
1-C
20alkyl, C
6-C
20aryl, C
1-C
20heterocyclic radical, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, formamido-, C
1-C
20alkyl amido, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, sulfoamido or C
1-C
20alkylsulfonamido;
R
6and R
7be hydrogen, C independently
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
6-C
20aryl, C
6-C
20aryloxy, C
2-C
20heterocyclic radical, sulfoxide group, sulfuryl, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, connection C
1-C
20the carbonyl of alkoxyl group, formamido-, C
1-C
20alkyl amido, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, sulfoamido, C
1-C
20alkylsulfonamido, halogen, nitro or itrile group;
R
8and R
9be substituted or unsubstituted C independently
1-C
20alkyl, C
1-C
20alkoxyl group, C
6-C
20aryl, C
6-C
20aryloxy or C
2-C
20heterocyclic radical;
In formula III a, preferably, R
4and R
5be aryl; R
6and R
7be hydrogen.
Better, the structural formula of L is formula III a or III d; R
4and R
5be mesityl; R
6and R
7be hydrogen or III d independently; R
8and R
9be cyclohexyl.
In another preferred embodiment of the present invention, in formula II a-II c,
Metal (M) is ruthenium;
L
1and L
2be chlorion;
L is III a or III d; Wherein R
4, R
5, R
6, R
7, R
8and R
9identical with aforementioned definitions;
M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;
During p=1, L
3for the one or more pyridyl be substituted in ortho position, a position and contraposition, the nitrogen-atoms of pyridyl connects parent, and between pyridyl, the substituting group of position and contraposition is independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkyl siloxy, C
6-C
15aryloxy, C
1-C
15alkyl amine group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, C
1-C
15alkyl amido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, sulfoamido or C
1-C
15alkylsulfonamido;
During n=1, p=0, X
1and Y
1be nitrogen, oxygen, sulphur, CH independently
2, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
15alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; X
1the parent that each group represented connects is Y
1, the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; Y
1the parent that each group represented connects is X
1, the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
15alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; In formula Ia, the parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; In formula Ib, the parent that the group that Y represents connects is aromatic ring, and the parent that the group that in Ic, Y represents connects is for connecting R
3carbon;
During m=1, X is nitrogen, oxygen, sulphur, CH, CH
2, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
1-C
15imido grpup; Such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is Y, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
between can be singly-bound or double bond;
R
1for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy or substituted or unsubstituted C
2-C
15heterocyclic radical;
R
2for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, substituted or unsubstituted C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, aldehyde radical, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
R
3for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, connection C
1-C
15the carbonyl of alkyl, connection C
6-C
15the carbonyl of aryl, connection C
2-C
15the carbonyl of heterocyclic radical, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, connection C
6-C
15the carbonyl of arylamino, connection C
2-C
15the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
20heterocyclic radical, C
1-C
20alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, C
1-C
15alkyl sulphonyl, C
6-C
20aryl sulfonyl or C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, sulfuryl, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, aldehyde radical, connection C
1-C
15the carbonyl of alkyl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, substituted or unsubstituted C
1-C
15alkyl, connection C
1-C
15amino alkylsulfonyl or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
20heterocyclic radical, C
1-C
20alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, C
1-C
15alkyl sulphonyl, C
6-C
20aryl sulfonyl or C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
2for hydrogen, halogen, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
6-C
15aryl, C
6-C
15aryloxy, C
2-C
15heterocyclic aryl, aldehyde radical, connection C
1-C
15the carbonyl of alkyl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkylamino or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
15aryl, C
2-C
15heterocyclic radical, C
1-C
15alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane siloxy, C
6-C
15aryl, C
6-C
15aryloxy, C
2-C
15heterocyclic aryl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
15aryl, C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical; Or Rc, Rd and atom N connect into ring;
E
4, E
5, E
6and E
7be hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted C independently
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, substituted or unsubstituted C
2-C
15heterocyclic radical, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, connection C
6-C
15the carbonyl of arylamino, connection C
2-C
15the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, substituted or unsubstituted C
1-C
15alkylsulfonamido, connection C
1-C
15the sulphonyl of alkylamino, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
20aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
15alkyl sulphonyl, substituted or unsubstituted C
6-C
15aryl sulfonyl or substituted or unsubstituted C
2-C
15heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring.
Better, in formula II a-II c,
M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;
During p=1, L
3for the one or more pyridyl be substituted in ortho position, a position and contraposition, the nitrogen-atoms of pyridyl connects parent, and between pyridyl, the substituting group of position and contraposition is independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
1-C
8alkylthio, C
1-C
8alkane is silica-based, C
1-C
8alkyl siloxy, C
6-C
12aryloxy, C
1-C
8alkyl amine group, substituted or unsubstituted C
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, formamido-, C
1-C
8alkyl amido, urea groups, substituted or unsubstituted C
1-C
8alkyl urea groups, sulfoamido or C
1-C
8alkylsulfonamido;
During n=1, p=0, X
1for oxygen, CH
2, substituted or unsubstituted C
6-C
12aryl; Y
1for oxygen, nitrogen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imino-; Wherein, X
1the parent that each group represented connects is Y
1, Y
1the parent that each group represented connects is X
1;
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imido grpup or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; In formula Ia, the parent that the group that Y represents connects is X, and in formula Ib, the parent that the group that Y represents connects is aromatic ring, and the parent that the group that in Ic, Y represents connects is for connecting R
3carbon;
During m=1, X is nitrogen, oxygen, methyne, methylene radical, carbonyl; Y is nitrogen, oxygen, substituted or unsubstituted C
6-C
12aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is Y, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group; The parent that the group that Y represents connects is X, and the part wherein connecting the other end can be each group itself, also can be the various substituting groups of group;
between can be singly-bound or double bond;
R
1for hydrogen or substituted or unsubstituted C
6-C
12aryl;
R
2for methyl, sec.-propyl, substituted or unsubstituted C
1-C
8alkyl or substituted or unsubstituted C
6-C
12aryl;
R
3for hydrogen, substituted or unsubstituted C
1-C
8alkyl, substituted or unsubstituted C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, C
2-C
12heterocyclic aryl, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
8alkyl formyl radical, substituted or unsubstituted C
6-C
12aryl formyl radical or substituted or unsubstituted C
2-C
12heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E is hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, connection C
1-C
8the carbonyl of alkyl, connection C
1-C
8the carbonyl of alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, connection C
1-C
8the carbonyl of alkylamino, connection C
6-C
12the carbonyl of arylamino, connection C
2-C
12the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
8the alkylsulfonyl of alkyl amine group; Or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
8aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
2for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, C
2-C
12heterocyclic aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, substituted or unsubstituted C
1-C
8alkyl, formyl radical, substituted or unsubstituted C
1-C
8alkyl formyl radical, substituted or unsubstituted C
6-C
12aryl formyl radical; Or Rc, Rd and atom N connect into ring;
E
4, E
5, E
6and E
7be hydrogen, halogen, nitro, substituted or unsubstituted C independently
1-C
8alkyl, substituted or unsubstituted C
1-C
8alkoxyl group, substituted or unsubstituted C
1-C
8alkylamino, formamido-, substituted or unsubstituted C
1-C
8alkyl amido, connection C
1-C
8the carbonyl of alkylamino, connection C
6-C
12the carbonyl of arylamino, connection C
2-C
12the carbonyl of heterocyclylamino group, connection C
1-C
8the carbonyl of alkoxyl group, sulfoamido, substituted or unsubstituted C
6-C
12aryl, substituted or unsubstituted C
6-C
12aryloxy or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl, substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring.
In of the present invention one best enforcement, in formula II a-II c,
M is ruthenium; L is
thricyclohexyl phosphorus; L
1and L
2be chlorine;
N=0 or 1;
During n=0, p=0 or 1; During n=1, p=0;
During p=1, L
3for the pyridyl ligands that a position and/or contraposition are substituted, the nitrogen-atoms of pyridyl connects parent, and between pyridyl, the substituting group of position and contraposition is respectively halogen, C
1-C
3alkoxyl group, C
1-C
6alkyl amine group, substituted or unsubstituted C
6-C
12aryl;
During n=1, p=0, X
1for CH
2or phenyl; Y
1for oxygen or carbonyl;
During m=0, Y is C
1-C
4alkylamino or C
1-C
3alkoxyl group;
During m=1, X is carbonyl, CH
2, CH or phenmethyl; Y be nitrogen, NH,
c
1-C
4alkoxyl group, C
5heterocyclic oxy group or C
1-C
3alkane siloxy; Singly-bound or double bond is can be between X and Y;
R
1for hydrogen, C
6the phenmethyl that aryl or nitro replace;
R
2for C
1-C
3alkyl or C
1-C
3alkoxyl group;
R
3for hydrogen or C
6aryl;
E is halogen, nitro, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, C
1-C
8alkyl amino sulfonyl, C
6-C
12n-aryl sulfonyl;
E
1and E
2for hydrogen, halogen, C independently
1-C
4alkyl or C
1-C
4alkoxyl group; E
3for hydrogen;
E
4, E
5and E
7for being hydrogen, C independently
1-C
4alkyl or C
1-C
4alkoxyl group;
E
6for hydrogen, halogen, C
1-C
4alkyl or C
1-C
6alkoxyl group;
In Ia, as n=0, R
2for hydrogen, halogen, C
1-C
4alkyl or C
1-C
4alkoxyl group.
Three of object of the present invention is to provide a kind of preparation method of metal complex, and it can be obtained by any one of following three kinds of methods:
Method one comprises following three steps:
The structural formula of above-mentioned metal complex intermediate (Va, Vb, Vc) is as follows:
1) under protection of inert gas, the substituted or unsubstituted Tosylhydrazone such as shown in SM-2 is generated Cabbeen transition state in the anhydrous organic solvent of inorganic strong alkali; Wherein, R
a, R
b, R
c, R
dand R
ealone be hydrogen, C
1-C
8alkyl or C
1-C
8alkoxyl group;
2) under protection of inert gas, step 1) the Cabbeen transition state that obtains and ML
1l
2(PPh)
3reaction, generates metal complex intermediate compound IV; Wherein, M, L
1and L
2definition with described in any one of claim 5-11, but L
1and L
2be not all RCOO
-;
3) under protection of inert gas, step 2) the metal complex intermediate that obtains and complex ligands Ia, Ib or Ic reaction generate metal complex intermediate Va, Vb or Vc; Wherein, Va, Vb or Vc are L in IIa, IIb or IIc is PPh
3time compound, wherein M, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3described in the same;
Preferably, L
1and L
2be chlorine.
Wherein, step 1) in, described R
a, R
b, R
c, R
dand R
epreferably be hydrogen; Described inorganic strong alkali is preferably one or more in sodium methylate, sodium ethylate, sodium tert-butoxide and sodium hydrogen, and better is sodium ethylate; The consumption of described inorganic strong alkali is preferably 1-3 times of SM-2 molar weight, and better is 1.5-2 times; Described anhydrous organic solvent is preferably one or more in anhydrous methanol, ethanol, the trimethyl carbinol and tetrahydrofuran (THF), and better is dehydrated alcohol; The consumption of described anhydrous organic solvent is preferably 5-30 times of SM-2 molar weight, and better is 15 times; The temperature of described reaction is preferably 45-75 DEG C, and that better is 55-65 DEG C;
Step 2) in, the temperature of described reaction is preferably-50 DEG C to-85 DEG C, and better is-65 DEG C to-75 DEG C; Described ML
1l
2l
3consumption be preferably the 0.3-1.0 of SM-2 molar weight doubly, better be 0.6-0.7 times; Described ML
1l
2(PPh)
3be preferably RuCl
2p (Ph
3)
3;
Step 3) in, the temperature of described reaction is preferably-50 DEG C to-85 DEG C, and better is-65 DEG C to-75 DEG C; The consumption of described complex ligands Ia, Ib or Ic is preferably 1-3 times of complex intermediate molar weight, and better is 1.5-2 times;
Above-mentioned steps 1)-step 3) in, time of reaction all with detection reaction completely till.
Work as ML
1l
2l is RuCl
2p (Ph
3)
3time, Va, Vb and Vc of generation are as follows:
Method two: by described in method one Va, Vb or Vc under protection of inert gas respectively with except PPh
3outer other react generation following metal complex IIa, IIb or IIc to the complex ligands L of electronics, wherein, and p=0, M, L, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3definition ditto described in, but L is not PPh
3;
Wherein, preferably, in metal complex IIa, IIb or IIc of generation, L be thricyclohexyl phosphorus or
mes=2,4,6-trimethylphenyl; The temperature of described reaction is preferably 20 DEG C to 75 DEG C, and better when reacting with complex ligands IIIa is 60 DEG C to 75 DEG C, and better when reacting with complex ligands IIId is 20 DEG C to 35 DEG C; The consumption of described IIIa or IIId is preferably 1-3 times of the molar weight of complex intermediate Va, Vb or Vc, and better is 1.5-2 times;
Method three: react to the complex ligands L of electronics with other except thricyclohexyl phosphorus respectively under protection of inert gas IIa, IIb or IIc and generate following metal complex IIa, IIb or IIc; wherein; as in IIa, IIb or IIc of reactant: p=0, M, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3definition ditto described in, L is thricyclohexyl phosphorus; As in IIa, IIb or IIc of resultant: p=0, M, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3definition ditto described in, but L is not thricyclohexyl phosphorus;
Method four: under protection of inert gas, by resultant IIa, IIb or IIc in method one to method three described in either method and the complex ligands L giving electronics
3reaction generates IIa, IIb or IIc, wherein, in IIa, IIb or IIc of the resultant of present method: p=1, M, L, L
1, L
2, L
3, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3described in the same; In method four, the temperature of described reaction is preferably 20 DEG C to 35 DEG C.
In method one to method four, preferably, L
1and L
2be chlorine.
Here each reaction conditions in method three and method four is all the normal condition of this two class reaction.
In the present invention, when Z is CH
2time, metal complex ligand i a of the present invention can be prepared by following reaction:
Wherein, the normal condition that each condition all can be this type of Suzuki reaction is reacted.In like manner, when Z is CH
2time, Ib and Ic also can by this class response preparation.
Wherein Y, Y
1, R
1, R
2, E, E
1, E
2, and E
3definition with aforementioned.
Metal complex of the present invention can also be prepared by other two kinds of methods, and be prior art, their route is as follows:
preparation method one:
Each reaction conditions in this route is the normal condition of this few class reaction.
In this route, the Z in Ia, Ib or Ic is tolysulfonyl-2-hydrazono-(TsNHN).The phenyl aldehyde first replaced from the electron withdrawing group such as amino-sulfonyl and sulphonamide and tolysulfonyl hydrazine reaction generate Ia, Ib or Ic, then under protection of inert gas, in the ethanolic soln of sodium ethylate or sodium methylate, generate Cabbeen, afterwards and RuCl
2p (Ph
3)
3reaction generates the ruthenium complex (Va-Vc) containing triphenyl phosphorus; ruthenium complex (Va-Vc) generates the ruthenium complex (IIa-IIc) that part (L) is III d again under protection of inert gas with thricyclohexyl phosphorus reaction, to be reacted by the complex compound (IIa-IIc) that complex compound (Va-Vc) or obtained part are III d generate catalytic activity better complex compound catalyst II a-II c that part is III a according to chemically reactive under protection of inert gas with five-ring part (IIIa).
preparation method two:
IIa and IIb equally can route preparation thus.Each reaction conditions in this route is the normal condition of this few class reaction; Wherein, EWG is electron-withdrawing group, L be thricyclohexyl phosphorus or
mes is 2,4,6-trimethylphenyl.
In above-mentioned two kinds of syntheti c routes, M is ruthenium (Ru), L
1=L
2=Cl; Y, Y
1, R
1, R
2, E, E
1, E
2, and E
3definition the same.
In the present invention, described heterocyclic radical is preferably heterocyclic aryl.
The metal complex that four of object of the present invention is to provide above-mentioned formula II a-II c does the application of catalyzer in olefin metathesis replacement(metathesis)reaction.
Wherein, described olefin metathesis replacement(metathesis)reaction is preferably the olefin metathesis replacement(metathesis)reaction of intramolecular cyclization, intermolecular olefin metathesis replacement(metathesis)reaction (CM) or intermolecular cycloolefin ring opening metathesis polymerzation (ROMP).
The described cycloolefin for olefinic polyreaction (ROMP) is preferably tensioned cycloolefin structure or polycyclic olefin structure, described cycloolefin structure or polycyclic olefin structure are substituted or non-substituted structure, and they contain F, Cl, Br, N, O, Si, S, P, B, C in one or more ring
6-C
15aromatic series and C
4-C
15one or more in aromatic heterocycle substituting group.
In a preferred embodiments of the present invention, described cycloolefin structure contains 4 or 5 or 7-16 carbon atom, or multiple heteroatoms or heteroatom group; Described polycyclic olefin structure is the polycyclic olefin structure containing 2 to 6 rings; Described polycyclic olefin is that one or more hydrogen in cyclopentadiene or its molecule are by C
1-C
15saturated or undersaturated alkyl, substituted or unsubstituted C
1-C
15amido, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
1-C
15heterocyclic oxy group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
6-C
15arylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, methanoyl, formamido-, substituted or unsubstituted C
1-C
15alkyl carbonyloxy, substituted or unsubstituted C
1-C
15alkyl amido, substituted or unsubstituted C
6-C
15arylcarbonyloxy or substituted or unsubstituted C
6-C
15the derivative that aryl carboxamides base replaces.
In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIa and VIb:
Wherein:
A is O, S, C
1-C
15saturated or undersaturated alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15aryloxy, substituted or unsubstituted C
1-C
15heterocyclic oxy group, substituted or unsubstituted C
1-C
15alkylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
1-C
15alkyl amine group, substituted or unsubstituted C
1-C
15arylamine group, substituted or unsubstituted C
1-C
15alkyl amido, substituted or unsubstituted C
1-C
15aryl carboxamides base or substituted or unsubstituted C
1-C
15heterocyclic radical formamido-;
R
10and R
11be hydrogen, halogen, substituted or unsubstituted C independently
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, C
6-C
15aryloxy, C
6-C
15aryl, C
2-C
15heterocyclic radical, C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15alkyl amido, C
1-C
15alkylsulfonamido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, ionic liquid monomer, liquid crystal monomer, active drug molecule; In formula VIa, R
10and R
11be not linked to be ring texture or be linked to be ring texture.
In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIIa-VIIb:
Wherein:
A is O, S, C
1-C
15saturated or undersaturated alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15aryloxy, substituted or unsubstituted C
1-C
15heterocyclic oxy group, substituted or unsubstituted C
1-C
15alkylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15alkyl amido, substituted or unsubstituted C
1-C
15aryl carboxamides base or substituted or unsubstituted C
1-C
15heterocyclic radical formamido-;
R
12for substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, C
6-C
15aryloxy, C
6-C
15aryl, C
2-C
15heterocyclic radical, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15formamido-, C
1-C
15alkylsulfonamido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule;
R
13and R
14be substituted or unsubstituted C independently
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, C
6-C
15aryloxy, C
6-C
15aryl, C
2-C
15heterocyclic radical, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15formamido-, C
1-C
15alkylsulfonamido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule.
In the present invention, described intermolecular cycloolefin ring opening metathesis polymerzation is preferably for preparing the polyreaction of macromolecule polymer material, and the organic solvent of reaction is preferably one or more in methylene dichloride, ethylene dichloride, chloroform, toluene, dimethylbenzene, chlorobenzene and ionic liquid.When the raw material cycloolefin reacted or polycyclic olefin are liquid, organic solvent can not be added.
In another preferred embodiments of the present invention, the described high molecular polymer obtained by intermolecular cycloolefin ring opening metathesis polymerzation, for such as formula shown in VIc, VId, VIe, VIIc, VIId, Poly-DCPD;
Wherein, R
10, R
11, R
12, R
13and R
14be hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C independently
1-C
20alkyl, C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20aryloxy, C
1-C
20heterocyclyloxy base, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
2-C
20heterocyclic radical, substituted or unsubstituted C
6-C
20aryl, C
6-C
20aryloxy, connection C
1-C
20the carbonyl of alkyl, connection C
6-C
20the carbonyl of aryl, connection C
2-C
20the carbonyl of heterocyclic radical, connection C
6-C
20the carbonyl of aryloxy, connection C
6-C
20the carbonyl of heterocyclyloxy base, connect substituted or unsubstituted C
1-C
20oxygen base carbonyl, aminoacyl, the substituted or unsubstituted C of connection of saturated or unsaturated alkyl
1-C
20carbonyl, connection C that saturated or unsaturated alkyl is amino
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido, substituted or unsubstituted C
2-C
20heterocyclic radical urea groups, connection C
1-C
20the alkylsulfonyl of alkylamino, connection C
6-C
20the alkylsulfonyl of arylamino or connection C
2-C
20the alkylsulfonyl of heterocyclylamino group; n
1be 10
2-10
4; m
1be 10
2-10
4.
Preferably, above-mentioned high molecular polymer is in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD:
R
10, R
11, R
12, R
13and R
14be hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C independently
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15heterocyclic oxy group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkyl siloxy, C
2-C
15heterocyclic radical, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, connection C
1-C
15the carbonyl of alkyl, connection C
6-C
15the carbonyl of aryl, connection C
2-C
15the carbonyl of heterocyclic radical, connect substituted or unsubstituted C
1-C
15the oxygen base carbonyl of saturated or unsaturated alkyl, connect C
6-C
15the carbonyl of aryloxy, connection C
6-C
15the carbonyl of heterocyclyloxy base, aminoacyl, the substituted or unsubstituted C of connection
1-C
15carbonyl, connection C that saturated or unsaturated alkyl is amino
6-C
15the carbonyl of arylamino, connection C
2-C
15the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, substituted or unsubstituted C
6-C
15aryl-ureido, substituted or unsubstituted C
2-C
15heterocyclic radical urea groups, connection C
1-C
15the alkylsulfonyl of alkylamino, connection C
6-C
15the alkylsulfonyl of arylamino, connection C
2-C
15the alkylsulfonyl of heterocyclylamino group; n
1be 10
2-10
4; m
1be 10
2-10
4.
Better, described high molecular polymer is in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD:
R
10, R
11, R
12, R
13and R
14be hydrogen, halogen, substituted or unsubstituted C independently
1-C
8alkyl, C
1-C
8alkoxyl group, C
1-C
8alkylthio, C
1-C
8alkane is silica-based, C
1-C
8alkyl siloxy, C
2-C
8heterocyclic radical, substituted or unsubstituted C
6-C
12aryl, substituted or unsubstituted C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkyl, connection C
6-C
12the carbonyl of aryl, connection C
2-C
8the carbonyl of heterocyclic radical, connect substituted or unsubstituted C
1-C
8the oxygen base carbonyl of saturated or unsaturated alkyl, connect C
6-C
12the carbonyl of aryloxy, connection C
6-C
8the carbonyl of heterocyclyloxy base, aminoacyl, the substituted or unsubstituted C of connection
1-C
8carbonyl, connection C that saturated or unsaturated alkyl is amino
6-C
12the carbonyl of arylamino, connection C
2-C
8the carbonyl of heterocyclylamino group, connection C
1-C
8the alkylsulfonyl of alkylamino, connection C
6-C
12the alkylsulfonyl of arylamino, connection C
2-C
8the alkylsulfonyl of heterocyclylamino group; n
1be 10
2-10
4; m
1be 10
2-10
4.
