CN104262403B - A kind of metal complex part, metal complex and its preparation method and application, high molecular polymer and its preparation method and application - Google Patents
A kind of metal complex part, metal complex and its preparation method and application, high molecular polymer and its preparation method and application Download PDFInfo
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- CN104262403B CN104262403B CN201410411705.2A CN201410411705A CN104262403B CN 104262403 B CN104262403 B CN 104262403B CN 201410411705 A CN201410411705 A CN 201410411705A CN 104262403 B CN104262403 B CN 104262403B
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- alkyl
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- carbonyl
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- 150000004696 coordination complex Chemical group 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 title claims description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 302
- -1 small molecule cycloolefins Chemical class 0.000 claims abstract description 140
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229920002521 macromolecule Polymers 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims description 381
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 372
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 308
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 252
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 252
- 239000001257 hydrogen Substances 0.000 claims description 150
- 229910052739 hydrogen Inorganic materials 0.000 claims description 150
- 238000006467 substitution reaction Methods 0.000 claims description 125
- 150000002431 hydrogen Chemical class 0.000 claims description 121
- 239000002585 base Substances 0.000 claims description 118
- 125000003545 alkoxy group Chemical group 0.000 claims description 77
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 77
- 125000000217 alkyl group Chemical group 0.000 claims description 75
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 57
- 229910052736 halogen Inorganic materials 0.000 claims description 52
- 150000002367 halogens Chemical class 0.000 claims description 51
- 229910052760 oxygen Inorganic materials 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 43
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- 125000003282 alkyl amino group Chemical group 0.000 claims description 36
- 239000003446 ligand Substances 0.000 claims description 36
- 229910052710 silicon Inorganic materials 0.000 claims description 30
- 238000005865 alkene metathesis reaction Methods 0.000 claims description 28
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 26
- 125000000266 alpha-aminoacyl group Chemical group 0.000 claims description 25
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- 125000001769 aryl amino group Chemical group 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001925 cycloalkenes Chemical group 0.000 claims description 18
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 16
- 125000002252 acyl group Chemical group 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 14
- 125000004104 aryloxy group Chemical group 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000005649 metathesis reaction Methods 0.000 claims description 13
- 125000003368 amide group Chemical group 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000003857 carboxamides Chemical class 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000037429 base substitution Effects 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical compound CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 claims 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- 239000002861 polymer material Substances 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims 1
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1012
- 229910052786 argon Inorganic materials 0.000 description 506
- 239000007789 gas Substances 0.000 description 505
- 239000012327 Ruthenium complex Substances 0.000 description 410
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 228
- 230000015572 biosynthetic process Effects 0.000 description 132
- 238000003786 synthesis reaction Methods 0.000 description 131
- 238000001914 filtration Methods 0.000 description 128
- 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
- 239000012043 crude product Substances 0.000 description 123
- USPLDBATMHXKKD-UHFFFAOYSA-N dichloromethane;pentane Chemical compound ClCCl.CCCCC USPLDBATMHXKKD-UHFFFAOYSA-N 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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 119
- 150000003254 radicals Chemical class 0.000 description 113
- 238000012360 testing method Methods 0.000 description 113
- 125000004433 nitrogen atom Chemical group N* 0.000 description 59
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 50
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 50
- 238000007363 ring formation reaction Methods 0.000 description 50
- 125000001424 substituent group Chemical group 0.000 description 36
- 125000001841 imino group Chemical group [H]N=* 0.000 description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 30
- 238000000034 method Methods 0.000 description 27
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 22
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 20
- 229910052707 ruthenium Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 13
- 125000003375 sulfoxide group Chemical group 0.000 description 13
- 238000003556 assay Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 8