Best, described high molecular polymer is in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD:
In VIc:
A is CH
2or oxygen;
R
11and R
10alone for connect C
1-C
3the oxygen base carbonyl of saturated or unsaturated alkyl, connect C that is non-substituted or that replaced by CN
6-C
12the carbonyl of aryloxy, to connect by C
6-C
12the C that aryl replaces
1-C
3the carbonyl of alkoxyl group, to connect by C
6-C
12aryloxy replace alkoxyl group carbonyl, connect do not replace or CN replace C
6-C
12aryloxy, connection C
1-C
3the amino carbonyl of saturated or unsaturated alkyl, to connect by C
6the C that aryl replaces
1-C
3the carbonyl of alkylamino or connection C
2-C
5the carbonyl of heterocyclic radical;
In VIIc:
A is CH
2, oxygen;
R
12for C
1-C
5saturated or undersaturated alkyl, by C
1-C
3the C that alkoxyl group replaces
1-C
3alkyl, the C be optionally substituted by a hydroxyl group
1-C
3alkyl, by C
1-C
3the C that alkyl acyloxy replaces
1-C
3alkyl, by C
6-C
12the C that aryl replaces
1-C
3alkyl, be connected C
1-C
3the C of the carbonyl substituted of alkoxyl group
1-C
3alkyl, by C
1-C
3the C that carbalkoxy replaces
6-C
12aryl, quilt
the aryl replaced or C
1-C
3alkoxyl group;
In VIId:
A is CH
2or oxygen;
R
14and R
13be C
1-C
3alkyl.
The invention still further relates to a kind of such as formula the high molecular polymer shown in VIc, VId, VIe, VIIc, VIId and Poly-DCPD, wherein, R
10, R
11, R
12, R
13, R
14, n
1and m
1as mentioned above.
Described high molecular polymer can be obtained by any one in following two kinds of methods:
Method one: when raw material monomer is liquid, it comprises the following steps:
Under protection of inert gas, raw material monomer and metal complex catalyst of the present invention carry out reacting by heating, can obtain VIc, VId, VIe, VIIc, VIId or Poly-DCPD.
Method two: when raw material monomer be solid or liquid time, it comprises the following steps:
Under protection of inert gas, in anhydrous organic solvent, raw material monomer and metal complex catalyst of the present invention are progressively warming up to 75 DEG C of reactions from 20 DEG C, can obtain VIc, VId, VIe, VIIc, VIId or Poly-DCPD.
In described method one: the consumption of catalyzer is preferably the 0.5%-10% of raw material monomer molar weight, the temperature of reacting by heating is preferably 30-120 DEG C; In described method two: the consumption of catalyzer is preferably the 0.01%-5% of raw material monomer molar weight, anhydrous organic solvent is preferably ethylene dichloride (DCE).
When high molecular polymer is Poly-DCPD, it can be obtained by method one, and step is as follows:
Wherein, n
1be 10
2-10
4; m
1be 10
2-10
4.
In the luxuriant diene monomers of liquid dicyclo (DCPD), pass into argon gas to rush oxygen, add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, between 30-120 degree, after reacting by heating several minutes, reaction solution becomes sticky thick heat release gradually, and finally polymerization obtains poly-dicyclo luxuriant diene polymeric solid product (Poly-DCPD).Polymer P oly-DCPD solid has good hardness (>80Gpa), modulus in flexure (>20Gpa) and heat-drawn wire (>200 DEG C).
When high molecular polymer is VIc, it can be obtained by method two, and step is as follows:
1) under protection of inert gas, olefinic monomer raw material VIa is dissolved in anhydrous solvent (as ethylene dichloride DCE), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, reaction is intensification (20-75 DEG C) reacting by heating progressively, and reaction solution becomes sticky thick gradually;
2) reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, suction filtration dry after polymer solids product (VIc), productive rate is 80-98%; Wherein, R
10, R
11, n
1definition with aforementioned.
The invention further relates to the application of high molecular polymer in the effective carrier of preparation high strength and the explosion-proof lamp of high rigidity, tire material, polymer medicament prodrug, tooth patching material, Liquid Crystalline Polymeric Materials, conductive polymer novel material, masking or spinning material.
In the present invention, described alkyl is comprise the representative examples of saturated aliphatic alkyl having and specify carbonatoms object side chain or straight chain; As at " C
1-C
10alkyl " in be defined as the group being included in and there is in straight chain or branched structure 1,2,3,4,5,6,7,8,9 or 10 carbon atom.Such as, " C
1-C
10alkyl " specifically comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, nonyl and decyl etc.
Described " alkoxyl group " represent alkyl be connected with Sauerstoffatom after generation group, i.e. " RO-", R is alkyl.
Described " aryl " refer to any stable can up to the monocycle of 7 atoms or bicyclic carbocyclic in each ring, wherein at least one ring is aromatic nucleus; The example of above-mentioned aryl unit comprises phenyl, naphthyl, tetralyl, 2,3-indanyls, xenyl, phenanthryl, anthryl or acenaphthenyl (acenaphthyl).Be appreciated that at aryl substituent be two ring substituents, and one of them ring is in the situation of non-aromatic ring, connection is undertaken by aromatic ring.
" heterocyclic aryl " represents can up to the stable monocycle of 7 atoms or two rings in each ring, and wherein at least one ring is aromatic nucleus and is selected from the heteroatoms of O, N and S containing 1-4; Heterocyclic aryl in this range of definition includes but not limited to: acridyl, carbazyl, cinnolines base, quinoxalinyl, pyrazolyl, indyl, benzotriazole base, furyl, thienyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, oxazolyl, isoxazolyl, indyl, pyrazinyl, pyridazinyl, pyridyl, pyrimidyl, pyrryl, tetrahydroquinoline.As the definition of following heterocycle, " heterocyclic aryl " it should also be understood that to be the N-oxide derivative comprising any nitrogen-containing hetero aryl.Heterocyclic aryl substituting group is two ring substituents and ring is non-aromatic ring or under not comprising heteroatomic situation wherein, is appreciated that to connect and carries out respectively by aromatic ring or by the heteroatoms comprising ring.
" alkylthio " represent alkyl be connected with sulphur atom after generation group, i.e. " RS-", R is alkyl.
" aryloxy " represent aryl be connected with Sauerstoffatom after generation group, i.e. " RO-", R is aryl.
" virtue is amino " refers to " NH
3" in a hydrogen replaced by aryl after amino.
" alkyl imino " refers to the imino-being connected with alkyl, on the carbon that alkyl can be connected in imino-or on nitrogen; " alkyl imino of replacement " refer to the one or more hydrogen in alkyl imino be substituted after group.
" amino of replacement " is " NH
3" in any one or more hydrogen be substituted after group.Substituting group can be C
6-C
20aryl, formyl radical, C
1-C
20the C of alkyl acyl, replacement
1-C
20the C of alkyl acyl, alkyl sulphonyl, replacement
1-C
20alkyl sulphonyl etc.
Wherein, " alkyl sulphonyl " is connected with the group of alkyl for the sulphur atom on alkylsulfonyl, " alkyl sulphonyl of replacement " for the one or more hydrogen in alkyl sulphonyl be substituted with a substituent after group; " alkyl acyl " is connected to the acyl group of alkyl for the carbon atom in acyl group or nitrogen-atoms, " alkyl acyl of replacement " for any one or more hydrogen in alkyl acyl be substituted with a substituent after group.
" heterocyclic radical " is containing the one or more fragrance be selected from the heteroatoms of O, N and S or nonaromatic heterocycles, and comprises bicyclic groups.Therefore, " heterocyclic radical " comprises above-mentioned heterocyclic aryl and its dihydro or tetrahydrochysene analogue.Other example of " heterocyclic radical " includes but not limited to following: benzimidazolyl-, benzofuryl, benzopyrazoles base, benzotriazole base, benzothienyl, benzoxazolyl, carbolinyl, furyl, imidazolyl, indolinyl, indyl, indazolyl, isobenzofuran-base, pseudoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, oxazolyl, oxazoline, isoxazoline, oxygen cyclobutyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridopyridine base, pyridazinyl, pyridyl, pyrimidyl, pyrryl, quinazolyl, quinolyl, quinoxalinyl, THP trtrahydropyranyl, thiadiazolyl group, thiazolyl, thienyl, triazolyl, azetidinyl, Isosorbide-5-Nitrae-alkyl dioxin, six hydrogen azatropylidene bases, piperazinyl, piperidyl, pyrrolidyl, morpholinyl, thio-morpholinyl, dihydrobenzo imidazolyl, dihydro benzo furyl, dihydrobenzo thienyl, Er hydrogen benzoxazolyl, dihydrofuran base, glyoxalidine base, indolinyl, dihydro-isoxazole base, dihydro isothiazolyl, Er Qing oxadiazolyl, dihydro-oxazole base, dihydro pyrazinyl, pyrazoline base, dihydropyridine base, dihydro-pyrimidin base, pyrrolin base, dihydroquinoline base, dihydro tetrazyl, thiodiazoline base, dihydro-thiazolyl, dihydro-thiophene base, dihydro triazolyl, dihydro azetidinyl, methylenedioxyphenyl formyl radical, tetrahydrofuran base and tetrahydro-thienyl and N-oxide compound thereof.Heterocyclic radical can be connected with central element through carbon atom or heteroatoms.
" heterocyclic radical of replacement " for hydrogen any one or more in heterocyclic radical be substituted with a substituent after group.
" alkyl amido " in succession the group of alkyl for the carbon in formamido-or nitrogen, " the alkyl amido of replacement " for any one or more hydrogen in alkyl amido be substituted with a substituent after group.
" siloxy " for structural formula be R
1r
2r
3the group of SiO-; " alkyl siloxy " is R
1r
2r
3r in SiO-
1, R
2and R
3in have one at least for alkyl, all the other are the group of hydrogen; " alkyl siloxy of replacement " for the one or more hydrogen in alkyl siloxy be substituted after group.
" alkyl amido " for the hydrogen on carbon in formamido-or the hydrogen on nitrogen replaced by alkyl after generation group; " the alkyl amido of replacement " for the one or more hydrogen in alkyl amido be substituted with a substituent after group.
" alkane is silica-based " is structure R
1r
2r
3in Si-, R
1, R
2and R
3in have one at least for alkyl, all the other are the group of hydrogen.
" aminoacyl " for structural formula is
group.
The group " connecting the carbonyl of alkylamino " for being formed after the nitrogen connection alkyl in aminoacyl; Group after one or more hydrogen in the carbonyl that " carbonyl of the connection alkylamino of replacement " is connection alkylamino are substituted.
" alkyl urea groups " for the one or more hydrogen on nitrogen in urea groups replaced by alkyl after group; " the alkyl urea groups of replacement " for the one or more hydrogen in alkyl urea groups be substituted after group.
Raw material involved in the present invention and reagent except specified otherwise all commercially.
Positive progressive effect of the present invention is:
1, the present invention is by design and synthetic metals complex ligands and corresponding metal especially ruthenium complex; the substituting group of abundant research different ligands and the catalytic activity of the position of substitution on catalyzer thereof and the impact of stability; result shows that metal complex catalyst of the present invention has the catalytic activity of higher olefin metathesis replacement(metathesis)reaction, and the adjacent alkoxystyrene complex ligands with electron withdrawing group replacements such as amino-sulfonyl, sulfoamido, carbonyl, chlorine significantly improves catalytic activity and the stability of respective metal complex compound.Metal complex catalyst of the present invention can be effective to intramolecular alkene ring closure reaction, intermolecular cycloolefin ring-opening polymerization etc., there is industry using value widely, for the field such as new chemical materials and pharmaceutical synthesis provides a kind of new synthetic method by olefin metathesis replacement(metathesis)reaction.
2, the novel metal complexes structural formula of design and synthesis of the present invention is formula II a-II c, the diversity of its chemical catalysis performance and physicals and application thereof selects comparatively Grubbs-Hoveyda catalyzer to increase significantly and improve, and optimize the preparation method of metal complex, reduce preparation cost largely, the industrialization for the catalyzed reaction of metal complex is produced provides an effective practical novel method.
3, the present invention be have developed by high molecular polymer novel material of the different performance prepared under different monomer process conditions and preparation method thereof by the catalyzed ring opening polymerization reaction of cycloolefin.
4, the main application of high molecular polymer novel material that prepared by the present invention is the novel material such as effective novel vector, tooth patching material, Liquid Crystalline Polymeric Materials, conductive polymer of the explosion-proof novel material of high strength and high rigidity, tire novel material, polymer medicament prodrug, also can be used for masking and novel material is prepared in spinning.The development that can be human society in field of new provides how better product innovation.
Embodiment:
The present invention is according to data (the patent US20070043180A1 researched and developed about olefin metathesis reaction catalyzer, WO2007003135A1, WO96004289A1, WO97003096A1, US 20020107138A1, US 6921735B2 and chemistry meeting magazine J.Am.Chem.Soc.1999, 121, 791-799, J.Am.Chem.Soc.2000, 122, 8168-8179), by dissimilar complex ligands (3a-3cz, 5a-5z, 7a-7t, 9a-9j, 11a-11j) prepare dissimilar metal Ru complex compound (4a-4u with the complex reaction of ruthenium complex intermediate, 6a-6v, 8a-8e, 10a-10e, 12a-12f), and have studied the structure of dissimilar complex ligands and substituent effect to the impact of its respective metal complex catalysis activity respectively by the catalytic cyclization of alkene and ring-opening polymerization, and have extensively studied dissimilar metal complex catalyst prepares different performance macromolecular material by alkene ring-opening polymerization, and further research and development optimize dissimilar novel complex compound for the preparation of the high molecular polymer novel material and preparation method thereof of different performance and multiple use.
Below adopt complex ligands (3a-3cz) to synthesize ruthenium complex 4a-4cz according to relevant documents and materials:
Be below the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 4a-4cz:
Be below the synthesis of ruthenium complex 4a-4cz:
The synthesis of embodiment 1 ruthenium complex 4a
Add the DCM of part 3a (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4a, productive rate: 32% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4a)
1hNMR (400MHz, CDCl
3): δ 18.68 (s, Ru=CH), 7.23-6.65 (m, 10H, aromatic H), 6.36 (dd, J=2.8,9.6Hz, 1H, aromatic H), 6.03 (d, J=12.8Hz, 1H, NCH
2), 4.14-3.90 (m, 4H, NCH
2cH
2n), 3.85 (s, 3H, OCH
3), 3.47 (d, J=12.8Hz, 1H, NCH
2), 2.89-1.62 (m, 18H, aromatic CH
3).
The synthesis of embodiment 2 ruthenium complex 4b:
Add the DCM of part 3b (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4b, productive rate: 35% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4b)
1hNMR (400MHz, CDCl
3): δ 19.28 (d, J=8.4Hz, Ru=CH), 7.45 (d, J=8.8Hz, 2H, aromatic H), 7.31-7.16 (m, 3H, aromatic H), 6.83 (d, J=8.8Hz, 2H, aromatic H), 5.13 (t, J=12.4Hz, 1H, NH), 7.96 (d, J=12.4Hz, 1H, NCH
2), 3.85 (d, J=12.4Hz, 1H, NCH
2), 3.80 (s, 3H, OCH
3), 2.28-1.24 (m, 33H, PCy
3).
The synthesis of embodiment 3 ruthenium complex 4c:
Add the DCM of part 3c (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4c, productive rate: 14% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4c)
1hNMR (400MHz, CDCl
3): δ 18.99 (s, Ru=CH), 7.483-7.444 (m, 1H, aromatic H), (7.192-6.862 m, 7H, aromatic H), 6.715-6.662 (m, 1H, aromatic H), 5.293 (t, J=13.2Hz, 1H, NHCH
2), 4.19-3.58 (m, 8H, NHCH
2, NCH
2cH
2n, NCH
3), 2.52-2.37 (m, 18H, aromatic CH
3).
The synthesis of embodiment 4 ruthenium complex 4d:
Add the DCM of part 3d (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4d, productive rate: 13% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4d)
1hNMR (400MHz, CDCl
3): δ 19.42 (d, J=8.8Hz, Ru=CH), 7.65 (d, J=9.2Hz, 2H, aromatic H), 7.35-7.17 (m, 3H, aromatic H), 6.93 (d, J=9.2Hz, 2H, aromatic H), 5.76 (d, J=12.4Hz, 1H, NH), 3.80 (s, 3H, OCH
3), 3.70 (d, J=12.4Hz, 1H, NH), 2.57 (s, 3H, OCH
3), 2.29-1.21 (m, 33H, PCy
3).
The synthesis of embodiment 5 ruthenium complex 4e:
Add the DCM of part 3e (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4e, productive rate: 13% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4e)
1hNMR (400MHz, CDCl
3): δ 18.90 (s, Ru=CH), 7.21-7.15 (m, 1H, aromatic H), 7.05-6.94 (m, 5H, aromatic H), 6.87 (m, 2H, aromatic H), 6.66-6.60 (m, 3H, aromatic H), 6.38 (dd, J=2.4,9.6Hz, 1H, aromatic H), 5.293 (t, J=13.2Hz, 1H, NHCH
2), 4.19-3.55 (m, 8H, NHCH
2, NCH
2cH
2n, NCH
3), 2.86-2.10 (m, 18H, aromatic CH
3).
The synthesis of embodiment 6 ruthenium complex 4f:
Add the DCM of part 3f (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4f, productive rate: 28% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4f)
1hNMR (400MHz, CDCl
3): δ 7.69-7.60 (m, 2H, aromatic H), 7.58-7.50 (m, 2H, aromatic H), 7.47-7.41 (m, 1H, aromatic H), 7.26-7.22 (m, 1H, aromatic H), 6.6.91-6.83 (m, 2H, aromatic H), 5.32 (t, J=12.4Hz, 1H, NH), 4.97 (d, J=12.4Hz, 1H, NCH
2), 3.87 (d, J=12.4Hz, 1H, NCH
2), 3.78 (s, 3H, OCH
3), 2.38-1.13 (m, 33H, PCy
3).
The synthesis of embodiment 7 ruthenium complex 4g:
Add the DCM of part 3g (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4g, productive rate: 7% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4a)
1hNMR (400MHz, CDCl
3): δ 18.83 (s, Ru=CH), 7.51-7.49 (m, 1H, aromatic H), 7.17-7.06 (m, 5H, aromatic H), 6.95 (m, 1H, aromatic H), 6.88 (m, 1H, aromatic H), 6.77 (m, 1H, aromatic H), 6.68-6.65 (m, 3H, aromatic H), 6.11 (d, J=12.8Hz, 1H, NCH
2), 4.4-3.89 (m, 4H, NCH
2cH
2n), 3.83 (s, 3H, OCH
3), 3.45 (d, J=12Hz, 1H, NCH
2), 2.86-1.56 (m, 21H, NCH
3, aromatic CH
3).
The synthesis of embodiment 8 ruthenium complex 4h:
Add the DCM of part 3h (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4h, productive rate: 29% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4h)
1hNMR (400MHz, CDCl
3): δ 19.31 (d, J=8.4Hz, Ru=CH), 7.57-7.50 (m, 4H, aromatic H), 7.31-7.29 (m, 1H, aromatic H), 7.148 (d, J=5.6Hz, 1H, aromatic H), 6.84-6.81 (m, 2H, aromatic H), 5.78 (d, J=12Hz, 1H, NCH
2), 3.71 (s, 3H, OCH
3), 3.62 (d, J=12Hz, 1H, NCH
2), 2.51 (s, 3H, NCH
3), 2.22-1.13 (m, 33H, PCy
3).
The synthesis of embodiment 9 ruthenium complex 4j:
Add the DCM of part 3j (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4j, productive rate: 37% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4j)
1hNMR (400MHz, CDCl
3): δ 18.83 (s, Ru=CH), 7.50-6.39 (m, 11H, aromatic H), 5.21 (t, J=12.4Hz, 1H, NH), 4.69-3.46 (m, 9H, NHCH
2, NCH
2cH
2n, OCH
3), 2.62-2.08 (m, 18H, aromatic CH
3).
The synthesis of embodiment 10 ruthenium complex 4k:
Add the DCM of part 3k (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4k, productive rate: 52% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4k)
1hNMR (400MHz, CDCl
3): δ 19.35 (d, J=9.9Hz, Ru=CH), 8.11 (d, J=8.1Hz, 1H, aromatic H), 7.34-6.85 (m, 6H, aromatic H), 5.48 (d, J=12Hz, 1H, NCH
2), 5.27 (t, J=6Hz, 1H, NH), 3.93 (d, J=12Hz, 1H, NCH
2), 3.88 (s, 3H, OCH
3), 2.33-1.24 (m, 33H, PCy
3).
The synthesis of embodiment 11 ruthenium complex 4m:
Add the DCM of part 3m (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4m, productive rate: 84% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4m)
1hNMR (400MHz, CDCl
3): δ 18.89 (s, Ru=CH), 7.60-6.45 (m, 11H, aromatic H), 5.13-3.52 (m, 8H, NHCH
2, NCH
2cH
2n, OCH), 2.95-2.10 (m, 18H, aromatic CH
3), 0.95 (d, J=6.4Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 12 ruthenium complex 4n:
Add the DCM of part 3n (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4n, productive rate: 58% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4n)
1hNMR (400MHz, CDCl
3): δ 19.55 (d, J=9.9Hz, Ru=CH), 8.14 (d, J=8.1Hz, 1H, aromatic H), 7.36-6.83 (m, 6H, aromatic H), 5.46 (d, J=12Hz, 1H, NCH
2), 5.13 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.90 (d, J=12Hz, 1H, NCH
2), 2.30-1.25 (m, 39H, PCy
3).
The synthesis of embodiment 13 ruthenium complex 4p:
Add the DCM of part 3p (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4p, productive rate: 10% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4p)
1hNMR (400MHz, CDCl
3): δ 18.97 (s, Ru=CH), 7.50-6.58 (m, 11H, aromatic H), 5.26-3.52 (m, 8H, NHCH
2, NCH
2cH
2n, OCH), 3.48-2.07 (m, 18H, aromatic CH
3), 1.23 (d, J=6.4Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 14 ruthenium complex 4n:
Add the DCM of part 3q (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4q, productive rate: 31% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4q)
1hNMR (400MHz, CDCl
3): δ 19.56 (d, J=9.9Hz, Ru=CH), 8.20 (d, J=8.1Hz, 1H, aromatic H), 7.66-6.84 (m, 6H, aromatic H), 5.46 (d, J=12Hz, 1H, NCH
2), 5.22 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.95 (d, J=12Hz, 1H, NCH
2), 2.34-0.87 (m, 39H, PCy
3).
The synthesis of embodiment 15 ruthenium complex 4r:
Add the DCM of part 3r (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4r, productive rate: 14% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4n)
1hNMR (400MHz, CDCl
3): δ 18.91 (s, Ru=CH), 7.53-6.62 (m, 12H, aromatic H), 5.31 (t, J=12.4Hz, 1H, NH), 4.73-3.53 (m, 9H, NHCH
2, NCH
2cH
2n, OCH
3), 2.56-1.78 (m, 18H, aromatic CH
3).
The synthesis of embodiment 16 ruthenium complex 4s:
Add the DCM of part 3s (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4s, productive rate: 37% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4s)
1hNMR (400MHz, CDCl
3): δ 19.55 (d, J=9.9Hz, Ru=CH), 8.20 (d, J=8.1Hz, 1H, aromatic H), 7.64-6.86 (m, 7H, aromatic H), 5.52 (d, J=12Hz, 1H, NCH
2), 5.35 (t, J=6Hz, 1H, NH), 3.96 (d, J=12Hz, 1H, NCH
2), 3.91 (s, 3H, OCH
3), 2.34-1.22 (m, 33H, PCy
3).
The synthesis of embodiment 17 ruthenium complex 4t:
Add the DCM of part 3t (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid 4t with methyl alcohol or pentane-DCM washing, impure, thick productive rate: 21%, nothing
1hNMR analytical results.
The synthesis of embodiment 18 ruthenium complex 4u:
Add the DCM of part 3u (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid 4u with methyl alcohol or pentane-DCM washing, impure, thick productive rate: 7%, nothing
1hNMR analytical results.
The synthesis of embodiment 19 ruthenium complex 4v:
Add the DCM of part 3v (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4v, productive rate: 45% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4v)
1hNMR (400MHz, CDCl
3): δ 18.914 (s, Ru=CH), 7.535 (dd, J=1.2,8.0Hz, 1H, aromatic H), 7.225 (m, 1H, aromatic H), 7.056-6.947 (m, 5H, aromatic H), 6.810 (m, 1H, aromatic H), 6.712 (d, J=8.0Hz, 1H, aromatic H), 6.651 (t, J=7.6Hz, 1H, aromatic H), 6.462 (dd, J=2.4,9.6Hz, 1H, aromatic H), 5.198 (t, J=11.2Hz, 1H, NH), 4.658 (d, J=11.2Hz, 1H, NCH
2), 4.180-3.857 (m, 6H, NCH
2cH
2n, OCH
2), 3.549 (d, J=11.2Hz, 1H, NCH
2), 2.790-2.000 (m, 18H, aromatic CH
3), 1.19 (m, OCH
2cH
3).
The synthesis of embodiment 20 ruthenium complex 4w:
Add the DCM of part 3w (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4w, productive rate: 7% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4w)
1hNMR (400MHz, CDCl
3): δ 16.500 (s, Ru=CH), 7.680 (m, 1H, aromatic H), 7.099 (s, 4H, aromatic H), 6.984-6.800 (m, 6H, aromatic H), 4.650 (m, 1H, OCH), 4.229-4.178 (m, 6H, NCH
2, NCH
2cH
2n), 3.884 (s, 3H, OCH
3), 2.645 (s, 3H, NCH
3), 2.495 (s, 12H, aromatic CH
3), 2.347 (s, 6H, 18H, aromatic CH
3), 0.912 (m, 6H, OCH (CH
3)
2).
The synthesis of embodiment 21 ruthenium complex 4x:
Add the DCM of part 3x (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4x, productive rate: 40% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4x)
1hNMR (400MHz, CDCl
3): δ 16.517 (s, Ru=CH), 7.580 (m, 1H, aromatic H), 7.094 (s, 4H, aromatic H), 6.925-6.597 (m, 6H, aromatic H), 4.521 (m, 1H, NH), 4.352 (s, 2H, NCH
2), 4.180 (s, 4H, NCH
2cH
2n), 3.887 (s, 6H, OCH
3), 2.494 (s, 12H, aromatic CH
3), 2.402 (s, 6H, aromatic CH
3).
The synthesis of embodiment 22 ruthenium complex 4y:
Add the DCM of part 3y (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4y, productive rate: 50% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4y)
1hNMR (400MHz, CDCl
3): δ 19.034 (s, Ru=CH), 8.376 (d, J=2.0Hz, 1H, aromatic H), 7.690 (d, J=1.6.0Hz, 1H, aromatic H), (7.437 d, J=7.6Hz, 1H, aromatic H), 7.206-7.029 (m, 5H, aromatic H), 6.834-6.590 (m, 3H, aromatic H), (5.240 t, J=12Hz, 1H, NH), 4.660 (d, J=12Hz, 1H, NCH
2), 4.451 (m, 1H, OCH
3), 4.202-4.051 (m, 4H, NCH
2cH
2n), 3.615 (d, J=12Hz, 1H, NCH
2), 2.692-2.026 (m, 18H, aromatic CH
3), 1.177 (d, J=5.6Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 23 ruthenium complex 4z:
Add the DCM of part 3z (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4z, productive rate: 49% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4z)
1hNMR (400MHz, CDCl
3): δ 16.524 (s, Ru=CH), 7.590 (m, 1H, aromatic H), 7.092 (s, 4H, aromatic H), 6.916-6.838 (m, 4H, aromatic H), 6.752-6.657 (m, 2H, aromatic H), 4.590 (m, 1H, NH, OCH), 4.347 (s, 2H, NCH
2), 4.179 (s, 4H, NCH
2cH
2n), 3.886 (s, 3H, OCH
3), 2.493 (s, 12H, aromatic CH
3), 2.399 (s, 6H, 18H, aromatic CH
3), 0.931 (m, 6H, OCH (CH
3)
2).
The synthesis of embodiment 24 ruthenium complex 4aa
Add the DCM of part 3aa (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4aa, productive rate: 55% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4aa)
1h-NMR (400MHz, CDCl
3): δ 19.454 (d, J=9.6Hz, Ru=CH), 8.175 (d, J=7.6Hz, 1H, aromatic H), (7.397-7.325 m, 2H, aromatic H), (7.205-7.113 m, 2H, aromatic H), (6.949-6.880 m, 2H, aromatic H), 5.523 (m, 1H, NCH
2), 5.225 (m, 1H, NH), 4.159-3.942 (m, 3H, NCH
2, OCH
2), 2.358-0.812 (m, 36H, PCy
3, OCH
2cH
3).
The synthesis of embodiment 25 ruthenium complex 4ab
Add the DCM of part 3ab (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ab, productive rate: 8% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ab)
1h-NMR (400MHz, CDCl
3): δ 19.110 (s, 1H, Ru=CH), 8.364 (dd, J=2.0,8.0Hz, 1H, aromatic H), 7.289-6.646 (m, 10H, aromatic H), 5.303 (t, J=13.6Hz, 1H, NCH
2), 4.226 (d, J=13.2Hz, 1H, NCH
2), 4.104 (s, 3H, OCH
3), 3.800 (s, 4H, NCH
2cH
2n), 3.686 (d, J=13.2Hz, 1H, NCH
2), 2.646-2.075 (m, 18H, aromatic CH
3).
The synthesis of embodiment 26 ruthenium complex 4ac
Add the DCM of part 3ac (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ac, productive rate: 63% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ac)
1h-NMR (400MHz, CDCl
3): δ 17.370 (d, J=4.4Hz, Ru=CH), 7.740-7.674 (m, 2H, aromatic H), 7.111 (d, J=8.4Hz, aromatic H), 6.893-6.826 (m, 2H, aromatic H), (6.758-6.663 m, 2H, aromatic H), (4.656 s, 1H, NH), 4.479 (s, 2H, NCH
2), 4.334 (s, 3H, OCH
3), 3.896 (s, 3H, OCH
3), 2.345-1.272 (m, 33H, 18H, PCy
3).
The synthesis of embodiment 27 ruthenium complex 4ad
Add the DCM of part 3ad (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ad, productive rate: 3% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ad)
1h-NMR (400MHz, CDCl
3): δ 18.639 (s, 1H, Ru=CH), 7.542-7.470 (m, 2H, aromatic H), 7.287-7.692 (m, 10H, aromatic H), 5.513 (d, J=13.2Hz, 1H, NCH
2), 4.152 (d, J=13.2Hz, 1H, NCH
2), 4.083-3.769 (m, 7H, NCH
2cH
2n, OCH
3), 3.195 (s, 3H, NCH
3), 2.409 (m, 18H, aromatic CH
3).
The synthesis of embodiment 28 ruthenium complex 4ae
Add the DCM of part 3ae (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ae, productive rate: 50% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ae)
1h-NMR (400MHz, CDCl
3): δ 19.034 (s, 1H, Ru=CH), 8.376 (d, J=2.0Hz, 1H, aromatic H), 7.690 (d, J=1.6.0Hz, 1H, aromatic H), 7.437 (d, J=7.6Hz, 1H, aromatic H), (7.206-7.029 m, 5H, aromatic H), 6.834-6.590 (m, 3H, aromatic H), 5.240 (t, J=12Hz, 1H, NH), 4.660 (d, J=12Hz, 1H, NCH
2), 4.451 (m, 1H, OCH
3), 4.202-4.051 (m, 4H, NCH
2cH
2n), 3.615 (d, J=12Hz, 1H, NCH
2), 2.692-2.026 (m, 18H, aromatic CH
3), 1.177 (d, J=5.6Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 29 ruthenium complex 4af
Add the DCM of part 3af (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4af, productive rate: 15% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4af)
1h-NMR (400MHz, CDCl
3): δ 18.541 (s, 1H, Ru=CH), 7.446 (d, J=8.0Hz, 1H, aromatic H), 7.239-7.191 (m, 4H, aromatic H), 7.058-6.958 (m, 6H, aromatic H), 6.143 (d, J=13.2Hz, 1H, NCH
2), 5.393 (d, J=13.2Hz, 1H, NCH
2), 4.074-3.770 (m, 7H, NCH
2cH
2n, OCH
3), 3.518 (s, 3H, NCH
3), 2.648-2.303 (m, 18H, aromatic CH
3).
The synthesis of embodiment 30 ruthenium complex 4ag
Add the DCM of part 3ag (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ag, productive rate: 4% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ag)
1h-NMR (400MHz, CDCl
3): δ 19.093 (s, 1H, Ru=CH), 7.514-6.701 (m, 13H, aromatic H), 5.310 (m, 1H, NH), 4.300 (d, J=12.9Hz, 1H, NCH
2), 4.044 (s, 4H, NCH
2cH
2n), 3.612 (d, J=12.9Hz, 1H, NCH
2), 2.452 (s, 12H, aromatic CH
3), 2.332 (s, 6H, aromatic CH
3).
The synthesis of embodiment 31 ruthenium complex 4ah
Add the DCM of part 3ah (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ah, productive rate: 5% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ah)
1h-NMR (400MHz, CDCl
3): δ 19.093 (s, 1H, Ru=CH), 7.503-6.691 (m, 12H, aromatic H), 5.274 (m, 1H, NH), 4.330 (d, J=12.9Hz, 1H, NCH
2), 4.043 (s, 4H, NCH
2cH
2n), 3.586 (d, J=12.9Hz, 1H, NCH
2), 2.445 (s, 12H, aromatic CH
3), 2.371 (s, 6H, aromatic CH
3).
The synthesis of embodiment 32 ruthenium complex 4am
Add the DCM of part 3am (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4am, productive rate: 40% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4am)
1h-NMR (400MHz, CDCl
3): δ 18.83 (s, 1H, Ru=CH), 7.36-6.14 (m, 10H, aromatic H), 5.12 (t, J=12.4Hz, 1H, NH), 4.50-3.42 (m, 12H, NHCH
2, NCH
2cH
2n, OCH
3), 2.62-2.05 (m, 18H, aromatic CH
3).
The synthesis of embodiment 33 ruthenium complex 4an
Add the DCM of part 3an (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4an, productive rate: 51% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4an)
1h-NMR (400MHz, CDCl
3): δ 18.90 (s, 1H, Ru=CH), 7.60-6.36 (m, 10H, aromatic H), 5.25 (t, J=12Hz, 1H, NH), 4.78 (d, J=12Hz, 1H, NCH
2), 4.05 (s, 4H, NCH
2cH
2n), 3.53 (s, 3H, OCH
3), 3.43 (d, J=12Hz, 1H, NCH
2), 2.56-2.13 (m, 21H, aromatic CH
3).
The synthesis of embodiment 34 ruthenium complex 4ap
Add the DCM of part 3ap (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ap, productive rate: 50% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ap)
1h-NMR (400MHz, CDCl
3): δ 18.90 (s, 1H, Ru=CH), 7.38-6.37 (m, 9H, aromatic H), 4.85 (m, 2H, NH, NCH
2), 3.99 (s, 4H, NCH
2cH
2n), 3.80 (d, J=12Hz, 1H, NCH
2), 3.31 (s, 3H, OCH
3), 2.69-0.85 (m, 38H, C (CH3)
3, aromatic CH
3).
The synthesis of embodiment 35 ruthenium complex 4aq
Add the DCM of part 3aq (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4aq, productive rate: 37% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4aq)
1h-NMR (400MHz, CDCl
3): δ 19.08 (s, 1H, Ru=CH), 7.97-6.33 (m, 10H, aromatic H), 5.08 (m, 2H, NH, OCH), 4.34 (m, 1H, NCH
2), 4.02 (s, 4H, NCH
2cH
2n), 3.41 (m, 1H, NCH
2), 2.53-2.31 (m, 18H, aromatic CH
3), 1.29 (s, 9H, C (CH3)
3), 0.89-0.87 (m, 6H, OCH (CH
3)
2).
The synthesis of embodiment 36 ruthenium complex 4ar
Add the DCM of part 3ar (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ar, productive rate: 54% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ar)
1h-NMR (400MHz, CDCl
3): δ 18.85 (s, 1H, Ru=CH), 7.26-6.07 (m, 10H, aromatic H), 5.04 (t, J=13.2Hz, 1H, NH), 4.48 (m, 1H, NCH
2), 4.39-4.33 (m, 2H, OCH), 4.15-4.02 (m, 4H, NCH
2cH
2n), 3.65 (m, 1H, NCH
2), 2.66-2.05 (m, 18H, aromatic CH
3), 1.55 (m, 6H, OCH (CH
3)
2), 1.38 (m, 6H, OCH (CH
3)
2).
The synthesis of embodiment 37 ruthenium complex 4as
Add the DCM of part 3as (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4as, productive rate: 46% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4as)
1h-NMR (400MHz, CDCl
3): δ 18.98 (s, 1H, Ru=CH), 7.66-6.39 (m, 10H, aromatic H), 5.17 (t, J=13.2Hz, 1H, NH), 4.71 (d, J=13.2Hz, 1H, NCH
2), 4.36 (m, 1H, OCH), 4.06 (brs, 4H, NCH
2cH
2n), 3.42 (d, J=13.2Hz, 1H, NCH
2), 2.63-2.09 (m, 21H, aromatic CH
3), 1.09 (m, 6H, OCH (CH
3)
2).
The synthesis of embodiment 38 ruthenium complex 4at
Add the DCM of part 3at (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4at, productive rate: 37% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4at)
1h-NMR (400MHz, CDCl
3): δ 19.46 (d, J=9.9Hz, Ru=CH), 8.15 (d, J=8.1Hz, 1H, aromatic H), 7.33-7.13 (m, 3H, aromatic H), 6.46 (m, 2H, aromatic H), 5.26 (m, 2H, NCH
2), 3.79 (s, 3H, OCH
3), 3.76 (s, 3H, OCH
3), 2.26-1.25 (m, 33H, PCy
3).
The synthesis of embodiment 39 ruthenium complex 4aw
Add the DCM of part 3aw (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4aw, productive rate: 8% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4aw)
1h-NMR (400MHz, CDCl
3): δ 19.43 (d, J=9.9Hz, Ru=CH), 8.57 (d, J=8.1Hz, 1H, aromatic H), 7.26-6.78 (m, 5H, aromatic H), 5.29 (m, 2H, OCH, NH), 4.53 (m, 1H, NCH
2), 3.72 (m, 1H, NCH
2), 2.26-1.24 (m, 48H, PCy
3, C (CH3)
3, OCH (CH
3)
2).
The synthesis of embodiment 40 ruthenium complex 4az
Add the DCM of part 3az (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4az, productive rate: 31% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4az)
1h-NMR (400MHz, CDCl
3): δ 18.53 (s, 1H, Ru=CH), 7.26-5.75 (m, 10H, aromatic H), 4.88 (d, J=11.2Hz, 1H, NCH
2), 4.52-4.43 (m, 2H, OCH), 4.14-3.88 (m, 5H, NCH
2, NCH
2cH
2n), 2.98-1.39 (m, 27H, NCH
3, aromatic CH
3, OCH (CH
3)
2).
The synthesis of embodiment 41 ruthenium complex 4ba
Add the DCM of part 3ba (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ba, productive rate: 44% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ba)
1h-NMR (400MHz, CDCl
3): δ 18.99 (s, 1H, Ru=CH), 7.45-6.36 (m, 9H, aromatic H), 5.05 (m, 2H, OCH, NH), 3.98-3.91 (m, 5H, NCH
2, NCH
2cH
2n), 3.72 (d, J=13.2Hz, 1H, NCH
2), 2.48-2.34 (m, 19H, C (CH3)
3, aromatic CH
3), 1.45-0.95 (m, 21H, OCH (CH
3)
2, C (CH3)
3).
The synthesis of embodiment 42 ruthenium complex 4bb
Add the DCM of part 3bb (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bb, productive rate: 42% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bb)
1h-NMR (400MHz, CDCl
3): 19.02 (s, 1H, Ru=CH), 7.21-6.82 (m, 8H, aromatic H), 6.40 (dd, J=9.6Hz, 1.6Hz, aromatic H), 5.206 (m, 1H, NH), 4.06-4.00 (m, 5H, NCH
2, NCH
2cH
2nH), 3.7 (s, 3H, OCH
3), 3.54 (d, J=13.2Hz, 1H, NCH
2), 2.48-2.18 (m, 24H, aromatic CH
3).
The synthesis of embodiment 43 ruthenium complex 4be
Add the DCM of part 3be (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4be, productive rate: 48% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4be)
1h-NMR (400MHz, CDCl
3): δ 18.88 (s, 1H, Ru=CH), 7.57-6.44 (m, 11H, aromatic H), 5.36 (t, J=13.2Hz, 1H, NH), 4.16-4.02 (m, 5H, NCH
2, NCH
2cH
2n), 4.01 (d, J=13.2Hz, 1H, NCH
2), 2.75-2.00 (m, 19H, CH (CH
3)
2, aromatic CH
3), 1.01-0.90 (m, 6H, CH (CH3)
2).
The synthesis of embodiment 44 ruthenium complex 4bg
Add the DCM of part 3bg (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bg, productive rate: 52% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bg)
1h-NMR (400MHz, CDCl
3): δ 18.95 (s, 1H, Ru=CH), 7.43-6.36 (m, 10H, aromatic H), 4.00 (m, 6H, NCH
2, NCH
2cH
2n), 2.67-2.06 (m, 20H, CH (CH
3)
2, aromatic CH
3), 0.90-0.83 (m, 12H, CH (CH3)
2).
The synthesis of embodiment 45 ruthenium complex 4bj
Add the DCM of part 3bj (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bj, productive rate: 64% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bj)
1h-NMR (400MHz, CDCl
3): δ 18.88 (s, 1H, Ru=CH), 7.25-6.36 (m, 9H, aromatic H), 5.40 (t, J=13.2Hz, 1H, NH), 4.14-4.00 (m, 6H, NCH
2, NCH
2cH
2n), 2.77-1.90 (m, 27H, aromatic CH
3).
The synthesis of embodiment 46 ruthenium complex 4bk
Add the DCM of part 3bk (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bk, productive rate: 26% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bk)
1h-NMR (400MHz, CDCl
3): δ 18.91 (s, 1H, Ru=CH), 7.63-6.42 (m, 10H, aromatic H), 5.27 (t, J=13.2Hz, 1H, NH), 4.13-4.01 (m, 5H, NCH
2, NCH
2cH
2n), 3.44 (d, J=13.2Hz, 1H, NCH
2), 2.46-2.00 (m, 21H, aromatic CH
3).
The synthesis of embodiment 47 ruthenium complex 4bn
Add the DCM of part 3bn (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bn, productive rate: 38% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bn)
1h-NMR (400MHz, CDCl
3): δ 18.75 (s, 1H, Ru=CH), 7.26-6.21 (m, 9H, aromatic H), 4.05-3.85 (m, 5H, NCH
2, NCH
2cH
2n), 3.72 (s, 3H, OCH
3), 3.34 (d, J=13.2Hz, 1H, NCH
2), 2.82-0.95 (m, 30H, NCH
3, aromatic CH
3).
The synthesis of embodiment 48 ruthenium complex 4br
Add the DCM of part 3br (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4br, productive rate: 14% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4br)
1h-NMR (400MHz, CDCl
3): δ 18.89 (s, 1H, Ru=CH), 7.69-6.43 (m, 10H, aromatic H), 5.23 (dd, J=13.2,11.3Hz, 1H, NH), 4.16-3.94 (m, 5H, NCH
2, NCH
2cH
2n), 3.46 (d, J=11.3Hz, 1H, NCH
2), 2.62-1.00 (m, 21H, aromatic CH
3).
The synthesis of embodiment 49 ruthenium complex 4bs
Add the DCM of part 3bs (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bs, productive rate: 17% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bs)
1h-NMR (400MHz, CDCl
3): δ 19.53 (d, J=9.9Hz, Ru=CH), 8.43 (d, J=8.1Hz, 1H, aromatic H), 7.57-6.79 (m, 5H, aromatic H), 5.43 (dd, J=13.2,11.3Hz, 1H, NH), 4.60 (d, J=13.2Hz, 1H, NCH
2), 3.72 (d, J=11.3Hz, 1H, NCH
2), 2.29-0.95 (m, 36H, PCy
3, aromatic CH
3).
The synthesis of embodiment 50 ruthenium complex 4bv
Add the DCM of part 3bv (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bv, productive rate: 90% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bv)
1h-NMR (400MHz, CDCl
3): δ 18.75 (s, 1H, Ru=CH), 7.50-7.44 (m, 2H, aromatic H), (7.04-6.36 m, 9H, aromatic H), 5.32-5.21 (m, 1H, NH), 4.65 (d, J=13.2Hz, 1H, NCH
2), 4.16-4.04 (m, 4H, NCH
2cH
2n), 3.59 (s, 3H, OCH
3), 3.48 (d, J=13.2Hz, 1H, NCH
2), 2.62-2.32 (m, 18H, aromatic CH
3).