- 150000002118 epoxides Chemical class 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 5
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 150000003222 pyridines Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000005422 alkyl sulfonamido group Chemical group 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002971 oxazolyl group Chemical group 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000002098 pyridazinyl group Chemical group 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance 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
- MCMWRWKXPXXZAS-UHFFFAOYSA-N 6-chloro-3-[3-(4-chloro-3,5-dimethylphenoxy)propyl]-1h-indole-2-carboxylic acid Chemical compound CC1=C(Cl)C(C)=CC(OCCCC=2C3=CC=C(Cl)C=C3NC=2C(O)=O)=C1 MCMWRWKXPXXZAS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 125000005257 alkyl acyl group Chemical group 0.000 description 2
- 125000005277 alkyl imino group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002393 azetidinyl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 150000003948 formamides Chemical class 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000000623 heterocyclic 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
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 229940002612 prodrug Drugs 0.000 description 2
- 239000000651 prodrug Substances 0.000 description 2
- 125000003226 pyrazolyl 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
- 238000012827 research and development Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- QYMGRIFMUQCAJW-UHFFFAOYSA-N 1,2-dihydropyrazine Chemical compound C1NC=CN=C1 QYMGRIFMUQCAJW-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical class CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-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
- GMAWQTHVIIUMFA-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenoxy)acetyl]-n-(2-sulfanylethyl)piperidine-4-carboxamide Chemical compound C1CC(C(=O)NCCS)CCN1C(=O)COC1=CC=C(Cl)C=C1Cl GMAWQTHVIIUMFA-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-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
- LMOJCFKMCAPGGY-UHFFFAOYSA-N 2-[8-(1,3-benzothiazol-2-ylcarbamoyl)-3,4-dihydro-1h-isoquinolin-2-yl]-5-[3-(4-pyrazolo[3,4-d]pyrimidin-1-ylphenoxy)propyl]-1,3-thiazole-4-carboxylic acid Chemical compound C1=CC=C2SC(NC(=O)C=3C=CC=C4CCN(CC4=3)C3=NC(=C(S3)CCCOC=3C=CC(=CC=3)N3C4=NC=NC=C4C=N3)C(=O)O)=NC2=C1 LMOJCFKMCAPGGY-UHFFFAOYSA-N 0.000 description 1
- HHOGMIYMABYION-UHFFFAOYSA-N 2-amino-1h-pyrimido[4,5-d]pyrimidin-4-one Chemical compound C1=NC=C2C(=O)NC(N)=NC2=N1 HHOGMIYMABYION-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 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
- GKQLYSROISKDLL-UHFFFAOYSA-N EEDQ Chemical compound C1=CC=C2N(C(=O)OCC)C(OCC)C=CC2=C1 GKQLYSROISKDLL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- VXDNQJCXIVLMQW-YFKPBYRVSA-N [(2s)-1-(2-amino-6-oxo-3h-purin-9-yl)-3-hydroxypropan-2-yl]oxymethylphosphonic acid Chemical compound N1C(N)=NC(=O)C2=C1N(C[C@@H](CO)OCP(O)(O)=O)C=N2 VXDNQJCXIVLMQW-YFKPBYRVSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl 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
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 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
- 125000005056 dihydrothiazolyl group Chemical group S1C(NC=C1)* 0.000 description 1
- 125000005058 dihydrotriazolyl group Chemical group N1(NNC=C1)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002547 isoxazolines Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- RMFJTEMHOPPQER-UHFFFAOYSA-N n-(carbamoylamino)formamide Chemical group NC(=O)NNC=O RMFJTEMHOPPQER-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- QPUMEZIFDXYGPG-UHFFFAOYSA-N piperazine 1H-pyrrole Chemical compound N1CCNCC1.N1C=CC=C1 QPUMEZIFDXYGPG-UHFFFAOYSA-N 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
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009329 sexual behaviour Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 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
Landscapes
- 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 kind of metal complex part, metal complex and its preparation method and application.Its metal complex II c of present invention structural formula is as follows.The metal complex of the present invention has catalytic activity higher, the advantages of the diversity of structure and physical property, and diversified optimum choice is provided for the catalytic applications of various raw materials.The invention also discloses the various functions macromolecule new material of the catalyzed ring opening polymerization of various types of small molecule cycloolefins reaction (ROMP) generation and its application, structure is as follows：
Description
The application is Application No. 2009101757906, and the applying date is September in 2009 27, a kind of entitled " gold
Belong to complex ligands, metal complex and its preparation method and application, high molecular polymer and its preparation method and application " it is special
The divisional application of profit application.
Technical field
The present invention relates to a kind of part, complex compound and its preparation method and application, a kind of polymer and preparation method thereof and
Using being specifically related to a kind of metal complex part, metal complex and its preparation method and application, a kind of high molecular polymerization
Thing and its preparation method and application.