The synthesis of embodiment 51 ruthenium complex 4bw
Add the DCM of part 3bw (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bw, productive rate: 49% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bw)
1h-NMR (400MHz, CDCl
3): δ 19.39 (d, J=10Hz, Ru=CH), 8.11 (d, J=8Hz, 1H, aromatic H), 7.64-7.06 (m, 2H, aromatic H), 7.16-6.87 (m, 4H, aromatic H), (5.47 m, 1H, NH), 5.24 (m, 1H, NCH
2), 3.92 (d, J=13.6Hz, 1H, NCH
2), 3.80 (s, 3H, OCH
3), 2.30-0.87 (m, 33H, PCy
3).
The synthesis of embodiment 52 ruthenium complex 4bx
Add the DCM of part 3bx (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4bx, productive rate: 65% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4bx)
1h-NMR (300MHz, CDCl3): δ 18.82 (s, 1H, Ru=CH), 7.47-7.43 (m, 2H, aromatic H), 7.01-6.56 (m, 9H, aromatic H), 5.12-5.09 (m, 1H, NH), 4.56-4.45 (m, 2H, OCH, NHCH
2), 4.40-4.15 (m, 4H, NCH
2cH
2n), 3.48-3.45 (m, 1H, NHCH
2), 2.64-2.04 (m, 18H, aromatic CH
3), 1.10 (d, J=6.4Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 53 ruthenium complex 4cc
Add the DCM of part 3cc (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cc, productive rate: 23% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cc)
1h-NMR (300MHz, CDCl3): δ 18.97 (s, 1H, Ru=CH), 8.54-8.45 (m, 2H, aromatic H), 6.66-6.96 (m, 8H, aromatic H), 4.16-4.10 (m, 1H, NH), 4.03 (s, 4H, NCH
2cH
2n), 2.63-1.75 (m, 22H, NHCH
2, aromatic CH
3), 0.92 (d, J=7.6Hz, OCH (CH
3)
2), 0.83 (d, J=7.6Hz, OCH (CH
3)
2).
The synthesis of embodiment 54 ruthenium complex 4cd
Add the DCM of part 3cd (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cd, productive rate: 42% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cd)
1h-NMR (400MHz, CDCl
3): δ 19.02 (s, 1H, Ru=CH), 7.87 (dd, J=8,1.2Hz, 1H, aromatic H), 7.44 (dd, J=7.2,1.2Hz, 1H, aromatic H), 7.25-7.03 (m, 9H, aromatic H), (5.37-5.30 m, 1H, NH), 4.76-4.74 (m, 1H, NCH
2), 4.16-4.01 (m, 4H, NCH
2cH
2n), 3.58-3.54 (m, 4H, NCH
2, OCH
3), 2.75 (s, 6H, NCH
3), 2.73-1.98 (m, 18H, aromatic CH
3).
The synthesis of embodiment 55 ruthenium complex 4cf
Add the DCM of part 3cf (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cf, productive rate: 32% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cf)
1h-NMR (300MHz, CDCl3): δ 19.03 (s, 1H, Ru=CH), 7.48-6.63 (m, 10H, aromatic H), 5.53 (m, 1H, NH), 4.81-4.78 (m, 1H, NHCH
2), 4.00 (s, 4H, NCH
2cH
2n), 2.51-2.49 (m, 1H, NHCH
2), 2.51-2.32 (m, 18H, aromatic CH
3), 1.12 (d, J=7.6Hz, OCH (CH
3)
2), 1.04 (d, J=7.6Hz, OCH (CH
3)
2).
The synthesis of embodiment 56 ruthenium complex 4cg
Add the DCM of part 3cg (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cg, productive rate: 51% with methyl alcohol or pentane-DCM washing.
After testing,
1h-NMR (300MHz, CDCl
3): δ 19.06 (s, 1H, Ru=CH), 7.87 (d, J=7.6Hz, 1H, aromatic H), 7.42 (d, J=7.6Hz, 1H, aromatic H), 7.29 (d, J=12Hz, 1H, aromatic H), 7.11-6.56 (m, 8H, aromatic H), 5.22-5.19 (m, 1H, NH), 4.63-4.64 (m, 1H, NHCH
2), 4.45-4.42 (m, 1H, OCH), 4.14-4.01 (m, 4H, NCH
2cH
2n), 3.56-3.53 (m, 1H, NHCH
2), 3.12-3.07 (m, 4H, NCH
2), 2.67-2.36 (m, 18H, aromatic CH
3), 1.99-1.00 (m, 24H, CH
2cH
2cH
2cH
3, OCH (CH
3)
2).
The synthesis of embodiment 57 ruthenium complex 4ch
Add the DCM of part 3ch (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ch, productive rate: 74% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ch)
1h-NMR (300MHz, CDCl3): δ 19.06 (s, 1H, Ru=CH), 7.87 (d, J=7.6Hz, 1H, aromatic H), 7.42 (d, J=7.6Hz, 1H, aromatic H), 7.11-6.56 (m, 9H, aromatic H), (5.27-5.20 m, 1H, NH), 4.64-4.61 (m, 1H, NHCH
2), 4.46-4.44 (m, 1H, OCH), 4.14-4.01 (m, 4H, NCH
2cH
2n), 3.59-3.56 (m, 1H, NHCH
2), 3.12-3.07 (m, 4H, NCH
2), 2.75 (s, 6H, NCH
3), 2.67-2.36 (m, 18H, aromatic CH
3), 1.13 (d, J=6.0Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 58 ruthenium complex 4cj
Add the DCM of part 3cj (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cj, productive rate: 77% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cj)
1h-NMR (400MHz, CDCl
3): δ 19.56 (d, J=9.6Hz, Ru=CH), 8.21 (d, J=8.0Hz, 1H, aromatic H), 8.09 (d, J=2Hz, 1H, aromatic H), 8.10 (dd, J=7.6,2Hz, 1H, aromatic H), 7.34-6.87 (m, 4H, aromatic H), 5.47-5.44 (m, 1H, NH), 5.33-5.27 (m, 1H, NCH
2), 4.62-4.56 (m, 1H, OCH), 3.99-3.96 (m, 1H, NCH
2), 2.80 (s, 6H, NCH
3), 2.30-1.24 (m, 39H, PCy
3, OCH (CH
3)
2).
The synthesis of embodiment 59 ruthenium complex 4ck
Add the DCM of part 3ck (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ck, productive rate: 47% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ck)
1h-NMR (400MHz, CDCl
3): δ 18.99 (s, 1H, Ru=CH), 7.88 (dd, J=8,2Hz, 1H, aromatic H), 7.44 (dd, J=7.2,1.2Hz, 1H, aromatic H), 7.28-6.63 (m, 9H, aromatic H), (5.35-5.28 m, 1H, NH), 4.75-4.72 (m, 1H, NCH
2), 4.16-4.12 (m, 4H, NCH
2cH
2n), 3.61 (s, 3H, OCH
3), 3.56-3.52 (m, 4H, NCH
2), 3.10-3.06 (m, 4H, NCH
2), 2.63-2.05 (m, 18H, aromatic CH
3), 1.37-0.98 (m, 14H, CH
2cH
2cH
3).
The synthesis of embodiment 60 ruthenium complex 4cm
Add the DCM of part 3cm (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cm, productive rate: 27% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cm)
1h-NMR (400MHz, CDCl
3): δ 19.03 (s, 1H, Ru=CH), 7.60 (d, J=7.6Hz, 1H, aromatic H), 7.43 (d, J=3.6Hz, 1H, aromatic H), 7.14 (s, 1H, aromatic H), 7.09-7.00 (m, 5H, aromatic H), 6.81-6.57 (m, 3H, aromatic H), 5.22 (m, 1H, NH), 4.64-4.61 (m, 1H, NCH
2), 4.64-4.42 (m, 2H, OCH, NH), 4.15-4.02 (m, 4H, NCH
2cH
2n), 3.16 (m, 1H, NCH
2), 3.17 (m, 1H, NCH), 2.67-2.00 (m, 18H, aromatic CH
3), 1.85-1.00 (m, 16H, CH
2cH
2, OCH (CH
3)
2).
The synthesis of embodiment 61 ruthenium complex 4cn
Add the DCM of part 3cn (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cn, productive rate: 26% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cn)
1h-NMR (400MHz, CDCl
3): δ 18.96 (s, 1H, Ru=CH), 7.95 (d, J=7.6Hz, 1H, aromatic H), 7.45 (d, J=8Hz, 1H, aromatic H), 7.35 (s, 1H, aromatic H), 7.07-7.03 (m, 5H, aromatic H), 6.78-6.65 (m, 3H, aromatic H), 5.31 (m, 1H, NH), 4.76-4.73 (m, 1H, NCH
2), 4.38-4.37 (m, 1H, NH), 4.14-4.03 (m, 4H, NCH
2cH
2n), 3.60 (s, 3H, OCH
3), 3.56-3.53 (m, 1H, NCH
2), 3.14-3.13 (m, 1H, NCH), 2.66-1.27 (m, 34H, aromatic CH
3, CH
2cH
2, OCH (CH
3)
2).
The synthesis of embodiment 62 ruthenium complex 4cp
Add the DCM of part 3cp (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cp, productive rate: 68% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cp)
1h-NMR (400MHz, CDCl
3): δ 18.90 (s, 1H, Ru=CH), 7.27-6.77 (m, 9H, aromatic H), (6.41 d, J=8.0Hz, 1H, aromatic H), 5.43 (t, J=13.2Hz, 1H, NH), 4.18-4.00 (m, 5H, NCH
2, NCH
2cH
2n), 3.25 (d, J=13.6Hz, NCH
2), 2.76-1.27 (m, 24H, aromatic CH
3).
The synthesis of embodiment 63 ruthenium complex 4cr
Add the DCM of part 3cr (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cr, productive rate: 59% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cr)
1h-NMR (400MHz, CDCl
3): δ 18.82 (s, 1H, Ru=CH), 8.15 (dd, J=6.4,1.2Hz, 2H, aromatic H), 7.51 (d, J=1.2Hz, 1H, aromatic H), 7.44 (d, J=1.2Hz, 1H, aromatic H), 7.05-6.99 (m, 5H, aromatic H), 8.15 (d, J=6.4Hz, 2H, aromatic H), 6.59-6.56 (m, 1H, aromatic H), (5.22 m, 1H, NH), 4.63 (m, 1H, NHCH
2), 4.41 (m, 1H, OCH), 3.96 (m, 4H, NCH
2cH
2n), 3.55-3.52 (m, 1H, NHCH
2), 2.66-2.33 (m, 18H, aromatic CH
3), 1.14 (d, J=6.4Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 64 ruthenium complex 4cs
Add the DCM of part 3cs (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cs, productive rate: 82% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cs)
1h-NMR (400MHz, CDCl
3): δ 18.73 (s, 1H, Ru=CH), 7.45-6.60 (m, 7H, aromatic H), 6.44 (dd, J=8.0,1.2Hz, 1H, aromatic H), 6.38 (dd, J=7.6,2.4Hz, 1H, aromatic H), 5.06 (m, 1H, NH), 4.17-3.92 (m, 7H, NCH
2, NCH
2cH
2n, OCH
2), 3.55 (m, 1H, NCH
2), 2.44-1.00 (m, 7H, aromatic CH
3).
The synthesis of embodiment 65 ruthenium complex 4ct
Add the DCM of part 3ct (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4ct, productive rate: 57% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4ct)
1h-NMR (400MHz, CDCl
3): δ 19.40 (d, J=10Hz, Ru=CH), 7.40 (d, J=7.6Hz, 1H, aromatic H), 7.31-7.29 (m, 2H, aromatic H), 7.26 (dd, J=7.6,2Hz, 1H, aromatic H), 6.84-6.82 (m, 2H, aromatic H), 5.15 (m, 1H, NH), 4.93 (m, 1H, NCH
2), 3.96-3.83 (m, 3H, OCH
2, NCH
2), 2.28-1.00 (m, 40H, PCy
3, CH
2cH
2cH
3).
The synthesis of embodiment 66 ruthenium complex 4cu
Add the DCM of part 3cu (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cu, productive rate: 65% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cu)
1h-NMR (400MHz, CDCl
3): δ 18.68 (s, 1H, Ru=CH), 7.28-6.96 (m, 10H, aromatic H), 6.37 (d, J=8.5Hz, 1H, aromatic H), 5.31 (m, 3H, NCH
2, OCH
2), 4.71-4.01 (m, 5H, NH, NCH
2cH
2n), 3.58 (d, J=12.8Hz, 1H, NCH
2), 2.89-1.29 (m, 21H, OCH
2cH
3, aromatic CH
3).
The synthesis of embodiment 67 ruthenium complex 4cw
Add the DCM of part 3cw (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cw, productive rate: 85% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cw)
1h-NMR (400MHz, CDCl
3): δ 18.68 (s, 1H, Ru=CH), 7.28-6.42 (m, 10H, aromatic H), 6.37 (d, J=8.5Hz, 1H, aromatic H), 5.05 (m, 1H, NCH
2), 4.06-3.93 (m, 7H, NH, NCH
2cH
2n, OCH
2), 3.57 (d, J=12.8Hz, 1H, NCH
2), 2.89-1.29 (m, 29H, CH
2cH
3, aromatic CH
3).
The synthesis of embodiment 68 ruthenium complex 4cy
Add the DCM of part 3cy (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cy, productive rate: 70% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cy)
1h-NMR (400MHz, CDCl
3): δ 18.68 (s, 1H, Ru=CH), 7.28-6.61 (m, 10H, aromatic H), 6.41 (d, J=8.5Hz, 1H, aromatic H), 5.05 (m, 1H, NCH
2), 4.52-4.06 (m, 6H, NH, NCH
2cH
2n, OCH), 3.57 (d, J=12.8Hz, 1H, NCH
2), 2.89-1.29 (m, 24H, CH
2cH
3, aromatic CH
3).
The synthesis of embodiment 69 ruthenium complex 4cz
Add the DCM of part 3cz (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 4cz, productive rate: 64% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4cz)
1h-NMR (400MHz, CDCl
3): δ 19.28 (d, J=8.4Hz, Ru=CH), 7.46 (d, J=8.8Hz, 2H, aromatic H), 7.40-7.18 (m, 3H, aromatic H), 6.84 (d, J=8.8Hz, 2H, aromatic H), 5.21 (t, J=12.4Hz, 1H, NH), 4.93 (d, J=12.4Hz, 1H, NCH
2), 4.50 (m, 1H, OCH), 3.90-3.86 (m, 1H, NCH
2), 2.30-1.21 (m, 39H, CH
2cH
3, PCy
3).
Below adopt complex ligands (5a-5z) to synthesize ruthenium complex 6a-6z according to relevant documents and materials:
Be below the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 6a-6z:
The synthesis of embodiment 70 ruthenium complex 6a
Add the DCM of part 5a (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6a, productive rate: 79% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6a)
1hNMR (400MHz, CDCl
3): δ 18.529 (s, 1H, Ru=CH), 8.587 (s, 1H, N=CH), 7.283-6.490 (m, 11H, aromatic H), 4.160 (s, 4H, NCH
2cH
2n), 2.50 (s, 12H, aromatic CH
3), 2.42 (s, 6H, aromatic CH
3).
The synthesis of embodiment 71 ruthenium complex 6b:
Add the DCM of part 5b (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6b, productive rate: 77% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6a)
1hNMR (400MHz, CDCl
3): δ 19.197 (d, J=10.8Hz, Ru=CH), 8.819 (d, J=9.2Hz, 1H, N=CH), 7.835 (m, 1H, aromatic H), 7.795 (d, J=8.4Hz, 1H, aromatic H), 7.453 (m, 4H, aromatic H), 2.459-1.291 (m, 33H, PCy
3).
The synthesis of embodiment 72 ruthenium complex 6c:
Add the DCM of part 5c (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6c, productive rate: 96% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6c)
1hNMR (400MHz, CDCl
3): δ 18.516 (s, 1H, Ru=CH), 8.599 (s, 1H, N=CH), 7.283-7.133 (m, 7H, aromatic H), 7.017 (d, J=8.8Hz, 1H, aromatic H), 6.800 (m, 1H, aromatic H), 6.091 (d, J=8.8Hz, 1H, aromatic H), 4.160 (s, 4H, NCH
2cH
2n), 3.837 (s, 3H, OCH
3), 2.514 (m, 18H, aromatic CH
3).
The synthesis of embodiment 73 ruthenium complex 6d:
Add the DCM of part 5d (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6d, productive rate: 65% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6d)
1hNMR (400MHz, CDCl
3): δ 19.639 (d, J=11.6Hz, Ru=CH), 8.868 (d, J=13.6Hz, 1H, N=CH), (7.865-7.842 m, 3H, aromatic H), (7.430-7.97 m, 2H, aromatic H), (6.999-6.976 m, 2H, aromatic H), 3.768 (s, 3H, OCH
3), 2.310-1.074 (m, 33H, PCy
3).
The synthesis of embodiment 74 ruthenium complex 6e:
Add the DCM of part 5e (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6e, productive rate: 31% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6e)
1hNMR (400MHz, CDCl
3): δ 18.731 (s, 1H, Ru=CH), 8.619 (s, 1H, N=CH), (7.670-7.456 m, 3H, aromatic H), (7.113 s, 4H, aromatic H), (6.779-6.651 m, 5H, aromatic H), 4.131 (s, 4H, NCH
2cH
2n), 3.810 (s, 3H, OCH
3), 2.493 (m, 18H, aromatic CH
3).
The synthesis of embodiment 75 ruthenium complex 6f:
Add the DCM of part 5f (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6f, productive rate: 7% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6f)
1hNMR (400MHz, CDCl
3): δ 19.373 (d, J=11.7Hz, Ru=CH), 8.836 (d, J=9.3Hz, 1H, N=CH), 7.877-7.682 (m, 6H, aromatic H), 6.974 (d, J=8.7Hz, 2H, aromatic H), 3.885 (s, 3H, OCH
3), 2.496-1.275 (m, 33H, PCy
3).
The synthesis of embodiment 76 ruthenium complex 6g:
Add the DCM of part 5g (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6g, productive rate: 24% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6g)
1hNMR (400MHz, CDCl
3): δ 18.741 (s, 1H, Ru=CH), 8.602 (s, 1H, N=CH), 7.692-7.485 (m, 3H, aromatic H), 7.120-7.042 (m, 8H, aromatic H), 6.798 (d, J=8.7Hz, 1H, aromatic H), 4.131 (s, 4H, NCH
2cH
2n), 2.495 (m, 18H, aromatic CH
3).
The synthesis of embodiment 77 ruthenium complex 6h:
Add the DCM of part 5h (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6h, productive rate: 27% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6h)
1hNMR (400MHz, CDCl
3): δ 18.95 (d, J=6.4Hz, Ru=CH), 10.26 (d, J=9.2Hz, 1H, N=CH), 7.985-7.256 (m, 8H, aromatic H), 2.430-0.854 (m, 33H, PCy
3).
The synthesis of embodiment 78 ruthenium complex 6j:
Add the DCM of part 5j (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6j, productive rate: 38% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6j)
1hNMR (400MHz, CDCl
3): δ 18.751 (s, 1H, Ru=CH), 8.647 (s, 1H, N=CH), 7.710-6.789 (m, 13H, aromatic H), 4.197 (s, 4H, NCH
2cH
2n), 2.490 (m, 18H, aromatic CH
3).
The synthesis of embodiment 79 ruthenium complex 6k:
Add the DCM of part 5k (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6k, productive rate: 15% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6k)
1hNMR (400MHz, CDCl
3): δ 19.45 (d, J=6.4Hz, Ru=CH), 8.868 (d, J=9.3Hz, 1H, N=CH), 7.896-7.259 (m, 9H, aromatic H), 2.491-1.268 (m, 33H, PCy
3).
The synthesis of embodiment 80 ruthenium complex 6m:
Add the DCM of part 5m (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6m, productive rate: 17% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6m)
1hNMR (400MHz, CDCl
3): δ 18.595 (s, 1H, Ru=CH), 8.579 (s, 1H, N=CH), 7.480-7.292 (m, 2H, aromatic H), 7.016 (d, J=8.8Hz, 2H, aromatic H), (6.743-6.687 m, 3H, aromatic H), 4.165 (s, 4H, NCH
2cH
2n), 3.845 (s, 3H, OCH
3), 2.519 (m, 18H, aromatic CH
3).
The synthesis of embodiment 81 ruthenium complex 6n:
Add the DCM of part 5n (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6n, productive rate: 40% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6n)
1hNMR (400MHz, CDCl
3): δ 18.522 (s, 1H, Ru=CH), 8.592 (s, 1H, N=CH), 7.292-6.838 (m, 10H, aromatic H), 6.838-6.818 (m, 1H, aromatic H), 4.167 (s, 4H, NCH
2cH
2n), 2.517 (m, 18H, aromatic CH
3).
The synthesis of embodiment 82 ruthenium complex 6p:
Add the DCM of part 5p (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6p, productive rate: 47% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6p)
1hNMR (400MHz, CDCl
3): δ 19.214 (d, J=11.2Hz, Ru=CH), 8.819 (d, J=9.2Hz, 1H, N=CH), 7.893-7.858 (m, 3H, aromatic H), 7.507-7.416 (m, 4H, aromatic H), 2.501-1.573 (m, 33H, PCy
3).
The synthesis of embodiment 83 ruthenium complex 6q:
Add the DCM of part 5q (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6q, productive rate: 33% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6q)
1hNMR (400MHz, CDCl
3): δ 18.541 (s, 1H, Ru=CH), 8.634 (s, 1H, N=CH), 7.292-6.849 (m, 11H, aromatic H), 6.849-6.835 (m, 1H, aromatic H), 4.169 (s, 4H, NCH
2cH
2n), 2.510 (m, 18H, aromatic CH
3).
The synthesis of embodiment 84 ruthenium complex 6r:
Add the DCM of part 5r (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6r, productive rate: 8% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6r)
1hNMR (400MHz, CDCl
3): δ 19.25 (d, J=10.8Hz, Ru=CH), 8.856 (d, J=9.2Hz, 1H, N=CH), 7.894 (m, 3H, aromatic H), 7.521-7.428 (m, 5H, aromatic H), 2.508-1.742 (m, 33H, PCy
3).
The synthesis of embodiment 85 ruthenium complex 6s:
Add the DCM of part 5s (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6s, productive rate: 37% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6s)
1hNMR (400MHz, CDCl
3): δ 16.52 (s, 1H, Ru=CH), 8.43 (s, 1H, N=CH), (8.10 s, 1H, aromatic H), 7.46-7.22 (m, 2H, aromatic H), 7.73-6.96 (m, 8H, aromatic H), 4.19 (s, 4H, NCH
2cH
2n), 3.947 (s, 3H, OCH
3), 3.87 (s, 3H, OCH
3), 2.49 (s, 12H, aromatic CH
3), 2.48 (s, 6H, aromatic CH
3).
The synthesis of embodiment 86 ruthenium complex 6t:
Add the DCM of part 5t (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains greenish yellow solid product 6t, productive rate with methyl alcohol or pentane-DCM washing:--%.
After testing, ruthenium complex (6t)
1hNMR (400MHz, CDCl
3): δ 17.43 (d, J=4.8Hz, Ru=CH), 8.56 (s, 1H, N=CH), 8.32-8.10 (m, 2H, aromatic H), 7.28-6.96 (m, 5H, aromatic H), 4.40 (s, 3H, OCH
3), 3.86 (s, 3H, OCH
3), 2.33-1.30 (m, 33H, PCy
3).
The synthesis of embodiment 87 ruthenium complex 6u:
Add the DCM of part 5u (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains gray solid product 6u, productive rate: 17% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6u)
1hNMR (400MHz, CDCl
3): δ 17.40 (d, J=11.1Hz, Ru=CH), 8.519 (m, 1H, N=CH), 8.333-8.190 (m, 4H, aromatic H), 7.405-7.175 (m, 3H, aromatic H), 4.39 (s, 3H, OCH
3), 2.31-0.82 (m, 33H, PCy
3).
The synthesis of embodiment 88 ruthenium complex 6v
Add the DCM of part 5v (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains red solid product 6v, productive rate: 28% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to purification assays ruthenium complex 6v's
1h-NMR structure, but its impure ruthenium complex 6v can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 89 ruthenium complex 6w
Add the DCM of part 5w (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 6w, productive rate: 22% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6w)
1h-NMR (400MHz, CDCl
3): δ 18.659 (s, 1H, Ru=CH), 8.556 (s, 1H, N=CH), (7.499-7.337 m, 2H, aromatic H), (7.256 s, 4H, aromatic H), (7.004-6.397 m, 5H, aromatic H), 4.138 (s, 4H, NCH
2cH
2n), 3.805 (s, 3H, OCH
3), 2.493 (m, 18H, aromatic CH
3).
The synthesis of embodiment 90 ruthenium complex 6y
Add the DCM of part 5y (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 6y, productive rate: 9% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6y)
1h-NMR (400MHz, CDCl
3): δ 18.96 (s, 1H, Ru=CH), 8.43 (s, 1H, N=CH), 7.42-6.94 (m, 9H, aromatic H), 6.39 (d, J=9.2Hz, 1H, aromatic H), 4.01 (s, 4H, NCH
2cH
2n), 2.67-2.28 (m, 20H, aromatic CH, aromatic CH
3), 0.92 (d, J=7.6Hz, OCH (CH
3)
2), 0.83 (d, J=7.6Hz, OCH (CH
3)
2).
The synthesis of embodiment 91 ruthenium complex 6z
Add the DCM of part 5z (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 6z, productive rate: 9% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (6z)
1h-NMR (400MHz, CDCl
3): δ 18.60 (s, 1H, Ru=CH), 9.88 (s, 1H, N=CH), 7.79-6.96 (m, 8H, aromatic H), 6.54 (d, J=9.2Hz, 1H, aromatic H), 4.18 (s, 4H, NCH
2cH
2n), 2.48-2.31 (m, 27H, aromatic CH
3).
Below adopt complex ligands (7a-7t) to synthesize ruthenium complex 8a-8t according to pertinent data:
Be below the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 8a-8t:
The synthesis of embodiment 92 ruthenium complex 8a
Add the DCM of part 7a (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8a, productive rate: 32% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8a)
1hNMR (400MHz, CDCl
3): δ 16.80 (s, 1H, Ru=CH), 7.07 (s, 4H, aromatic H), 6.94 (m, 1H, aromatic H), 6.30 (d, J=6.4Hz, 1H, aromatic H), 4.11 (s, 4H, NCH
2cH
2n), 2.69 (s, 6H, NCH
3), 2.49 (s, (s, 12H, aromatic CH
3), 2.42 (s, 6H, aromatic CH
3).
The synthesis of embodiment 93 ruthenium complex 8b
Add the DCM of part 7b (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8b, productive rate: 79% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8b)
1hNMR (400MHz, CDCl
3): δ 16.695 (s, 1H, Ru=CH), 7.368 (m, 1H, aromatic H), (7.037-6.91 m, 6H, aromatic H), 6.717 (d, J=7.6Hz, 1H, aromatic H), 5.050 (d, J=11.6Hz, 1H, NCH
2), 3.876-3.846 (m, 4H, NCH
2cH
2n), 3.519 (s, 3H, OCH
3), 3.438 (d, J=11.6Hz, 1H, NCH
2), 2.85-1.50 (m, 21H, NCH
3, aromatic CH
3).
The synthesis of embodiment 94 ruthenium complex 8c
Add the DCM of part 7c (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8c, productive rate: 9% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8c)
1hNMR (400MHz, CDCl
3): δ 16.967 (s, 1H, Ru=CH), 8.400 (dd, J=8.8,2.4Hz, 1H, aromatic H), 7.65 (d, J=2.4Hz, 1H, aromatic H), 7.29 (d, J=8.8Hz, 1H, aromatic H), (7.07 s, 4H, aromatic H), 4.199 (s, 4H, NCH
2cH
2n), 2.567 (s, 6H, N (CH
3)
2, 2.473 (s, 12H, aromatic CH
3), 2.390 (s, 6H, aromatic CH
3).
The synthesis of embodiment 95 ruthenium complex 8d
Add the DCM of part 7d (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8d, productive rate: 24% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8d)
1hNMR (400MHz, CDCl
3): δ 16.691 (s, 1H, Ru=CH), 8.356 (dd, J=8.8,2.4Hz, 1H, aromatic H), 7.618 (d, J=2.4Hz, 1H, aromatic H), 7.180 (d, J=8.8Hz, 1H, aromatic H), 7.167-6.999 (m, 4H, aromatic H), 4.164-3.795 (m, 6H, aromatic H), 2.838-2.076 (m, 21H, NCH
3, aromatic CH
3), 0.574 (t, J=6.8Hz, 3H, CH
2cH
3).
The synthesis of embodiment 96 ruthenium complex 8e
Add the DCM of part 7e (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8e, productive rate: 74% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8e)
1hNMR (400MHz, CDCl
3): δ 16.559 (s, 1H, Ru=CH), 8.331 (dd, J=8.4,2.4Hz, 1H, aromatic H), 7.563 (d, J=2.4Hz, 1H, aromatic H), 7.197-6.939 (m, 5H, aromatic H), 5.215 (d, J=11.2Hz, 1H, NCH
2), 4.210-3.959 (m, 4H, NCH
2cH
2n), 3.559 (s, 3H, OCH
3), 3.535 (d, J=11.2Hz, 1H, NCH
2), 2.938-0.923 (m, 21H, NCH
3, aromatic CH
3).
The synthesis of embodiment 97 ruthenium complex 8f
Add the DCM of part 7f (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8f, productive rate: 8% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8f)
1hNMR (400MHz, CDCl
3): δ 16.820 (s, 1H, Ru=CH), 7.171-7.007 (m, 7H, aromatic H), 6.773 (d, J=2Hz, 1H, aromatic H), 6.602 (d, J=2.8Hz, 1H, aromatic H), 6.550 (d, J=8.4Hz, 1H, aromatic H), 4.116 (s, 4H, NCH
2cH
2n), 3.262 (s, 3H, OCH
3), 2.734 (s, 3H, NCH
3), 2.572-2.260 (m, 18H, aromatic CH
3).
The synthesis of embodiment 98 ruthenium complex 8g
Add the DCM of part 7g (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8g, productive rate: 9% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8g)
1h-NMR (400MHz, CDCl
3): δ 17.661 (m, 1H, Ru=CH), 7.573 (d, J=2Hz, 1H, aromatic H), 7.477 (d, J=3Hz, 1H, aromatic H), 7.433 (dd, J=2,8.4Hz, 1H, aromatic H), 7.270 (d, J=3Hz, 1H, aromatic H), 6.983 (d, J=8.4Hz, 1H, aromatic H), 4.626 (d, J=13.2Hz, 1H, NCH
2), 3.978 (d, J=13.2Hz, 1H, NCH
2), 3.646 (s, 3H, OCH
3), 2.836 (s, 3H, NCH
3), 2.412-0.837 (m, 33H, PCy
3).
The synthesis of embodiment 99 ruthenium complex 8h
Add the DCM of part 7h (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8h, productive rate: 37% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8h)
1h-NMR (400MHz, CDCl
3): δ 16.843 (s, 1H, Ru=CH), 7.184 (d, J=8.4Hz, 1H, aromatic H), 7.807 (m, 5H, aromatic H), (6.748 m, 1H, aromatic H), 6.619 (d, J=8.8Hz, 1H, aromatic H), 6.320 (d, J=8.4Hz, 1H, aromatic H), 4.294-4.238 (m, 1H, OCH), 4.109 (s, 4H, NCH
2cH
2n), 3.846 (d, J=14.0Hz, 1H, NCH
2), 3.094 (d, J=14.0Hz, 1H, NCH
2), 2.737 (s, 3H, NCH
3), 2.429-2.278 (m, 18H, aromatic CH
3), 1.095 (d, J=6Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 100 ruthenium complex 8j
Add the DCM of part 7h (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8j, productive rate: 48% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8j)
1h-NMR (400MHz, CDCl
3): δ 17.584 (d, J=6.0Hz, 1H, Ru=CH), 7.585-7.549 (m, 2H, aromatic H), 7.478 (d, J=8.4Hz, 1H, aromatic H), 7.223 (dd, J=2.4,8.8Hz, 1H, aromatic H), 7.137 (d, J=8.4Hz, 1H, aromatic H), 6.784 (d, J=8.8Hz, 1H, aromatic H), 4.802 (d, J=12.8Hz, 1H, NCH
2), 4.500-4.470 (m, 1H, OCH), 4.049 (d, J=12.8Hz, 1H, NCH
2), 2.704 (s, 3H, NCH
3), 2.384-0.780 (m, 39H, PCy
3, OCH (CH
3)
2).
The synthesis of embodiment 101 ruthenium complex 8k
Add the DCM of part 7k (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8k, productive rate: 77% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8k)
1h-NMR (400MHz, CDCl
3): δ 16.872 (s, 1H, Ru=CH), 7.409 (dd, J=2,8.4Hz, 1H, aromatic H), 7.187-7.132 (m, 5H, aromatic H), 7.031 (d, J=8.4Hz, 1H, aromatic H), 6.925 (d, J=7.2Hz, 1H, aromatic H), 6.772-6.757 (m, 2H, aromatic H), 6.652 (t, J=7.2Hz, 1H, aromatic H), 4.655 (d, J=12.4Hz, 1H, NCH
2), 4.477-4.432 (m, 1H, OCH), 4.015-3.983 (m, 5H, NCH
2cH
2n, NCH
2), 2.535-2.304 (m, 18H, aromatic CH
3), 2.246 (s, 3H, NCH
3), 1.285 (d, J=6Hz, 6H, OCH (CH
3)
2).
The synthesis of embodiment 102 ruthenium complex 8m
Add the DCM of part 7m (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8m, productive rate: 23% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8m)
1h-NMR (400MHz, CDCl
3): δ 17.718 (m, 1H, Ru=CH), 7.846 (d, J=6.4Hz, 1H, aromatic H), 7.572 (d, J=2Hz, 1H, aromatic H), 7.528 (dd, J=2.4,8.4Hz, 1H, aromatic H), 7.333-7.233 (m, 2H, aromatic H), 6.980-6.890 (m, 2H, aromatic H), 4.939 (d, J=12.4Hz, 1H, NCH
2), 4.588-4.543 (m, 1H, OCH), 4.245-4.207 (m, 1H, NCH
2), 2.639 (s, 3H, NCH
3), 2.418-0.810 (m, 39H, PCy
3, OCH (CH
3)
2).
The synthesis of embodiment 103 ruthenium complex 8q
Add the DCM of part 7q (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8q, productive rate: 59% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8g)
1h-NMR (400MHz, CDCl
3): δ 16.80 (s, 1H, Ru=CH), 8.18 (dd, J=8.8,2.4Hz, 1H, aromatic H), 7.46 (d, J=2.4Hz, 1H, aromatic H), 7.23 (d, J=8.8Hz, 1H, aromatic H), (7.07 s, 4H, aromatic H), 4.11 (s, 4H, NCH
2cH
2n), 3.91 (s, 3H, COOCH
3), 2.58 (s, 6H, N (CH
3)
2, 2.47 (s, 12H, aromatic CH
3), 2.43 (s, 6H, aromatic CH
3).
The synthesis of embodiment 104 ruthenium complex 8s
Add the DCM of part 7s (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8s, productive rate: 43% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8s)
1h-NMR (400MHz, CDCl
3): δ 16.64 (s, 1H, Ru=CH), 8.34 (dd, J=8.4,2.4Hz, 1H, aromatic H), 7.54 (d, J=2.4Hz, 1H, aromatic H), 7.25-6.93 (m, 5H, aromatic H), 5.17 (d, J=11.2Hz, 1H, NCH
2), 4.84-4.83 (m, 1H, OCH), 4.14-3.93 (m, 4H, NCH
2cH
2n), 3.45 (d, J=11.2Hz, 1H, NCH
2), 2.89-1.19 (m, 27H, NCH
3, aromatic CH
3, OCH (CH
3)
2).
The synthesis of embodiment 105 ruthenium complex 8t
Add the DCM of part 7t (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 8t, productive rate: 87% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (8t)
1h-NMR (400MHz, CDCl
3): δ 16.82 (s, 1H, Ru=CH), 7.12-7.02 (m, 5H, aromatic H), 6.64 (m, 1H, aromatic H), 6.51-6.48 (m, 1H, aromatic H), 4.15 (s, 4H, NCH
2cH
2n), 3.95-3.92 (m, 1H, NH, NCH
2), 3.74 (s, 3H, OCH
3), 2.50-2.37 (m, 18H, aromatic CH
3), 0.96 (d, J=6.4Hz, 1H, CH
3).
Below adopt complex ligands (9a-9j) to synthesize ruthenium complex 10a-10j according to pertinent data:
Be below the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 10a-10j:
The synthesis of embodiment 106 ruthenium complex 10a
Add the DCM of part 9a (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 10a, productive rate: 19% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to purification assays ruthenium complex 10a's
1hNMR structure, but its impure ruthenium complex 10a can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 107 ruthenium complex 10b
Add the DCM of part 9b (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1a (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 10b, productive rate: 15% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to purification assays ruthenium complex 10b's
1hNMR structure, but its impure ruthenium complex 10b can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 108 ruthenium complex 10c
Add the DCM of part 9c (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains red brown solid product 10c, productive rate: 4% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (10c)
1hNMR (400MHz, CDCl
3): δ 18.675 (s, 1H, Ru=CH), 8.436 (dd, J=8.4,2.4Hz, 1H, aromatic H), 8.200 (d, J=8.4Hz, 1H, aromatic H), 7.604 (d, J=2.4Hz, 1H, aromatic H), (7.132 s, 4H, aromatic H), 4.140 (s, 4H, NCH
2cH
2n), 3.973 (s, 3H, OCH
3), 2.481 (s, 12H, aromatic CH
3), 2.459 (s, 6H, aromatic CH
3).
The synthesis of embodiment 109 ruthenium complex 10d
Add the DCM of part 9d (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains yellow solid product 10d, productive rate: 34% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (10d)
1hNMR (400MHz, CDCl
3): δ 18.71 (s, 1H, Ru=CH), 8.42 (dd, J=9,2.4Hz, 1H, aromatic H), 8.18 (d, J=9Hz, 1H, aromatic H), 7.60 (d, J=2.4Hz, 1H, aromatic H), (7.13 s, 4H, aromatic H), 5.25 (m, 1H, OCH (CH
3)
2), 4.13 (s, 4H, NCH
2cH
2n), 2.46 (m, 18H, aromatic CH
3), 1.24 (d, 6H, J=6Hz, CH (CH
3)
2).
The synthesis of embodiment 110 ruthenium complex 10e
Add the DCM of part 9e (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 10e, productive rate: 34% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (10e)
1hNMR (400MHz, CDCl
3): δ 18.56 (s, 1H, Ru=CH), 7.977 (d, J=8.8Hz, 1H, aromatic H), 8.18 (dd, J=8.8,2.4Hz, 1H, aromatic H), 7.105 (s, 4H, aromatic H), 7.064 (d, J=2.4Hz, 1H, aromatic H), 5.226 (m, 1H, OCH (CH
3)
2), 4.114 (s, 4H, NCH
2cH
2n), 2.451 (m, 18H, aromatic CH
3), 1.281 (d, 6H, J=6Hz, CH (CH
3)
2).
The synthesis of embodiment 111 ruthenium complex 10f
Add the DCM of part 9f (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains yellow solid product 10f, productive rate: 41% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (10f)
1hNMR (400MHz, CDCl
3): δ 18.75 (s, 1H, Ru=CH), 8.446 (dd, J=8.8,1.6Hz, 1H, aromatic H), 8.208 (d, J=8.8Hz, 1H, aromatic H), 7.637 (d, J=1.6Hz, 1H, aromatic H), 7.388-7.250 (m, 2H), 7.168 (s, 4H, aromatic H), 6.828 (d, J=8.8Hz, 1H, aromatic H), 5.370 (s, 2H, OCH
2), 4.529 (m, 1H, OCH (CH
3)
2), 4.151 (s, 4H, NCH
2cH
2n), 2.511 (m, 18H, aromatic CH
3), 1.395 (d, 6H, J=6Hz, CH (CH
3)
2).
The synthesis of embodiment 112 ruthenium complex 10g
Add the DCM of part 9g (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 10g, productive rate: 53% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (10g)
1hNMR (400MHz, CDCl
3): δ 18.601 (s, 1H, Ru=CH), 8.011 (d, J=8.4Hz, 1H, aromatic H), 7.590 (dd, J=1.6,8.4Hz, 1H, aromatic H), 7.306-7.228 (m, 1H, aromatic H), 7.237 (dd, J=2.8,8.8Hz, 1H, aromatic H), 6.811 (d, J=8.8Hz, 1H, aromatic H), 6.713 (d, J=2.0Hz, 1H, aromatic H), 5.334 (s, 2H, OCH
2), 4.515 (m, 1H, OCH (CH
3)
2), 4.159 (s, 4H, NCH
2cH
2n), 2.514 (s, 12H, aromatic CH
3), 2.482 (s, 6H, aromatic CH
3), 1.277 (d, 6H, J=6Hz, CH (CH
3)
2).
The synthesis of embodiment 113 ruthenium complex 10h
Add the DCM of part 9h (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 10h, productive rate: 23% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (10h)
1hNMR (400MHz, CDCl
3): δ 18.603 (s, 1H, Ru=CH), 8.003 (d, J=8.8Hz, 1H, aromatic H), 7.553 (d, J=8.4Hz, 1H, aromatic H), 7.320-7.288 (m, 1H, aromatic H), 7.140 (s, 4H, aromatic H), 7.008-6.703 (m, 4H, aromatic H), 5.378 (s, 2H, OCH
2), 4.560 (m, 1H, OCH (CH
3)
2), 4.158 (s, 4H, NCH
2cH
2n), 2.712 (s, 12H, aromatic CH
3), 2.515 (s, 6H, aromatic CH
3), 1.315 (d, 6H, J=6Hz, CH (CH
3)
2).
The synthesis of embodiment 114 ruthenium complex 10j
Add the DCM of part 9j (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 10j, productive rate: 37% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (10j)
1h-NMR (400MHz, CDCl
3):
1h-NMR (400MHz, CDCl
3): δ 18.74 (s, 1H, Ru=CH), 8.21 (dd, J=8,2.4Hz, 1H, aromatic H), 8.08 (d, J=8Hz, 1H, aromatic H), 7.54 (d, J=2.4Hz, 1H, aromatic H), (7.12 s, 4H, aromatic H), 5.32 (m, 1H, OCH (CH
3)
2), 5.25 (m, 1H, OCH (CH
3)
2), 4.13 (s, 4H, NCH
2cH
2n), 2.47 (m, 18H, aromatic CH
3), 1.43 (d, J=6Hz, CH (CH
3)
2), 1.24 (d, 6H, J=6Hz, CH (CH
3)
2).
Below adopt complex ligands (11a-11j) to synthesize ruthenium complex 12a-12j according to pertinent data:
Be below the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of complex compound 12a-12j:
The synthesis of embodiment 115 ruthenium complex 12a
Add the DCM of ligand 1 1a (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12a, productive rate: 75% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12a, but its impure ruthenium complex 12a can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 116 ruthenium complex 12b
Add the DCM of ligand 1 1b (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12b, productive rate: 57% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12b, but its impure ruthenium complex 12b can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 117 ruthenium complex 12c
Add the DCM of ligand 1 1c (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12c, productive rate: 40% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12c, but its impure ruthenium complex 12c can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 118 ruthenium complex 12d
Add the DCM of ligand 1 1d (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12d, productive rate: 42% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12d, but its impure ruthenium complex 12d can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 119 ruthenium complex 12e
Add the DCM of ligand 1 1e (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12e, productive rate: 69% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12e, but its impure ruthenium complex 12e can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 120 ruthenium complex 12f
Add the DCM of ligand 1 1f (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12f, productive rate: 63% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12f, but its impure ruthenium complex 12f can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 121 ruthenium complex 12g
Add the DCM of ligand 1 1g (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12g, productive rate: 69% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12g, but its impure ruthenium complex 12g can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 122 ruthenium complex 12h
Add the DCM of ligand 1 1h (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12h, productive rate: 61% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12h, but its impure ruthenium complex 12h can be directly used in the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 123 ruthenium complex 12j
Add the DCM of ligand 1 1j (10mmol), CuCl (30mmol, 3eq) and 30mL drying after a 50mL two mouthfuls of flask argon replaces successively, then protect enclosed system with argon gas ball afterwards three times by argon replaces.Ruthenium complex 1b (12mmol) is added, room temperature reaction 0.5 hour under argon shield.Reaction terminates, and adds silica gel sand, obtain thick product through silica gel column chromatography after filtering in filtrate, then obtains green solid product 12j, productive rate: 46% with methyl alcohol or pentane-DCM washing.Product is not very stable, is difficult to the structure of purification assays ruthenium complex 12j, but its impure ruthenium complex 12j can be directly used in the reaction of olefin metathesis metathesis catalysis.
Below adopt ruthenium complex (13-SM) to synthesize ruthenium complex 13a-13ag according to pertinent data:
Be below the structural formula (1a:Cy=cyclohexyl, 1b:Mes=2,4,6-Three methyl Benzene) of ruthenium complex 13a-13ag:
The synthesis of embodiment 124 ruthenium complex 13a
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13a, productive rate: 47% after filtration.