Background technology
The research and development of olefin metathesis double decomposition ruthenium catalyst and the new and effective ruthenium complex catalyst of utilization pass through alkene
Catalysed metathesis ring-opening polymerisation (ROMP:Ring Opening Metathesis Polymerization) method prepare it is all kinds of
The multifunctional macromolecule such as high strength and high hardness new material oneself cause extensive attention.The wound of ruthenium complex catalyst in the field
The seminars such as beginning people Grubbs have reported different types of ruthenium complex catalyst and by associated olefinic catalysed metathesis open loop
Polymerisation and reaction and injection molding process (RIM:Reaction Injection Molding) technology prepare it is all kinds of multi-functional
Macromolecule new material, wherein the key for preparing all kinds of multifunctional macromolecule new materials is effective ROMP catalyst.
Olefin catalytic polymerization product (ROMP-RIM) has higher impact strength and bending modulus, is difficult by temperature shadow
Ring, there is a fabulous corrosion resistance, the very good mechanical properties such as low-density are built in traffic, electrical equipment, sports and amusement facility, building
The fields such as material, casting, communication are built all to have broad application prospects.Current main ROMP new material industrializations manufacturer is promise
Bel prize winner professor Grubbs provides the U.S. Materia Inc. of ROMP patented technologies and the Hercules public affairs in the U.S.
The ZEON companies of department, Goodrich companies and Japan.
Oneself has obtained industrial applications to some current olefin catalytic polymerization products, but its shortcoming passes through ruthenium catalyst open loop
The method of polymerization prepares intensity and modulus of all kinds of multi-functional macromolecule new materials etc. in above the average, needs further to be ground
Send out alkene ring-opening polymerization catalyst and its polymerization reaction monomer and processing technology more effective, reach the mesh for improving mechanical performance
's.
The content of the invention
The present invention is anti-in order to solve existing olefin metathesis reaction catalyst and associated olefinic catalysed metathesis ring-opening polymerisation
The shortcoming answered, the intensity and modulus of olefinic polymerization product are improved by researching and developing the performance of raising olefin metathesis reaction catalyst
Etc. mechanical performance.The novel metal complexes part of the present invention is characterized in the part constituted with oxygen atom and/or nitrogen-atoms
It can relatively stablize with metal especially ruthenium ion formation and have the metal complex catalyst of greater activity, the present invention is in metal complex
Different type, different physical characteristics, the part of different catalytically active are introduced in thing catalyst, so as to be chemical industry, medicine and height
The synthetically prepared of molecule new material provides more effective various, different activities metal complex catalysts, is olefin metathesis
Selection of the optimization of reaction and products thereof there is provided more catalysis techniques.
Therefore, an object of the present invention is to provide the olefin metathesis metal complex that a kind of structural formula is Formulas I a, Ib, Ic
Thing part：
Wherein, Z is CH2Or
M=0 or 1, n=0 or 1；
During n=1, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C20Alkyl, substitution or unsubstituted
C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, connection take
Generation or unsubstituted C1-C20The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy, imino group, substitution or
Unsubstituted C1-C20Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substitution or not taken
The C in generation6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution or
Unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20It is miscellaneous
Ring group formoxyl；Or Rc, Rd and N atom connection cyclization；X1The parent of each group connection represented is Y1, wherein connection Y portion
Point can be each group in itself or group various substituents, Y1The parent of each group connection represented is X1, wherein
Connect R2Part can be group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryloxy group,
Substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution or
Unsubstituted C1-C20The carbonyl of alkoxy, imino group, substituted or unsubstituted C1-C20Alkyl imino base or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocycle
Base, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution or unsubstituted
C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
In Formulas I a, the parent of group that Y is represented connection is X, wherein the part of the connection other end can be each group in itself or
The various substituents of group；In Formulas I b, the parent of group that Y is represented connection is the parent of the group connection that Y is represented in aromatic ring, Ic
For connection R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C20
Alkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy
Base, imino group, substituted or unsubstituted C1-C20Alkyl imino base, unsubstituted C1-C20Alkyl imino base or such as formula RcRdN- institutes
The group shown；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20It is miscellaneous
Ring group, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom are connected into
Ring；The parent of group that X is represented connection is Y, wherein the part of the connection other end can be each group in itself or group
Various substituents；The parent of group that Y is represented connection is X, wherein the part of the connection other end can be each group in itself,
Can be the various substituents of group；Between can be singly-bound or double bond；
R1For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy, the substituted or unsubstituted C of connection6-C20Fragrant oxygen