After testing, ruthenium complex (13a)
1h-NMR (400MHz, CDCl
3): δ 17.33 (s, 1H), 8.71 (s, 1H), 8.56 (d, J=3.2Hz, 1H), 7.84 (d, J=6.0Hz, 1H), 7.41-7.34 (m, 1H), (7.23-7.21 m, 1H), 7.01 (dd, J=3.2,9.6Hz), 5.23-5.21 (m, 1H), 2.37-0.90 (m, 33H).
The synthesis of embodiment 125 ruthenium complex 13b
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13b, productive rate: 48% after filtration.
After testing, ruthenium complex (13b)
1h-NMR (400MHz, CDCl
3): δ 16.49 (s, 1H), 8.90-8.50 (m, 2H), (7.86 d, J=7.2Hz, 1H), 7.47 (dd, J=2.0,7.2Hz, 1H), 7.33 (m, 1H), (7.27 m, 1H), 7.08 (s, 3H), 6.90 (d, J=1.6Hz, 1H), 6.74-6.72 (m, 1H), (4.87-4.84 m, 1H), 4.19 (s, 4H), 2.48-2.42 (m, 18H), 1.27 (d, J=4.0Hz, 6H).
The synthesis of embodiment 126 ruthenium complex 13d
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13d, productive rate: 42% after filtration.
After testing, ruthenium complex (13d)
1h-NMR (400MHz, CDCl
3): δ 17.33 (s, 1H), 8.55 (m, 4H), 7.71 (m, 1H), (7.50 m, 1H), 7.33-7.28 (m, 4H), 7.02 (m, 1H), 5.23 (m, 1H), 2.34-1.30 (m, 33H).
The synthesis of embodiment 127 ruthenium complex 13e
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13e, productive rate: 95% after filtration.
After testing, ruthenium complex (13e)
1h-NMR (400MHz, CDCl
3): δ 16.56 (s, 1H), 7.47 (dd, J=2.0,7.2Hz, 1H), 7.31-7.27 (m, 5H), 7.20-7.19 (m, 3H), 7.08-6.94 (m, 1H), 6.72 (d, J=6.4Hz, 1H), 4.85-4.81 (m, 1H), 4.18 (s, 3H), 3.85 (s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J=6.0Hz, 6H).
The synthesis of embodiment 128 ruthenium complex 13g
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13g, productive rate: 52% after filtration.
After testing, ruthenium complex (13g)
1h-NMR (400MHz, CDCl
3): δ 16.49 (s, 1H), 8.67 (m, 2H), 7.47 (d, J=5.6Hz, 1H), 7.37 (m, 3H), 7.08 (s, 3H), 6.73 (d, J=6.8Hz, 1H), 4.85-4.83 (m, 1H), 4.19 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H).
The synthesis of embodiment 129 ruthenium complex 13h
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13h, productive rate: 59% after filtration.
After testing, ruthenium complex (13h)
1h-NMR (400MHz, CDCl
3): δ 16.52 (s, 1H), 8.60-8.51 (m, 2H), 7.67 (d, J=8.0Hz, 2H), 7.46 (d, J=2.4Hz, 1H), (7.06 s, 4H), 6.88 (d, J=2.4Hz, 1H), 6.71 (d, J=8.0Hz, 2H), 4.84-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 18H), 1.24 (d, J=4.0Hz, 6H).
The synthesis of embodiment 130 ruthenium complex 13j
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13j, productive rate: 81% after filtration.
After testing, ruthenium complex (13j)
1h-NMR (400MHz, CDCl
3): δ 16.56 (s, 1H), 7.90 (d, J=3.2Hz, 2H), 7.83-7.30 (m, 9H), 7.21 (s, 4H), 6.72 (d, J=7.6Hz, 1H), (4.84-4.82 m, 1H), 4.19 (s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J=4.8Hz, 6H).
The synthesis of embodiment 131 ruthenium complex 13k
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13k, productive rate: 36% after filtration.
After testing, ruthenium complex (13k)
1h-NMR (400MHz, CDCl
3): δ 17.39 (s, 1H), 8.89 (s, 2H), 8.63 (d, J=3.2Hz, 2H), 7.86-6.98 (m, 6H), 6.99 (d, J=4.0Hz, 2H), 5.19 (m, 1H), 2.37-0.89 (m, 39H).
The synthesis of embodiment 132 ruthenium complex 13m
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13m, productive rate: 35% after filtration.
After testing, ruthenium complex (13m)
1h-NMR (400MHz, CDCl
3): δ 17.39 (s, 1H), 8.83 (d, J=15.6Hz, 2H), (8.61 s, 2H), 7.86-7.38 (m, 6H), 7.00 (m, 1H), 5.20 (m, 1H), 2.37-0.89 (m, 39H).
The synthesis of embodiment 133 ruthenium complex 13n
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13n, productive rate: 49% after filtration.
After testing, ruthenium complex (13n)
1h-NMR (400MHz, CDCl
3): δ 16.56 (s, 1H), 8.75 (d, J=3.2Hz, 2H), 8.07-7.47 (m, 8H), 7.21 (s, 4H), 6.72 (d, J=7.6Hz, 1H), (4.84-4.82 m, 1H), 4.19 (s, 4H), 2.69-2.31 (m, 18H), 1.24 (d, J=4.8Hz, 6H).
The synthesis of embodiment 134 ruthenium complex 13p
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13p, productive rate: 52% after filtration.
After testing, ruthenium complex (13p)
1h-NMR (400MHz, CDCl
3): δ 17.39 (s, 1H), 8.85 (s, 2H), 8.57 (d, J=3.2Hz, 2H), 7.85-7.02 (m, 7H), 5.20 (m, 1H), 3.88 (s, 3H), 2.37-0.89 (m, 39H).
The synthesis of embodiment 135 ruthenium complex 13q
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13q, productive rate: 81% after filtration.
After testing, ruthenium complex (13q)
1h-NMR (400MHz, CDCl
3): δ 16.56 (s, 1H), 7.53 (d, J=3.2Hz, 2H), 7.54-7.38 (m, 5H), 7.04-6.72 (m, 8H), 4.84-4.82 (m, 1H), (4.19 s, 3H), 3.80 (s, 4H), 2.69-2.31 (m, 18H), 1.26 (d, J=4.8Hz, 6H).
The synthesis of embodiment 136 ruthenium complex 13r
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13r, productive rate: 37% after filtration.
After testing, ruthenium complex (13r)
1h-NMR (400MHz, CDCl
3): δ 18.67 (s, 1H), 8.40 (m, 1H), 7.47-6.91 (m, 13H), 6.58 (m, 1H), 4.12 (m, 6H), (2.63-2.27 m, 19H), 1.00 (d, J=4.0Hz, 6H).
The synthesis of embodiment 137 ruthenium complex 13s
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13s, productive rate: 73% after filtration.
After testing,
1h-NMR (400MHz, CDCl
3): δ 18.67 (s, 1H), 8.43 (s, 1H), 7.45-7.35 (m, 3H), (7.19-6.93 m, 10H), 6.60 (d, J=7.6Hz, 1H), 4.15 (m, 6H), 2.52-2.28 (m, 19H), (1.08-0.89 m, 6H).
The synthesis of embodiment 138 ruthenium complex 13t
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13t, productive rate: 55% after filtration.
After testing, ruthenium complex (13t)
1h-NMR (400MHz, CDCl
3): δ 18.69 (s, 1H), 8.42 (s, 2H), 7.44-6.93 (m, 15H), 6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), (2.52-2.27 m, 18H), 0.98 (d, J=4.4Hz, 6H).
The synthesis of embodiment 139 ruthenium complex 13u
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13u, productive rate: 63% after filtration.
After testing, ruthenium complex (13u)
1h-NMR (400MHz, CDCl
3): δ 18.69 (s, 1H), 8.42 (s, 2H), 7.62-6.93 (m, 16H), 6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), (2.52-2.27 m, 18H), 0.98 (d, J=4.4Hz, 6H).
The synthesis of embodiment 140 ruthenium complex 13v
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13v, productive rate: 90% after filtration.
After testing,
1h-NMR (400MHz, CDCl
3): δ 18.69 (s, 1H), 8.42 (s, 2H), (7.86-6.93 m, 15H), 6.60 (dd, J=2.0,7.6Hz, 2H), (4.14 s, 6H), 3.87 (s, 3H), 2.52-2.27 (m, 18H), 0.98 (d, J=4.4Hz, 6H).
The synthesis of embodiment 141 ruthenium complex 13w
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13w, productive rate: 49% after filtration.
After testing, ruthenium complex (13w)
1h-NMR (400MHz, CDCl
3): δ 18.67 (s, 1H), 8.40 (m, 1H), 7.69-6.90 (m, 13H), 6.60 (m, 1H), 4.12 (m, 6H), (2.62-2.17 m, 19H), 1.00 (d, J=4.0Hz, 6H).
The synthesis of embodiment 142 ruthenium complex 13x
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13x, productive rate: 97% after filtration.
After testing, ruthenium complex (13x)
1h-NMR (400MHz, CDCl
3): δ 16.57 (s, 1H), 7.63-6.69 (m, 11H), 4.83-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 21H), 1.24 (d, J=4.0Hz, 6H).
The synthesis of embodiment 143 ruthenium complex 13y
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13y, productive rate: 81% after filtration.
After testing, ruthenium complex (13y)
1h-NMR (400MHz, CDCl
3): δ 16.85 (s, 1H), 8.40-6.83 (m, 15H), 4.95 (m, 1H), 4.16 (s, 3H), 3.80 (s, 4H), (2.46-2.23 m, 18H), 1.29 (d, J=4.4Hz, 6H).
The synthesis of embodiment 144 ruthenium complex 13z
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13z, productive rate: 78% after filtration.
After testing, ruthenium complex (13z)
1h-NMR (400MHz, CDCl
3): δ 16.85 (s, 1H), 8.42-7.07 (m, 15H), 4.95 (m, 1H), 4.19 (s, 4H), 2.45-2.29 (m, 18H), 1.29 (d, J=4.4Hz, 6H).
The synthesis of embodiment 145 ruthenium complex 13aa
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13aa, productive rate: 85% after filtration.
After testing, ruthenium complex (13aa)
1h-NMR (400MHz, CDCl
3): δ 16.85 (s, 1H), 8.47-6.85 (m, 16H), 4.94 (m, 1H), 4.19 (s, 4H), 2.40-2.29 (m, 18H), 1.29 (d, J=4.4Hz, 6H).
The synthesis of embodiment 146 ruthenium complex 13ab
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13ab, productive rate: 96% after filtration.
After testing, ruthenium complex (13ab)
1h-NMR (400MHz, CDCl
3): δ 17.00 (s, 1H), 8.47-6.82 (m, 11H), 4.90 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H).
The synthesis of embodiment 147 ruthenium complex 13ac
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13ac, productive rate: 95% after filtration.
After testing, ruthenium complex (13ac)
1h-NMR (400MHz, CDCl
3): δ 17.00 (s, 1H), 8.47-6.83 (m, 11H), 4.91 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H).
The synthesis of embodiment 148 ruthenium complex 13ad
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13ad, productive rate: 33% after filtration.
After testing, ruthenium complex (13ad)
1h-NMR (400MHz, CDCl
3): δ 18.65 (s, 1H), 8.56 (s, 1H), 7.84-6.40 (m, 15H), 4.22 (s, 4H), 3.80 (s, 3H), 2.49-2.29 (m, 18H).
The synthesis of embodiment 149 ruthenium complex 13ae
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13ae, productive rate: 68% after filtration.
After testing, ruthenium complex (13ae)
1h-NMR (400MHz, CDCl
3): δ 18.65 (s, 1H), 8.53 (s, 1H), 7.84-6.00 (m, 19H), 4.14 (s, 4H), 3.86 (s, 3H), 3.80 (s, 3H), 2.49-2.29 (m, 18H).
The synthesis of embodiment 150 ruthenium complex 13af
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13af, productive rate: 59% after filtration.
After testing, ruthenium complex (13af)
1h-NMR (400MHz, CDCl
3): δ 18.65 (s, 1H), 8.56 (s, 1H), 7.51-6.39 (m, 19H), 4.14 (s, 4H), 3.80 (s, 3H), 2.42-2.29 (m, 18H).
The synthesis of embodiment 151 ruthenium complex 13ag
Add ruthenium complex (0.1g) after a 25mL two mouthfuls of flask argon replaces, by argon replaces three times afterwards with argon gas ball protection enclosed system, then the pyridine (1mL) adding replacement was room temperature reaction 0.5 hour.Reaction terminates, and adds Skellysolve A (-10 DEG C, 20mL), obtains greenish yellow solid product 13ag, productive rate: 69% after filtration.
After testing, ruthenium complex (13ag)
1h-NMR (400MHz, CDCl
3): δ 18.65 (s, 1H), 8.56 (s, 1H), 7.50-6.39 (m, 20H), 4.14 (s, 4H), 3.80 (s, 3H), 2.42-2.29 (m, 18H).
For fully effectively optimizing the synthetic method of all kinds of ruthenium catalyst, reduce costs and resource consumption, the present invention have employed different synthetic routes to a few class ruthenium catalyst.When generating Cabbeen intermediate under the effect of raw material 4-SM at sodium ethylate, more directly and RuCl
2(PPh
3)
3reaction generates unstable ruthenium complex intermediate 4-1; The triphenyl phosphorus part of intermediate 4-1 can by another part PCy
3(4-2) stable ruthenium complex 4bf is generated.Ruthenium complex intermediate 4-1 or 4bf and part H
2iMes (4-3) directly replaces and generates the more stable and ruthenium catalyst 4be that catalytic activity is higher.Ruthenium complex 4be and part 4-chloropyridine (4-4) react direct complexing and generate 13s:
Be below an easy synthetic route of ruthenium complex intermediate 4-1, ruthenium catalyst 4be, 4bf and 13s:
The synthesis of embodiment 152 ruthenium complex 4bf
Ligand stock 4-SM (33g is added successively after a 500mL there-necked flask argon replaces, 100mmol, 1.0eq.) be dissolved in 300mL ethanol, add rapidly NaOEt (400mmol under stirring, 4.0eq.), be heated to 60 DEG C and react half an hour.120mL water is added again, with extraction into heptane (200mL × 3) after 30 minutes.Combining extraction liquid, with saturated sodium carbonate solution washing (150mL × 2), saturated common salt water washing (150mL × 2), is concentrated into about 50mL at 0 DEG C after anhydrous sodium sulfate drying.Productive rate calculates next step reaction by 50% and feeds intake.
By RuCl
2(PPh
3)
3(29g, 20mmol) is dissolved in 250mL methylene dichloride, is cooled to-78 DEG C, then adds the above-mentioned diazonium pentane solution (~ 60mL) of-70 DEG C.After 5 minutes, temperature of reaction slowly rises to room temperature, adds CuCl (14.7g, 100mmol).After 15 minutes, filter.After filtrate is concentrated, column chromatography purification, with gradient elution agent (2: 1 normal hexanes/methylene dichloride is to absolute dichloromethane).Concentrated by product section, n-hexane, vacuum-drying obtains the ruthenium complex intermediate 4-1 of 12.3g instability.
Intermediate 4-1 (15.0mmol) is dissolved in methylene dichloride (30mL), then adds three rings phosphorus (PCy
3, 30mmol, 2.0eq.), after reacting half an hour at 20 DEG C, obtain dark green solid with after chromatography column separation and purification product, obtain green solid product 4bf with after methyl alcohol and n-hexane drying, thick productive rate: 53%.Product 4bf is not very stable, is difficult to purification assays ruthenium complex 4bf's
1h-NMR structure, but its impure ruthenium complex 4bf can be directly used in preparation 4be or the reaction of olefin metathesis metathesis catalysis.
The synthesis of embodiment 153 ruthenium complex 4be
Ruthenium complex 4bf (5.0mmol) and H is added successively after a 50mL two mouthfuls of flask argon replaces
2iMes (H) (CCl
3) (4-3; 10.0mmol; what 2.0eq.) be dissolved in 30mL drying is dissolved in toluene; enclosed system is protected with argon gas ball afterwards three times again by argon replaces; be heated to 80 DEG C, reaction in 1.5 hours terminates rear crystallisation by cooling and filters, and obtains dark green solid thick product after adding silica gel column chromatography after filtering in filtrate; then stable green solid product 4be is obtained, productive rate: 59% with methyl alcohol or pentane-DCM washing.
After testing, ruthenium complex (4be)
1h-NMR (400MHz, CDCl
3): δ 18.88 (s, 1H, Ru=CH), 7.57-6.44 (m, 11H, aromatic H), 5.36 (t, J=13.2Hz, 1H, NH), 4.16-4.02 (m, 5H, NCH
2, NCH
2cH
2n), 4.01 (d, J=13.2Hz, 1H, NCH
2), 2.75-2.00 (m, 19H, CH (CH
3)
2, aromatic CH
3), 1.01-0.90 (m, 6H, CH (CH3)
2).
The preparation of ruthenium complex 13s is reacted direct complexing by above-mentioned ruthenium complex 4be and part 4-chloropyridine (4-4) and is formed, about the synthesis of the ruthenium complex 13s described in preparation experiment and analytical results detailed in Example 137.
The Application Example of ruthenium complex catalyst in olefin metathesis metathesis cyclization:
Be below the present inventor representational complex compound 14a, 14b before making the present invention in another patent delivered (US20070043180A1) and the structural formula of other four representational catalyzer 14c, 14d, 14e, 14f:
Some ruthenium complex catalysts in these ruthenium catalysts (14a-14f) and the present invention prepare the test of the high molecular polymer novel material of difference in functionality selectively for the catalytic cyclization reaction of following cycloolefin and ring-opening polymerization, and the catalytic effect of the roughly the same catalyzer listed with the present invention contrasts and discusses.
Ruthenium complex catalysed olefin metathesis reaction experimental procedure: the substrate of 50mg is placed in 25mL bis-mouthfuls of round-bottomed flasks, with the catalyzer adding methylene dichloride that 1mL newly steams and 5mg after argon replaces 5 times.Under argon shield, reaction mixture is at room temperature stirred to and reacts completely.The transformation efficiency of reaction is monitored by HPLC and is obtained.Below the catalytic activity research of ruthenium complex in the transposition replacement(metathesis)reaction of different alkene:
Effect example 1:
In order to contrast the catalytic activity of the ruthenium complex containing different substituents, catalytic activity and the relative catalytic activity of the existing different ruthenium complex replacement(metathesis)reactions to embodiment synthesis compare.
Metathesis cyclization reaction experiment in olefin hydrocarbon molecules: add 50mg reaction substrate 15 respectively in 25ml bis-neck bottle, inside is made to be full of argon gas with threeway displacement, 1.0ml methylene dichloride is added with syringe, after stirring at room temperature makes to dissolve completely, add the above-mentioned ruthenium complex catalyst (4a-4cz of 2mol% respectively, 6a-6z, 8a-8t, 10a-10j).Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr sampling, follow the tracks of reaction with HPLC and LC-MS.Calculate the transformation efficiency of product by normalized method, reaction result is in table 2.
Olefin metathesis metathesis cyclisation product (16)
1hNMR (400MHz, CDCl
3): δ=7.78 (d, 2H, J=8.21Hz), 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H). molecular weight (M+H
+): m/z calculated value is 300.1, and test value is 300.2.
The Activity Assessment of the Intra-molecular condensation catalyzer 4a-4cz of table 1-1. alkene 15
Except more than ten new catalyst listed in above-mentioned table 1-1 has good activity in ruthenium catalyst 4a-4cz, the activity of the ruthenium catalyst listed by all the other is poor, and the catalytic activity of substituting group electronic effect on the ruthenium complex that it is formed of Novel Ligands has as can be seen here affects very significantly.
The Activity Assessment of the Intra-molecular condensation catalyzer 6a-6z of table 1-2. alkene 15
Except 6s, 6t and 6v tri-new catalysts listed in above-mentioned table 1-2 have good activity in ruthenium catalyst 6a-6z, catalytic activity is obviously better than the similar catalyzer 14f that oneself knows.The activity of remaining ruthenium catalyst is very poor, and the catalytic activity of substituting group electronic effect on the ruthenium complex that it is formed of Novel Ligands has as can be seen here affects very significantly.
The Activity Assessment of the Intra-molecular condensation catalyzer 8a-8t of table 1-3. alkene 15
Except 8c, 8e and 8h tri-new catalysts listed in above-mentioned table 1-3 have good activity in ruthenium catalyst 8a-8t, catalytic activity is obviously better than the similar catalyzer 14d that oneself knows.The activity of the ruthenium catalyst listed by all the other is poor, and the catalytic activity of substituting group electronic effect on the ruthenium complex that it is formed of Novel Ligands has as can be seen here affects very significantly.
The Activity Assessment of the Intra-molecular condensation catalyzer 10a-10j of table 1-4. alkene 15
Except 10c, 10d, 10e, 10f and 10g five new catalysts listed in above-mentioned table 1-4 have good activity in ruthenium catalyst 10a-10j, catalytic activity is obviously better than the similar catalyzer 14e that oneself knows.The activity of remaining ruthenium catalyst is poor, and the catalytic activity of substituting group electronic effect on the ruthenium complex that it is formed of Novel Ligands has as can be seen here affects very significantly.
The Activity Assessment of the Intra-molecular condensation catalyzer 13a-13ag of table 1-5. alkene 15
Except four new catalysts listed in above-mentioned table 1-5 have poor activity in ruthenium catalyst 13a-13ag, the cyclisation activity of remaining ruthenium catalyst is very poor, and the catalytic activity of substituting group electronic effect on the ruthenium complex that it is formed of Novel Ligands has as can be seen here affects very significantly.But wherein some catalyzer 13a-13ag can be effective to cycloolefin ring-opening polymerization.
Several catalyzer having better activity except listing in above-mentioned each table in above-mentioned all kinds of New Ruthenium catalyzer, the cyclization (RCM) of all the other ruthenium catalysts prepared is active very poor, result shows novel complex ligands phenyl ring does not have substituent ruthenium complex (14f) and have the catalytic activity of substituent ruthenium complex (as 6g and 6m) very low, cannot cause the catalytic cyclization reaction (RCM) of alkene.In the present invention, the novel catalytic activity of substituting group electronic effect on the ruthenium complex that it is formed containing oxygen or nitrogen ligating atom part has and affects very significantly as can be seen here.Table 1-1,1-2,1-3,1-4,1-5 result shows, the specific activity of all kinds of new catalyst 4c, 4g, 4t, 4u, 4w, 4x, 4aa, 4ab, 4cf, 6s, 6u, 8c, 8e, 8h, 8k, 10c, 10d, 10e, 10f, 10g of the present invention to alkene 15 is better, ring closure reaction major part terminates in 1.5-3hr, is catalytic activity reasonable new olefin metathesis cyclization catalyzer in this field current.