The carbonyl of base, the substituted or unsubstituted C of connection6-C20The carbonyl of heterocyclic radical epoxide, substituted or unsubstituted C6-C20Aryl, substitution
Or unsubstituted C6-C20Aryloxy group or substituted or unsubstituted C2-C20Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, substituted or unsubstituted C1-C20Alkyl siloxy, substituted or unsubstituted C2-C20Heterocyclic radical, substitution or
Unsubstituted C6-C20Aryl, C6-C20Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution
Or unsubstituted C6-C20The carbonyl of aryl, the substituted or unsubstituted C of connection2-C20The carbonyl of heterocyclic radical or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently are hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom are connected into
Ring；
R3For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group,
Connect substituted or unsubstituted C1-C20The carbonyl of alkoxy, the substituted or unsubstituted C of connection6-C20The carbonyl of aryloxy group, connection
Substituted or unsubstituted C6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substitution or
Unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkane sulphur
Base, C1-C20Alkane silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, C6-C20Aryl, C6-C20Aryloxy group, connection C1-C20Alkane
The carbonyl of base, connection C6-C20The carbonyl of aryl, connection C2-C20The carbonyl of heterocyclic radical, connection C1-C20The carbonyl of alkoxy, connection
C6-C20The carbonyl of aryloxy group, connection C6-C20The carbonyl of heterocyclic radical epoxide, aminoacyl, connection C1-C20The carbonyl of alkyl amino,
Connect C6-C20The carbonyl of arylamino, connection C2-C20The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C20Alkane
Base urea groups, substituted or unsubstituted C6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20Alkane
The sulfonyl of base amino, connection C6-C20The sulfonyl of arylamino, connection C2-C20The sulfonyl of heterocyclylamino group or such as formula
RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20It is aryl, substituted or unsubstituted
C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution
Or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20
Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or
Person Rc, Rd and N atom connection cyclization；
E1For hydrogen, halogen, nitro, itrile group, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate,
C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, connection C1-C20The carbonyl of alkyl amino
Base, C6-C20Aryl, C6-C20Aryloxy group, sulfoxide group, sulfuryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection replace or not taken
The C in generation6-C20The carbonyl of aryl, the substituted or unsubstituted C of connection2-C20The carbonyl of heterocyclic radical, connection C1-C20The carbonyl of alkoxy
Base, connection C6-C20The carbonyl of arylamino, connection C2-C20The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C20
Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C6-C20Aryl-ureido or substitution do not take
The C in generation2-C20Heterocyclic radical urea groups；
E2For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkyl silicon
Epoxide, aminoacyl, connection C1-C20The carbonyl of alkyl amino, connection C6-C20The carbonyl of arylamino, connection C2-C20Heterocyclic radical
The carbonyl of amino, C6-C20Aryl, C6-C20Aryloxy group, C2-C20Heterocyclic aryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection
C6-C20The carbonyl of aryl, connection C2-C20The carbonyl of heterocyclic radical, connection C1-C20The carbonyl of alkoxy, connection C6-C20Aryloxy
Carbonyl, connection C2-C20The carbonyl of heterocyclylamino group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, first
Acyl group, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substitution or unsubstituted
C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Arylsulfonyl
Base or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization；
E3For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkyl siloxy, C6-C20Virtue
Epoxide, C6-C20Aryl, C2-C20Heterocyclic aryl, connection C1-C20The carbonyl of alkoxy, the substituted or unsubstituted C of connection6-C20Virtue
The carbonyl of epoxide, the substituted or unsubstituted C of connection6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substitution do not take
The C in generation1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl first
Acyl group, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substitution do not take
The C in generation6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom are connected into
Ring；
E4、E5、E6And E7Independently be hydrogen, it is halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkane siloxy, take
Generation or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, the substituted or unsubstituted C of connection1-C20Alkane
The carbonyl of base amino, the substituted or unsubstituted C of connection6-C20The carbonyl of arylamino, the substituted or unsubstituted C of connection2-C20It is miscellaneous
The carbonyl of ring group amino, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, the substituted or unsubstituted C of connection6-C20Aryl
Carbonyl, connect substituted or unsubstituted C2-C20The carbonyl of heterocyclic radical, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy
Base, the substituted or unsubstituted C of connection6-C20The carbonyl of aryloxy group, the substituted or unsubstituted C of connection6-C20The carbonyl of heterocyclic radical epoxide
Base, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substitution or unsubstituted
C6-C20Aryl-ureido or substituted or unsubstituted C2-C20Heterocyclic radical urea groups, substituted or unsubstituted C6-C20Aryl, substitution or
Unsubstituted C6-C20Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, it is substituted or unsubstituted
C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution do not take
The C in generation1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical first
Acyl group, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substitution do not take
The C in generation2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization.
In the present invention, preferably, in Formulas I a, Ib, Ic,
Z is CH2Or TsNHN=；
M=0 or 1, n=0 or 1；
During n=1, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C15Alkyl, substitution or unsubstituted
C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15Heterocyclic aryl, carbonyl, connection take
Generation or unsubstituted C1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, imino group, substitution or
Unsubstituted C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substitution or not taken
The C in generation6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, substitution or
Unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15It is miscellaneous
Ring group formoxyl；Or Rc, Rd and N atom connection cyclization；X1The parent of each group connection represented is Y1, wherein connecting another
The part at end can be each group in itself or group various substituents；Y1Represent each group connection parent be
X1, wherein connection the other end part can be each group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group,
Substituted or unsubstituted C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, connection replace or not taken
The C in generation1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15It is the carbonyl of alkoxy, imino group, substituted or unsubstituted
C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-
C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, substitution or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical first
Acyl group；Or Rc, Rd and N atom connection cyclization；In Formulas I a, the parent for the group connection that Y is represented is X, wherein connecting the other end
Part can be each group in itself or group various substituents；In Formulas I b, the parent for the group connection that Y is represented
For aromatic ring, the parent for the group connection that Y is represented in Ic is connection R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C15
Alkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy
Base, substituted or unsubstituted C1-C15Imido grpup；Such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, substitution or
Unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, take
Generation or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-
C15Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；The parent for the group connection that X is represented is Y, wherein connecting another
The part at end can be each group in itself or group various substituents；The parent for the group connection that Y is represented is X, its
It is middle connection the other end part can be each group in itself or group various substituents；Between can be single
Key or double bond；
R1For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, substituted or unsubstituted C6-C15Aryl, take
Generation or unsubstituted C6-C15Aryloxy group or substituted or unsubstituted C2-C15Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, substituted or unsubstituted C2-C15Heterocyclic radical, C6-C15Virtue
Base, C6-C15Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15
The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, it is formoxyl, substituted or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formyl
Base；Or Rc, Rd and N atom connection cyclization；
R3For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C6-C15Aryl, substitution or unsubstituted
C6-C15Aryloxy group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently are hydrogen, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl
Formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkane sulphur
Base, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, connection C1-C15Alkyl
Carbonyl, connection C6-C15The carbonyl of aryl, connection C2-C15The carbonyl of heterocyclic radical, connection C1-C15The carbonyl of alkoxy, aminoacyl
Base, connection C1-C15The carbonyl of alkyl amino, connection C6-C15The carbonyl of arylamino, connection C2-C15The carbonyl of heterocyclylamino group,
Urea groups, substituted or unsubstituted C1-C15Alkyl urea groups or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Aryl formoxyl, C2-C15Heterocyclic radical
Formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom
Connection cyclization；
E1For hydrogen, halogen, nitro, sulfuryl, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate,
C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, aldehyde radical, connection C1-C15The carbonyl of alkyl, connection
C1-C15The carbonyl of alkoxy, aminoacyl, connection C1-C15The carbonyl of alkyl amino, urea groups, substituted or unsubstituted C1-C15Alkane
Base urea groups, substituted or unsubstituted C1-C15Alkyl, connection C1-C15The sulfonyl of amino or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Virtue
Base formoxyl, C2-C15Heterocyclic radical formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclic radical sulphonyl
Base；Or Rc, Rd and N atom connection cyclization；