Effect example 2:
In order to contrast the catalytic activity of all kinds of ruthenium complex containing different substituents, existing catalytic activity and relative catalytic activity to there being better active ruthenium complex catalyst in above-described embodiment compares.
Olefin hydrocarbon molecules intramolecular cyclization reaction is tested: in 25ml bis-neck bottle, add 50mg reaction substrate 17 respectively, inside is made to be full of argon gas with threeway displacement, add 1.0ml methylene dichloride with syringe, after stirring at room temperature makes to dissolve completely, add the good ruthenium complex catalyst of above-mentioned specific activity of 2mol% respectively.Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr sampling, follow the tracks of reaction with HPLC and LC-MS.Calculate the transformation efficiency of product by normalized method, reaction result is in table 2.
Olefin metathesis metathesis cyclisation product (12)
1hNMR (400MHz, CDCl
3): δ=7.78 (d, 2H, J=8.21Hz), 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H). molecular weight (M+H
+): m/z calculated value is 300.1, and test value is 300.2.
The Activity Assessment of all kinds of catalyzer of Intra-molecular condensation of table 2. alkene 17
Table 2 result shows, the specific activity of all kinds of new catalyst 4c, 4t, 4x, 4af, 6s, 8e, 10d of the present invention to alkene 17 is better, ring closure reaction major part terminates in 1.5-3hr, is catalytic activity reasonable new olefin metathesis cyclization catalyzer in this field current.
Effect example 3:
In order to measure the difference between different high activated catalyst better, this patent devises on existing two electrophilic fluoro, alkene again two methyl substituted substrates 19, and substrate 19 imitates the difficult characteristic that transposition metathesis cyclisation occurs makes the activity difference between catalyzer (11a-j) measure out obviously.
Metathesis cyclization reaction experiment in olefin hydrocarbon molecules: add 50mg reaction substrate Multi substituted benzenes Vinyl Ether alkene 19 in 25ml bis-neck bottle respectively, inside is made to be full of argon gas with threeway displacement, 1.0ml methylene dichloride is added with syringe, after stirring at room temperature makes to dissolve completely, add the above-mentioned ruthenium complex catalyst (12a-12h) of 3mol% respectively.Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr sampling, follow the tracks of reaction with HPLC and LC-MS.Calculate the transformation efficiency of product by normalized method, dependent dynamics the results are shown in table 3.
Olefin metathesis metathesis cyclisation product (20)
1hNMR (CDCl
3: δ=7.26ppm): 7.15 (d, 1H, J=2.74Hz), 6.84 (d, 1H, J=2.34Hz), 6.34 (dt, 1H, J=1.95,9.78Hz), (5.86 d, 1H, J=9.78Hz), 4.95 (m, 2H).Molecular weight (M+H
+): m/z calculated value is 200.99, and test value is 201.1.
The Intra-molecular condensation catalytic activity assessment of table 3. alkene 19
Table 3 result shows, the activity of new catalyst 12a, 12b, 12d, 12e, 12g, 12h of the present invention to alkene 19 is fine, ring closure reaction major part terminated in 30 minutes, was the class new olefin metathesis cyclization catalyzer that in this catalytic cyclization field current, catalytic activity is best.
The Application Example of ruthenium complex catalyst in alkene ring-opening polymerization:
In order to research and develop the mechanical property of more effective alkene ring-opening polymerization catalyst and high molecular polymer novel material thereof further, measure the difference between different high activated catalyst better, research and develop contrast by the effect example 4-7 of following alkene ring-opening polymerization and improve the mechanical propertys such as the strength and modulus of olefin metathesis reaction catalyzer and high molecular polymer product.
Effect example 4:
Method one; Alkene ring-opening polymerization experiment (in solvent catalyzed polymerization): cyclooctene (21) raw material monomer is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after polymer solids product (22), productive rate is 70%-98%.
Method two; Alkene ring-opening polymerization experiment (solvent-free catalyzed polymerization): pass into argon gas and rush oxygen in liquid ring octene monomers (21), add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, between 20-120 degree, after reacting by heating several minutes, reaction solution becomes sticky thick heat release gradually, and finally polymerization obtains open loop high molecular polymer solid product (22).
Result shows, new catalyst 8c, 8d, 4j, 4m, 4p, 4r, 4c, 8c, 8e of the present invention specific activity to cyclooctene (21) polyreaction is better, catalytic polymerate (22) has good tensile strength and modulus (>1.5Gpa), is catalytic activity reasonable new olefin metathesis polymerization catalysts in this field current.Open loop high molecular polymer (22) heating energy melts and is dissolved in weak polar solvent (as sherwood oil, paraffin wet goods), and processing can be used for explosion-proof lamp or the spinning processing high-strength products of preparing high strength further.
Effect example 5:
Method one; Alkene ring-opening polymerization experiment (in solvent catalyzed polymerization): norbornylene (23) raw material monomer is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after polynorbornene solid product (24), productive rate is 75%-98%.
Method two; Alkene ring-opening polymerization experiment (solvent-free catalyzed polymerization): pass into argon gas and rush oxygen in liquid norbornene monomer (23), add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, between 25-100 DEG C, after reacting by heating several minutes, reaction solution becomes sticky thick heat release gradually, finally obtains polynorbornene solid product (24).
Result shows, new catalyst 4c, 4h, 4j, 4m, 4p, 4r, 8c, 8d, 8e of the present invention specific activity to norbornylene (23) is better, catalytic polymerization terminates in 10-60min, polynorbornene product (24) has good intensity, hardness and tensile modulus, is catalytic activity reasonable new olefin metathesis polymerization catalysts in this field current.Open loop high molecular polymer (24) further processing can be used for explosion-proof lamp or the spinning material of preparing high strength.
Effect example 6:
Method one; Alkene ring-opening polymerization experiment (in solvent catalyzed polymerization): by luxuriant for dicyclo diene (DCPD, 25) raw material monomer is dissolved in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, and alcohol immersion, suction filtration must gather the luxuriant diene of dicyclo (Poly-DCPD) solid product (26) after drying, and productive rate is 75%-98%.
Method two; Alkene ring-opening polymerization experiment (solvent-free catalyzed polymerization): at the luxuriant diene monomers (DCPD of liquid dicyclo, 25) pass into argon gas in rush oxygen, add the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out again fast, between 30-120 degree, after reacting by heating several minutes, reaction solution becomes sticky thick heat release gradually, and finally polymerization obtains the luxuriant diene of poly-dicyclo (Poly-DCPD) polymeric solid product (26).
Catalytic result shows, new catalyst 4c, 4h, 4j, 4m, 4p, 4am, 4be, 4bg, 4bx, 4cg, 8a, 8b, 8c, 8d, 8e, 8h, 8q of the present invention are better to the polymerization catalytic activity of alkene DCPD (25), are homogeneous catalysis specific activity good new olefin metathesis polymerization catalysts in this field current.Polyreaction is carried out better at 40-60 DEG C, and under differential responses condition, catalytic polymerization terminates in 10-60min.Especially use 4c, 4am, 4be, 4cg or and the luxuriant diene product of poly-dicyclo (26) that obtains of the new catalyst polyreaction such as 8h there is good intensity, hardness and modulus in flexure.
Polymkeric substance (26) the performance test results shows, Poly-DCPD solid polymer prepared by solvent-free catalyzed polymerization has good hardness (>80Gpa), modulus in flexure (>20Gpa) and heat-drawn wire (>200 DEG C), main performance index is better than same dicyclo of birdsing of the same feather flock together luxuriant diene (Poly-DCPD) product of Materia company of the current U.S. and Nippon Zeon.The multipolymers such as the antioxidant of interpolation a small amount of (0.1-5%) during catalyzed polymerization or linking agent can improve the poly-luxuriant diene product of dicyclo (26) physicals such as hardness and modulus, make the luxuriant diene of poly-dicyclo (26) product of different high strength, high rigidity, low temperature resistant, acid and alkali-resistance from now on by injection moulding complete processing (ROMP-RIM), in industry and life, tool has been widely used.
Effect example 7:
Alkene ring-opening polymerization is tested: be dissolved in by olefinic monomer (27) raw material in the anhydrous solvent (as ethylene dichloride DCE) of 15 times amount (15x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after white polymer solid product (28), productive rate is 80-98%.Open loop high molecular polymer (28) further processing can be used for the spinning material preparing high strength.
Effect example 8:
" Linker " is the group of shack olefinic monomer and functional group " G ", includes but not limited to O, S, C
1-C
15saturated or undersaturated alkyl, substituted or unsubstituted C
1-C
15amido, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
1-C
15heterocyclic oxy group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
6-C
15arylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, methanoyl, formamido-, substituted or unsubstituted C
1-C
15alkyl carbonyloxy, substituted or unsubstituted C
1-C
15alkyl amido, substituted or unsubstituted C
6-C
15arylcarbonyloxy, substituted or unsubstituted C
6-C
15aryl carboxamides base;
" G " is the compound with property or purposes, as the small molecule liquid crystal (29d, 29e, 29f) that can be connected with " Linker " and small-molecule drug (29g, " G " is medicine " Lipitor ") etc. material, generate after the monomer ring-opening polymerization of connection have specific characteristics can or the prodrug (30g) of purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix.
Following is the structure of high molecular polymer (30) of the catalyzed ring opening polymerization reaction preparation of cycloolefin:
Alkene ring-opening polymerization is tested: be dissolved in by olefinic monomer raw material (29) in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after polymer solids product (30), productive rate is 80%-98%.
Relevant good polymerization results is summed up and is listed as follows (table 4):
Table 4 result shows, can be polymerized under the New Ruthenium catalyst action that small molecule liquid crystal or medicine monomer go out in this project screening generation have specific characteristics can or the prodrug (30g) of purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix.Active testing result shows, new catalyst 4a, 4c, 4e, 4g, 6e, 6e and 13a of the present invention specific activity to olefinic monomer (29a-g) is better, polyreaction terminates in 5-15hr, and under the catalyzed polymerization condition optimized, productive rate is higher than 90%.Polymerization test result shows, ruthenium catalyst dissimilar in the present invention is solvent-free and have under solvent condition and have obvious difference to the catalytic activity of different monomers polymerization, especially some New Ruthenium catalyzer (as 4a, 6e) catalytic activity in cyclization is very low, but in polyreaction, then there is good catalytic activity in a solvent, in cyclisation (RCM) and the reaction of ring-opening polymerization (ROMP) two class, demonstrate good selectivity and catalytic activity thus.
Effect example 9:
Alkene ring-opening polymerization is tested: be dissolved in by olefinic monomer raw material in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add ruthenium catalyst (4a or 6e that this project etc. filters out again fast, 0.1 ‰-5%), react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after polymer solids, productive rate is 60%-98%.
Following is the structure of high molecular polymer 32 (VIc) of the catalyzed ring opening polymerization reaction preparation of cycloolefin:
Relevant good polymerization results is summed up and is listed as follows (table 5):
Table 5 result shows, the high molecular polymer that generation has higher-strength and modulus can be polymerized containing under the New Ruthenium catalyst action that the small molecule monomer (31a-31s) of difference in functionality group goes out in this project screening, the modulus of wherein testing after polymkeric substance 32a, 32b, 32n, 32q processing film forming and tensile strength are respectively 0.5-3.0Gpa and 20-40MPa, can be used for spinning processing.
Effect example 10:
Alkene ring-opening polymerization is tested: be dissolved in by olefinic monomer raw material 33 (VIIa) in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after polymer solids, productive rate is about 60%-98%.
Following be cycloolefin catalyzed ring opening polymerization reaction preparation high molecular polymer 34 (VIIc) structure:
Relevant good polymerization results is summed up and is listed as follows (table 6):
Table 6 result shows, the high molecular polymer (34) that generation has higher-strength and modulus can be polymerized containing under the New Ruthenium catalyst action that the small molecule monomer (33a-33s) of difference in functionality group goes out in this project screening, wherein polymkeric substance 34a, 34b, 34c, 34v, 34w, the modulus that 34x tests after processing film forming and tensile strength are respectively 1.0-16Gpa and 30-50MPa, wherein polymkeric substance 34c and 34x (modulus of film forming test is up to 16Gpa) is more suitable for spinning processing high-strength products, it is the family macromolecule polymer architecture that in the product obtained by alkene ring-opening polymerization (ROMP) at present, modulus is best.
Effect example 11:
Alkene ring-opening polymerization is tested: be dissolved in by olefinic monomer raw material 35 (VIIb) in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after polymer solids 36 (VIId), productive rate is about 85-98%.
Following be cycloolefin catalyzed ring opening polymerization reaction preparation high molecular polymer (VIId) structure:
Test result shows, modulus and the tensile strength of polymkeric substance 36a-36d are lower, are less than 0.5GPa and 10MPa respectively, and processing characteristics is not as 34c and 34x.
Effect example 12:
Two or more cycloolefin monomers raw materials (as 21,23,25,27,29,31,33 or 35) mixing in above-mentioned effect example 5-11 is dissolved in anhydrous solvent (as ethylene dichloride DCE), add the New Ruthenium catalyzer reacting by heating that this project screening goes out again, can prepare the high-molecular copolymer of different performance, concrete copolyreaction is as follows:
Alkene ring-opening polymerization is tested: be dissolved in by two or more cycloolefin monomers raw materials in the anhydrous solvent (as ethylene dichloride DCE) of 20 times amount (20x), oxygen caught up with by argon filling, add the ruthenium catalyst (0.1 ‰-5%) that this project etc. filters out again fast, react (20-75 DEG C) reacting by heating that preferably progressively heats up, reaction solution becomes sticky thick gradually.Reaction solution slowly to be toppled over after spending the night and is precipitated out in ethanol by reaction, alcohol immersion, suction filtration dry after polymer solids, productive rate is about 65%-98%.
Two or more cycloolefin monomers above-mentioned can prepare different high-molecular copolymer novel materials by copolyreaction under some catalyst actions of this Project-developing, about the structure of each analog copolymer is as follows:
Test result shows, the modulus that polymkeric substance 37j and 37u tests after processing film forming and tensile strength are respectively 2.0-10Gpa and 40-70MPa, can be used for film forming or spinning processing high-strength products.
Above-mentioned effect example 7-11 result shows, the class ROMP polymer architecture that in the structure product that to be the high molecular polymer (film forming modulus is up to 16Gpa) of 34c and 34x be is obtained by alkene ring-opening polymerization (ROMP) at present, modulus is best.Catalyzer 4a and 6e has good activity and selectivity.
Below the instrument related in embodiment and raw material are described as follows:
Ir data is the Fourier Transform AVATAR adopting Thermo Nicolet company
tM360E.S.P
tMradar stealthy materials analysis obtains, with cm
-1for unit represents.
Proton nmr spectra is that the analysis of Varian Mercury Plus 400 (400MHz) nuclear magnetic resonance spectrometer obtains.Chemical shift is that interior mark carrys out record with tetramethylsilane, in units of ppm, represent (CHCl
3: δ=7.26ppm).The data message of record is as follows: chemical shift and splitting point and coupling constant (s: singlet; D: doublet; T: triplet; Q: quartet; Br: broad peak; M: multiplet).
Mass-spectrometric data except other need, all adopts Finnigan Finnigan LCQ Advantage LC-MS instrument to analyze, respond all dry argon gas protect anhydrous and oxygen-free condition under operate.Solid metal-organic compound is stored in argon shield loft drier.
All column chromatography silica gel (200-300 order) is bought from Haiyang Chemical Plant, Qingdao.
Tetrahydrofuran (THF) and ether are through distillation and obtain, and add sodium Metal 99.5 and benzophenone wherein during distillation.Methylene dichloride, pentane and hexane process with hydrolith.Cl
2ru=CHPh (PCy
3) (H
2iMes) (Jason S.Kingsbury, Joseph P.A.Harrity, Peter J.Bonitatebus, Jr., Amir H.Hoveyda*, J.Am.Chem.Soc.1999,121,791 are prepared according to document; American Chemical Society's magazine 121 volume in 1999 791 pages).Other all chemical reagent are bought from Shanghai Reagent Company.
Claims (28)
1. structural formula is the metal complex of formula IIb:
Wherein, M is metal Ru, tungsten or nickel;
L is a kind of to the complex ligands of electronics;
L
1and L
2be halogen, RCOO independently
-or ArO
-negatively charged ion;
L
3for a kind of complex ligands giving electronics;
M=0 or 1, n=0 or 1; During n=0, p=0 or 1; During n=1, p=0;
During n=1, X
1for oxygen, CH
2, substituted or unsubstituted C
6-C
12aryl; Y
1for oxygen, nitrogen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imino-; Wherein, X
1the parent that each group represented connects is Y
1, Y
1the parent that each group represented connects is X
1;
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imido grpup or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; In formula IIb, the parent that the group that Y represents connects is aromatic ring;
During m=1, X is nitrogen, oxygen, methyne, methylene radical, carbonyl; Y is nitrogen, oxygen, substituted or unsubstituted C
6-C
12aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is the parent of the group connection that Y, Y represent is X;
between be singly-bound or double bond;
R
1for hydrogen or substituted or unsubstituted C
6-C
12aryl;
R
2for methyl, sec.-propyl, substituted or unsubstituted C
1-C
8alkyl or substituted or unsubstituted C
6-C
12aryl;
E is hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, connection C
1-C
8the carbonyl of alkyl, connection C
1-C
8the carbonyl of alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, connection C
1-C
8the carbonyl of alkylamino, connection C
6-C
12the carbonyl of arylamino, connection C
2-C
12the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
8the alkylsulfonyl of alkyl amine group; Or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
2for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, C
2-C
12heterocyclic aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, substituted or unsubstituted C
1-C
8alkyl, formyl radical, substituted or unsubstituted C
1-C
8alkyl formyl radical, substituted or unsubstituted C
6-C
12aryl formyl radical; Or Rc, Rd and atom N connect into ring.
2. metal complex according to claim 1, is characterized in that: in formula IIb,
N=0 or 1;
During n=1, X
1for CH
2or phenyl; Y
1for oxygen or carbonyl;
During m=0, Y is C
1-C
4alkylamino or C
1-C
3alkoxyl group;
During m=1, X is carbonyl, CH
2, CH or phenmethyl; Y be nitrogen, NH,
c
1-C
4alkoxyl group, C
5heterocyclic oxy group or C
1-C
3alkane siloxy; X and Y is singly-bound or double bond;
R
1for the phenyl that hydrogen, phenyl or nitro replace;
R
2for C
1-C
3alkyl or C
1-C
3alkoxyl group;
E is halogen, nitro, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, C
1-C
8alkyl amino sulfonyl, C
6-C
12n-aryl sulfonyl;
E
1and E
2for hydrogen, halogen, C independently
1-C
4alkyl or C
1-C
4alkoxyl group; E
3for hydrogen.
3. metal complex according to claim 1, is characterized in that: the structural formula of described L is following formula III a, III b, III c or III d:
Wherein, R
4and R
5be C independently
1-C
20alkyl, C
6-C
20aryl, C
1-C
20heterocyclic radical, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, formamido-, C
1-C
20alkyl amido, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, sulfoamido or C
1-C
20alkylsulfonamido;
R
6and R
7be hydrogen, C independently
1-C
20alkyl, C
1-C
20alkoxyl group, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
6-C
20aryl, C
6-C
20aryloxy, C
2-C
20heterocyclic radical, sulfoxide group, sulfuryl, aldehyde radical, connection C
1-C
20the carbonyl of alkyl, connection C
1-C
20the carbonyl of alkoxyl group, formamido-, C
1-C
20alkyl amido, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, sulfoamido, C
1-C
20alkylsulfonamido, halogen, nitro or itrile group;
R
8and R
9be substituted or unsubstituted C independently
1-C
20alkyl, C
1-C
20alkoxyl group, C
6-C
20aryl, C
6-C
20aryloxy or C
2-C
20heterocyclic radical.
4. metal complex according to claim 3, is characterized in that: in described formula III a, R
4and R
5be aryl; R
6and R
7be hydrogen.
5. metal complex according to claim 3, is characterized in that: the structural formula of described L is formula III a, wherein R
4and R
5be mesityl, R
6and R
7be hydrogen; Or be formula III d, wherein R
8and R
9be cyclohexyl.
6. the metal complex according to any one of claim 1-5, is characterized in that: in formula IIb,
Metal M is ruthenium;
M=0 or 1, n=0 or 1;
L
1and L
2be chlorion;
L is III a or III d; Wherein, R
4, R
5, R
6, R
7, R
8and R
9identical with the definition in any one of claim 1-5;
During n=0, p=0 or 1;
During p=1, L
3for the one or more pyridyl be substituted in ortho position, a position and contraposition, the nitrogen-atoms of pyridyl connects parent, and between pyridyl, the substituting group of position and contraposition is independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkyl siloxy, C
6-C
15aryloxy, C
1-C
15alkyl amine group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, C
1-C
15alkyl amido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, sulfoamido or C
1-C
15alkylsulfonamido;
During n=1, p=0, X
1and Y
1be nitrogen, oxygen, sulphur, CH independently
2, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
15alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; X
1the parent that each group represented connects is Y
1, Y
1the parent that each group represented connects is X
1;
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
15alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; In formula Ib, the parent that the group that Y represents connects is aromatic ring;
During m=1, X is nitrogen, oxygen, sulphur, CH, CH
2, carbonyl; Y is nitrogen, oxygen, CH, methylene radical, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
1-C
15imido grpup; Such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
15aryl, substituted or unsubstituted C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is the parent of the group connection that Y, Y represent is X;
between be singly-bound or double bond;
R
1for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy or substituted or unsubstituted C
2-C
15heterocyclic radical;
R
2for hydrogen, substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, substituted or unsubstituted C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, aldehyde radical, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, formyl radical, substituted or unsubstituted C independently
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical or substituted or unsubstituted C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, connection C
1-C
15the carbonyl of alkyl, connection C
6-C
15the carbonyl of aryl, connection C
2-C
15the carbonyl of heterocyclic radical, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, connection C
6-C
15the carbonyl of arylamino, connection C
2-C
15the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
20heterocyclic radical, C
1-C
20alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, C
1-C
15alkyl sulphonyl, C
6-C
20aryl sulfonyl or C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, sulfuryl, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
2-C
15heterocyclic radical, C
6-C
15aryl, C
6-C
15aryloxy, aldehyde radical, connection C
1-C
15the carbonyl of alkyl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, substituted or unsubstituted C
1-C
15alkyl, connection C
1-C
15amino alkylsulfonyl or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
20heterocyclic radical, C
1-C
20alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical, C
1-C
15alkyl sulphonyl, C
6-C
20aryl sulfonyl or C
2-C
20heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
2for hydrogen, halogen, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkane siloxy, C
6-C
15aryl, C
6-C
15aryloxy, C
2-C
15heterocyclic aryl, aldehyde radical, connection C
1-C
15the carbonyl of alkyl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, the substituted or unsubstituted C of connection
1-C
15the carbonyl of alkylamino or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
15aryl, C
2-C
15heterocyclic radical, C
1-C
15alkyl, formyl radical, C
1-C
15alkyl formyl radical, C
6-C
15aryl formyl radical, C
2-C
15heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15alkylthio, C
1-C
15alkane siloxy, C
6-C
15aryl, C
6-C
15aryloxy, C
2-C
15heterocyclic aryl, connection C
1-C
15the carbonyl of alkoxyl group, aminoacyl, connection C
1-C
15the carbonyl of alkylamino or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
15aryl, C
2-C
15heterocyclic radical, substituted or unsubstituted C
1-C
15alkyl, formyl radical, substituted or unsubstituted C
1-C
15alkyl formyl radical, substituted or unsubstituted C
6-C
15aryl formyl radical; Or Rc, Rd and atom N connect into ring.
7. metal complex according to claim 6, is characterized in that in formula IIb,
During n=0, p=0 or 1;
During p=1, L
3for the one or more pyridyl be substituted in ortho position, a position and contraposition, the nitrogen-atoms of pyridyl connects parent, and between pyridyl, the substituting group of position and contraposition is independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
1-C
8alkylthio, C
1-C
8alkane is silica-based, C
1-C
8alkyl siloxy, C
6-C
12aryloxy, C
1-C
8alkyl amine group, substituted or unsubstituted C
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, formamido-, C
1-C
8alkyl amido, urea groups, substituted or unsubstituted C
1-C
8alkyl urea groups, sulfoamido or C
1-C
8alkylsulfonamido;
During n=1, p=0, X
1for oxygen, CH
2, substituted or unsubstituted C
6-C
12aryl; Y
1for oxygen, nitrogen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imino-; Wherein, X
1the parent that each group represented connects is Y
1, Y
1the parent that each group represented connects is X
1;
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8imido grpup or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; In formula Ib, the parent that the group that Y represents connects is aromatic ring;
During m=1, X is nitrogen, oxygen, methyne, methylene radical, carbonyl; Y is nitrogen, oxygen, substituted or unsubstituted C
6-C
12aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkyl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group, imino-, substituted or unsubstituted C
1-C
8alkyl imino base or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, substituted or unsubstituted C independently
6-C
12aryl, substituted or unsubstituted C
2-C
12heterocyclic radical or substituted or unsubstituted C
1-C
8alkyl; Or Rc, Rd and atom N connect into ring; The parent that the group that X represents connects is the parent of the group connection that Y, Y represent is X;
between be singly-bound or double bond;
R
1for hydrogen or substituted or unsubstituted C
6-C
12aryl;
R
2for methyl, sec.-propyl, substituted or unsubstituted C
1-C
8alkyl or substituted or unsubstituted C
6-C
12aryl;
E is hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, connection C
1-C
8the carbonyl of alkyl, connection C
1-C
8the carbonyl of alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, connection C
1-C
8the carbonyl of alkylamino, connection C
6-C
12the carbonyl of arylamino, connection C
2-C
12the carbonyl of heterocyclylamino group, connect substituted or unsubstituted C
1-C
8the alkylsulfonyl of alkyl amine group; Or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, aryl, C independently
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
1for hydrogen, halogen, nitro, C
1-C
8alkyl, C
1-C
8alkoxyl group, connection C
1-C
8the carbonyl of alkylamino, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical, substituted or unsubstituted C
1-C
8alkyl sulphonyl, substituted or unsubstituted C
6-C
12aryl sulfonyl or substituted or unsubstituted C
2-C
12heterocyclyl sulfonyl; Or Rc, Rd and atom N connect into ring;
E
2for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, C
2-C
12heterocyclic aryl, connect substituted or unsubstituted C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, C
1-C
8alkyl, formyl radical, C
1-C
8alkyl formyl radical, C
6-C
12aryl formyl radical, C
2-C
12heterocyclic radical formyl radical; Or Rc, Rd and atom N connect into ring;
E
3for hydrogen, halogen, C
1-C
8alkyl, C
1-C
8alkoxyl group, C
6-C
12aryl, C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkoxyl group or such as formula R
cr
dgroup shown in N-; Wherein, Rc and Rd is hydrogen, C independently
6-C
12aryl, C
2-C
12heterocyclic radical, substituted or unsubstituted C
1-C
8alkyl, formyl radical, substituted or unsubstituted C
1-C
8alkyl formyl radical, substituted or unsubstituted C
6-C
12aryl formyl radical; Or Rc, Rd and atom N connect into ring.
8. metal complex according to claim 7, is characterized in that: in formula IIb,
M is ruthenium; L is,
thricyclohexyl phosphorus; L
1and L
2be chlorine;
N=0 or 1;
During n=0, p=0 or 1;
During p=1, L
3for the pyridyl ligands that a position and/or contraposition are substituted, the nitrogen-atoms of pyridyl connects parent, and between pyridyl, the substituting group of position and contraposition is independently halogen, C
1-C
3alkoxyl group, C
1-C
6alkyl amine group, substituted or unsubstituted C
6-C
12aryl;
During n=1, p=0, X
1for CH
2or phenyl; Y
1for oxygen or carbonyl;
During m=0, Y is C
1-C
4alkylamino or C
1-C
3alkoxyl group;
During m=1, X is carbonyl, CH
2, CH or phenmethyl; Y be nitrogen, NH,
c
1-C
4alkoxyl group, C
5heterocyclic oxy group or C
1-C
3alkane siloxy; X and Y is singly-bound or double bond;
R
1for hydrogen, C
6the phenyl that aryl or nitro replace;
R
2for C
1-C
3alkyl or C
1-C
3alkoxyl group;
E is halogen, nitro, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkoxy carbonyl, C
1-C
8alkyl amino sulfonyl, C
6-C
12n-aryl sulfonyl;
E
1and E
2for hydrogen, halogen, C independently
1-C
4alkyl or C
1-C
4alkoxyl group; E
3for hydrogen.
9. metal complex according to claim 8, is characterized in that: formula IIb is following arbitrary metal complex,
10. the preparation method of the metal complex described in any one of claim 1-9, is characterized in that: it is obtained by any one method of following four kinds of methods:
Method one comprises following three steps:
The structural formula of above-mentioned metal complex intermediate Vb is as follows:
1) under protection of inert gas, the substituted or unsubstituted Tosylhydrazone such as shown in SM-2 is generated Cabbeen transition state in the anhydrous organic solvent of inorganic strong alkali; Wherein, R
a, R
b, R
c, R
dand R
ealone be hydrogen, C
1-C
8alkyl or C
1-C
8alkoxyl group;
2) under protection of inert gas, step 1) the Cabbeen transition state that obtains and ML
1l
2(PPh)
3reaction, generates metal complex intermediate compound IV; Wherein, M, L
1and L
2definition with described in any one of claim 1-9, but L
1and L
2be not all RCOO
-;
3) under protection of inert gas, step 2) the metal complex intermediate that obtains and complex ligands Ib react and generate metal complex intermediate Vb; Wherein, Vb is L in IIb is PPh
3time compound, wherein M, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3described in any one of claim 1-9;
Method two: by the Vb described in method one under protection of inert gas respectively with except PPh
3outer other react the following metal complex IIb of generation to the complex ligands L of electronics, wherein, and p=0, M, L, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3definition with described in any one of claim 1-9, but L is not PPh
3;
Method three: react other under protection of inert gas and except thricyclohexyl phosphorus of IIb to the complex ligands L of electronics and generate following metal complex IIb, wherein, as in the IIb of reactant: p=0, M, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3definition with described in any one of claim 1-9, L is thricyclohexyl phosphorus; As in the IIb of resultant: p=0, M, L
1, L
2, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3definition with described in any one of claim 1-9, but L is not thricyclohexyl phosphorus;
Method four: under protection of inert gas, by the resultant IIb in method one to method three described in either method and the complex ligands L giving electronics
3reaction generates IIb, wherein, in the IIb of the resultant of present method: p=1, M, L, L
1, L
2, L
3, Y, Y
1, R
1, R
2, E, E
1, E
2and E
3described in any one of claim 1-9.
The preparation method of 11. metal complexs as claimed in claim 10, is characterized in that:
In method two, described except PPh
3outer other are thricyclohexyl phosphorus to the complex ligands L of electronics, or
mes=2,4,6-trimethylphenyl.
The preparation method of 12. metal complexs as described in claim 10 or 11, is characterized in that: in method one to method three, described L
1and L
2for chlorine.
The preparation method of 13. metal complexs as described in any one of claim 10 ~ 12, is characterized in that:
Step 1 in method one) in, described R
a, R
b, R
c, R
dand R
ebe hydrogen; Described inorganic strong alkali is one or more in sodium methylate, sodium ethylate, sodium tert-butoxide and sodium hydrogen; The consumption of described inorganic strong alkali is 1-3 times of SM-2 molar weight; Described anhydrous organic solvent is one or more in anhydrous methanol, ethanol, the trimethyl carbinol and tetrahydrofuran (THF); The consumption of described anhydrous organic solvent is 5-30 times of SM-2 molar weight; The temperature of described reaction is 45-75 DEG C;
Step 2 in method one) in, described ML
1l
2l
3for RuCl
2p (Ph
3)
3; The temperature of described reaction is-50 DEG C to-85 DEG C; Described ML
1l
2l
3consumption be the 0.3-1.0 of SM-2 molar weight doubly;
Step 3 in method one) in, the temperature of described reaction is-50 DEG C to-85 DEG C; The consumption of described complex ligands Ib is 1-3 times of complex intermediate molar weight;
In method two, the temperature of described reaction is 20 DEG C to 75 DEG C, is 60 DEG C to 75 DEG C when reacting with complex ligands IIIa, is 20 DEG C to 35 DEG C when reacting with complex ligands IIId; The consumption of described IIIa or IIId is 1-3 times of complex intermediate Vb molar weight;
In method four, the temperature of described reaction is 20 DEG C to 35 DEG C, described L
3consumption be the 1-5 of complex compound II molar weight doubly;
Step 1 in method one) to step 3) in, and method two is in method four, time of reaction all with detection reaction completely till.
14. metal complexs according to any one of claim 1-9, is characterized in that: described heterocyclic radical is heterocyclic aryl.
Metal complex described in 15. any one of claim 1-9 does the application of catalyzer in olefin metathesis replacement(metathesis)reaction.
16. application according to claim 15, is characterized in that: described olefin metathesis replacement(metathesis)reaction is the olefin metathesis replacement(metathesis)reaction of intramolecular cyclization, intermolecular olefin metathesis replacement(metathesis)reaction or intermolecular cycloolefin ring opening metathesis polymerzation.
17. application according to claim 16, is characterized in that: the described cycloolefin for polyreaction is tensioned cycloolefin structure or polycyclic olefin structure; They are substituted or non-substituted structures, and they contain F, Cl, Br, N, O, Si, S, P, B, C in one or more ring
6-C
15aromatic series and C
4-C
15one or more in aromatic heterocycle substituting group.
18. application according to claim 17, is characterized in that: described cycloolefin structure contains 4 or 5 or 7-16 carbon atom, or multiple heteroatoms or heteroatom group.
19. application according to claim 17, is characterized in that: described polycyclic olefin structure is the polycyclic olefin structure containing 2 to 6 rings.
20., according to the application described in claim 17, is characterized in that: described polycyclic olefin is that one or more hydrogen in cyclopentadiene or its molecule are by C
1-C
15saturated or undersaturated alkyl, substituted or unsubstituted C
1-C
15amido, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
6-C
15aryloxy, substituted or unsubstituted C
1-C
15heterocyclic oxy group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
6-C
15arylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, methanoyl, formamido-, substituted or unsubstituted C
1-C
15alkyl carbonyloxy, substituted or unsubstituted C
1-C
15alkyl amido, substituted or unsubstituted C
6-C
15arylcarbonyloxy or substituted or unsubstituted C
6-C
15the derivative that aryl carboxamides base replaces.
21., according to the application described in claim 19, is characterized in that: described polycyclic olefin is following polycyclic olefin structure VIa and VIb:
Wherein:
A is O, S, C
1-C
15saturated or undersaturated alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15aryloxy, substituted or unsubstituted C
1-C
15heterocyclic oxy group, substituted or unsubstituted C
1-C
15alkylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, substituted or unsubstituted C
1-C
15alkyl amine group, substituted or unsubstituted C
1-C
15arylamine group, substituted or unsubstituted C
1-C
15alkyl amido, substituted or unsubstituted C
1-C
15aryl carboxamides base or substituted or unsubstituted C
1-C
15heterocyclic radical formamido-;
R
10and R
11be hydrogen, halogen, substituted or unsubstituted C independently
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, C
6-C
15aryloxy, C
6-C
15aryl, C
2-C
15heterocyclic radical, C
2-C
15heterocyclic aryl, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15alkyl amido, C
1-C
15alkylsulfonamido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, ionic liquid monomer, liquid crystal monomer, active drug molecule; In formula VIa, R
10and R
11be not linked to be ring texture or be linked to be ring texture.
22., according to the application described in claim 19, is characterized in that: described polycyclic olefin is following polycyclic olefin structure VIIa-VIIb:
Wherein:
A is O, S, C
1-C
15saturated or undersaturated alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15aryloxy, substituted or unsubstituted C
1-C
15heterocyclic oxy group, substituted or unsubstituted C
1-C
15alkylthio, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15alkyl amido, substituted or unsubstituted C
1-C
15aryl carboxamides base or substituted or unsubstituted C
1-C
15heterocyclic radical formamido-;
R
12for substituted or unsubstituted C
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, C
6-C
15aryloxy, C
6-C
15aryl, C
2-C
15heterocyclic radical, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15formamido-, C
1-C
15alkylsulfonamido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule;
R
13and R
14be substituted or unsubstituted C independently
1-C
15alkyl, substituted or unsubstituted C
1-C
15alkoxyl group, substituted or unsubstituted C
1-C
15alkylthio, substituted or unsubstituted C
1-C
15alkane siloxy, C
6-C
15aryloxy, C
6-C
15aryl, C
2-C
15heterocyclic radical, connect substituted or unsubstituted C
1-C
15the carbonyl of alkoxyl group, formamido-, substituted or unsubstituted C
1-C
15formamido-, C
1-C
15alkylsulfonamido, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule.
23. application according to claim 16, is characterized in that: described intermolecular cycloolefin ring opening metathesis polymerzation is the polyreaction preparing macromolecule polymer material.
24. application according to claim 23, is characterized in that: the described organic solvent preparing the polyreaction of macromolecule polymer material is one or more in methylene dichloride, ethylene dichloride, chloroform, toluene, dimethylbenzene, chlorobenzene and ionic liquid.
25. application according to claim 23, is characterized in that: in described intermolecular cycloolefin ring opening metathesis polymerzation, when raw material cycloolefin or polycyclic olefin are liquid, do not add organic solvent.
26. application according to claim 23, is characterized in that: described high molecular polymer is for such as formula shown in VIc, VId, VIe, VIIc, VIId, Poly-DCPD;
Wherein, R
10, R
11, R
12, R
13and R
14be hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C independently
1-C
20alkyl, C
1-C
20alkoxyl group, substituted or unsubstituted C
1-C
20aryloxy, C
1-C
20heterocyclyloxy base, C
1-C
20alkylthio, C
1-C
20alkane is silica-based, C
1-C
20alkyl siloxy, C
2-C
20heterocyclic radical, substituted or unsubstituted C
6-C
20aryl, C
6-C
20aryloxy, connection C
1-C
20the carbonyl of alkyl, connection C
6-C
20the carbonyl of aryl, connection C
2-C
20the carbonyl of heterocyclic radical, connection C
6-C
20the carbonyl of aryloxy, connection C
6-C
20the carbonyl of heterocyclyloxy base, connect substituted or unsubstituted C
1-C
20oxygen base carbonyl, aminoacyl, the substituted or unsubstituted C of connection of saturated or unsaturated alkyl
1-C
20carbonyl, connection C that saturated or unsaturated alkyl is amino
6-C
20the carbonyl of arylamino, connection C
2-C
20the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
20alkyl urea groups, substituted or unsubstituted C
6-C
20aryl-ureido, substituted or unsubstituted C
2-C
20heterocyclic radical urea groups, connection C
1-C
20the alkylsulfonyl of alkylamino, connection C
6-C
20the alkylsulfonyl of arylamino or connection C
2-C
20the alkylsulfonyl of heterocyclylamino group; n
1be 10
2-10
4; m
1be 10
2-10
4.
27. application according to claim 26, is characterized in that: in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD,
R
10, R
11, R
12, R
13and R
14be hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C independently
1-C
15alkyl, C
1-C
15alkoxyl group, C
1-C
15heterocyclic oxy group, C
1-C
15alkylthio, C
1-C
15alkane is silica-based, C
1-C
15alkyl siloxy, C
2-C
15heterocyclic radical, substituted or unsubstituted C
6-C
15aryl, substituted or unsubstituted C
6-C
15aryloxy, connection C
1-C
15the carbonyl of alkyl, connection C
6-C
15the carbonyl of aryl, connection C
2-C
15the carbonyl of heterocyclic radical, connect substituted or unsubstituted C
1-C
15the oxygen base carbonyl of saturated or unsaturated alkyl, connect C
6-C
15the carbonyl of aryloxy, connection C
6-C
15the carbonyl of heterocyclyloxy base, aminoacyl, the substituted or unsubstituted C of connection
1-C
15carbonyl, connection C that saturated or unsaturated alkyl is amino
6-C
15the carbonyl of arylamino, connection C
2-C
15the carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C
1-C
15alkyl urea groups, substituted or unsubstituted C
6-C
15aryl-ureido, substituted or unsubstituted C
2-C
15heterocyclic radical urea groups, connection C
1-C
15the alkylsulfonyl of alkylamino, connection C
6-C
15the alkylsulfonyl of arylamino, connection C
2-C
15the alkylsulfonyl of heterocyclylamino group; n
1be 10
2-10
4; m
1be 10
2-10
4.
28. application according to claim 27, is characterized in that: in formula VIc, VId, VIe, VIIc, VIId, Poly-DCPD,
R
10, R
11, R
12, R
13and R
14be hydrogen, halogen, substituted or unsubstituted C independently
1-C
8alkyl, C
1-C
8alkoxyl group, C
1-C
8alkylthio, C
1-C
8alkane is silica-based, C
1-C
8alkyl siloxy, C
2-C
8heterocyclic radical, substituted or unsubstituted C
6-C
12aryl, substituted or unsubstituted C
6-C
12aryloxy, connection C
1-C
8the carbonyl of alkyl, connection C
6-C
12the carbonyl of aryl, connection C
2-C
8the carbonyl of heterocyclic radical, connect substituted or unsubstituted C
1-C
8the oxygen base carbonyl of saturated or unsaturated alkyl, connect C
6-C
12the carbonyl of aryloxy, connection C
6-C
8the carbonyl of heterocyclyloxy base, aminoacyl, the substituted or unsubstituted C of connection
1-C
8carbonyl, connection C that saturated or unsaturated alkyl is amino
6-C
12the carbonyl of arylamino, connection C
2-C
8the carbonyl of heterocyclylamino group, connection C
1-C
8the alkylsulfonyl of alkylamino, connection C
6-C
12the alkylsulfonyl of arylamino, connection C
2-C
8the alkylsulfonyl of heterocyclylamino group; n
1be 10
2-10
4; m
1be 10
2-10
4.
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| WO2018236191A1 (en) * | 2017-06-23 | 2018-12-27 | 광주과학기술원 | Ligand for forming ruthenium complex, ruthenium complex catalyst, production method therefor and use thereof |
| CN109134547A (en) * | 2017-06-28 | 2019-01-04 | 赞南科技(上海)有限公司 | A kind of ruthenium complex, preparation method and application |
| EP4112671A4 (en) * | 2020-02-27 | 2024-04-03 | Zeon Corporation | Copolymer formed by ring-opening copolymerization of cycloolefin, composition for insulating material, and insulating material |
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| WO2011079439A1 (en) * | 2009-12-30 | 2011-07-07 | Zannan Scitech Co., Ltd. | Highly active metathesis catalysts selective for romp and rcm reactions |
| RU2451692C2 (en) * | 2010-08-13 | 2012-05-27 | Закрытое Акционерное Общество "Сибур Холдинг" | Method of cleaning polymerisation equipment from low-solubility high-molecular weight polymer deposits (versions) |
| CN102603928B (en) * | 2011-01-11 | 2015-07-15 | 赞南科技(上海)有限公司 | Preparation method of hydrogenated nitrile rubber and degradation and hydrogenation method of butadiene type rubber |
| PL230302B1 (en) | 2012-02-27 | 2018-10-31 | Apeiron Synthesis Spolka Z Ograniczona Odpowiedzialnoscia | Metathesis catalysts containing onium groups |
| CN107233920A (en) * | 2016-03-29 | 2017-10-10 | 上海东杰高分子材料有限公司 | A kind of ruthenium complex catalyst |
| WO2017185324A1 (en) * | 2016-04-29 | 2017-11-02 | Xia, Ling | Group 8 transition metal catalysts and method for making same and process for use of same in olefin disproportionation reactions |
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| EP1765839B1 (en) * | 2004-06-09 | 2017-01-25 | UTI Limited Partnership | Transition metal carbene complexes containing a cationic substituent as catalysts of olefin metathesis reactions |
| CN1907992B (en) * | 2005-07-04 | 2012-03-28 | 赞南科技(上海)有限公司 | Ruthenium complex compound ligand, ruthenium complex compound, solid carrying ruthenium complex catalyst and preparation method and use thereof |
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| WO2018236191A1 (en) * | 2017-06-23 | 2018-12-27 | 광주과학기술원 | Ligand for forming ruthenium complex, ruthenium complex catalyst, production method therefor and use thereof |
| US11471867B2 (en) | 2017-06-23 | 2022-10-18 | Gwangju Institute Of Science And Technology | Ligand for forming ruthenium complex, ruthenium complex catalyst, production method therefor and use thereof |
| CN109134547A (en) * | 2017-06-28 | 2019-01-04 | 赞南科技(上海)有限公司 | A kind of ruthenium complex, preparation method and application |
| CN109134547B (en) * | 2017-06-28 | 2023-10-03 | 浙江赞昇新材料有限公司 | Ruthenium complex, preparation method and application thereof |
| EP4112671A4 (en) * | 2020-02-27 | 2024-04-03 | Zeon Corporation | Copolymer formed by ring-opening copolymerization of cycloolefin, composition for insulating material, and insulating material |
Also Published As
| Publication number | Publication date |
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| CN104262590B (en) | 2018-10-09 |
| CN104262403B (en) | 2017-07-18 |
| CN101684075A (en) | 2010-03-31 |
| CN104262403A (en) | 2015-01-07 |
| CN104211735B (en) | 2018-01-30 |
| CN104262590A (en) | 2015-01-07 |
| CN101684075B (en) | 2014-08-20 |
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