E2For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane silica
Base, C6-C15Aryl, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, aldehyde radical, connection C1-C15The carbonyl of alkyl, connection C1-C15Alcoxyl
The carbonyl of base, aminoacyl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl amino or such as formula RcRdGroup shown in N-；
Wherein, Rc and Rd independently are hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E3For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane siloxy, C6-C15Virtue
Base, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, connection C1-C15The carbonyl of alkoxy, aminoacyl, connection C1-C15Alkyl amino
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, substitution
Or unsubstituted C1-C15Alkyl, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15
Aryl formoxyl；Or Rc, Rd and N atom connection cyclization；
E4、E5、E6And E7Independently be hydrogen, it is halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, take
Generation or unsubstituted C2-C15Heterocyclic radical, aminoacyl, connection C1-C15The carbonyl of alkyl amino, connection C6-C15Arylamino
Carbonyl, connection C2-C15The carbonyl of heterocyclylamino group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, connection substitution or not
Substituted C1-C15The carbonyl of alkoxy, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, substituted or unsubstituted C1-C15
Alkylsulfonamido, connection C1-C15The sulphonyl of alkyl amino, substituted or unsubstituted C6-C15It is aryl, substituted or unsubstituted
C6-C15Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Virtue
Base, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl, substituted or unsubstituted C1-C15Alkyl sulphonyl, substitution or unsubstituted
C6-C15Aryl sulfonyl or substituted or unsubstituted C2-C15Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization.
In the present invention, more preferably, in Formulas I a, Ib, Ic,
Z is CH2Or
M=0 or 1, n=0 or 1；
During n=1, X1For oxygen, CH2, substituted or unsubstituted C6-C12Aryl；Y1For oxygen, nitrogen, carbonyl, connection substitution or not
Substituted C1-C8The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkoxy, imino group, substitution or unsubstituted
C1-C8Imino group；Wherein, X1The parent of each group connection represented is Y1, Y1The parent of each group connection represented is X1；
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkyl, connection replace or not taken
The C in generation1-C8The carbonyl of alkoxy, imino group, substituted or unsubstituted C1-C8Imido grpup or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, substituted or unsubstituted C1-C8Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substitution or
Unsubstituted C1-C8Alkyl；Or Rc, Rd and N atom connection cyclization；In Formulas I a, the parent for the group connection that Y is represented is X, formula
In Ib, the parent of group that Y is represented connection is that the parent of the group connection that Y is represented in aromatic ring, Ic is connection R3Carbon；
During m=1, X is nitrogen, oxygen, methine, methylene, carbonyl；Y is nitrogen, oxygen, substituted or unsubstituted C6-C12Aryl,
Connect substituted or unsubstituted C1-C8The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkoxy, imino group,
Substituted or unsubstituted C1-C8Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substitution
Or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substituted or unsubstituted C1-C8Alkyl；Or Rc,
Rd and N atoms connection cyclization；The parent for the group connection that X is represented is Y, wherein the part of the connection other end can be each group sheet
The various substituents of body or group；The parent of group that Y is represented connection is X, wherein the part of the connection other end can be with
Be each group in itself or group various substituents；Between can be singly-bound or double bond；
R1For hydrogen or substituted or unsubstituted C6-C12Aryl；
R2For methyl, isopropyl, substituted or unsubstituted C1-C8Alkyl or substituted or unsubstituted C6-C12Aryl；
R3For hydrogen, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C1-C8Alkoxy, C6-C12Aryl, C6-
C12Aryloxy group, C2-C12Heterocyclic aryl, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd
It independently is hydrogen, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Aryl formoxyl
Or substituted or unsubstituted C2-C12Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E is hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, connection C1-C8The carbonyl of alkyl, company
Meet C1-C8The carbonyl of alkoxy, connection C1-C8The carbonyl of alkyl amino, connection C1-C8The carbonyl of alkyl amino, connection C6-C12Virtue
The carbonyl of base amino, connection C2-C12The carbonyl of heterocyclylamino group, the substituted or unsubstituted C of connection1-C8The sulphonyl of alkyl amine group
Base；Or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, first
Acyl group, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl
Sulfonyl, substituted or unsubstituted C6-C12Aryl sulfonyl or substituted or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc,
Rd and N atoms connection cyclization；
E1For hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, connection C1-C8The carbonyl of alkyl amino, C6-C12Virtue
Base, C6-C12Aryloxy group, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C8Aryl sulfonyl takes
Generation or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization；
E2For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, C2-C12Heterocyclic aryl,
Connect substituted or unsubstituted C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E3For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, connection C1-C8Alkoxy
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, substitution
Or unsubstituted C1-C8Alkyl, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Virtue
Base formoxyl；Or Rc, Rd and N atom connection cyclization；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, substituted or unsubstituted C1-C8It is alkyl, substituted or unsubstituted
C1-C8Alkoxy, substituted or unsubstituted C1-C8Alkyl amino, formamido, substituted or unsubstituted C1-C8Alkyl formamides
Base, connection C1-C8The carbonyl of alkyl amino, connection C6-C12The carbonyl of arylamino, connection C2-C12The carbonyl of heterocyclylamino group,
Connect C1-C8The carbonyl of alkoxy, sulfoamido, substituted or unsubstituted C6-C12Aryl, substituted or unsubstituted C6-C12Fragrant oxygen
Base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Aryl, C2-C12It is miscellaneous
Ring group, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substitution or
Unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C12Aryl sulfonyl, substituted or unsubstituted C2-C12Heterocycle
Base sulfonyl；Or Rc, Rd and N atom connection cyclization.
In the optimal implementation of the present invention, in Formulas I a, Ib and Ic,
Z is CH2Or
N=0 or 1；
During n=1, X1For CH2Or phenyl；Y1For oxygen or carbonyl；
During m=0, Y is C1-C4Alkyl amino or C1-C3Alkoxy；
During m=1, X is carbonyl, CH2, CH or benzyl；Y be nitrogen, NH,C1-C4Alkoxy, C5Heterocycle
Epoxide or C1-C3Alkane siloxy；Can be singly-bound or double bond between X and Y；
R1The phenyl replaced for hydrogen, phenyl or nitro；
R2For C1-C3Alkyl or C1-C3Alkoxy；
R3For hydrogen or C6Aryl；
E is halogen, nitro, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkoxy carbonyl, C1-C8Alkyl amino sulfonyl,
C6-C12N-aryl sulfonyl；
E1And E2For independently hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy；E3For hydrogen；
E4、E5And E7Independently to be hydrogen, C1-C4Alkyl or C1-C4Alkoxy；
E6For hydrogen, halogen, C1-C4Alkyl or C1-C6Alkoxy；
In Ia, as n=0, R2For hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy.
The second object of the present invention is to provide the metal complex that a kind of structural formula is Formula II a, IIb, IIc：
Wherein, M is metal Ru (Ru), tungsten (W) or nickel (Ni)；
L1And L2It independently is halogen (Cl, Br-Or I), RCOO-Or ArO-Anion；
L3For a kind of complex ligands of electron；
L is a kind of complex ligands of electron；
Wherein, Z is CH2Or
M=0 or 1, n=0 or 1；During n=0, p=0 or 1；During n=1, p=0；
During n=1, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C20Alkyl, substitution or unsubstituted
C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, connection take
Generation or unsubstituted C1-C20The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy, imino group, substitution or
Unsubstituted C1-C20Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substitution or not taken
The C in generation6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution or
Unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20It is miscellaneous
Ring group formoxyl；Or Rc, Rd and N atom connection cyclization；X1The parent of each group connection represented is Y1, wherein connection Y portion
Point can be each group in itself or group various substituents, Y1The parent of each group connection represented is X1, wherein
Connect R2Part can be group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryloxy group,
Substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution or
Unsubstituted C1-C20The carbonyl of alkoxy, imino group, substituted or unsubstituted C1-C20Alkyl imino base or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocycle
Base, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution or unsubstituted
C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
In Formulas I a, the parent of group that Y is represented connection is X, wherein the part of the connection other end can be each group in itself or
The various substituents of group；In Formulas I b, the parent of group that Y is represented connection is the parent of the group connection that Y is represented in aromatic ring, Ic
For connection R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C20
Alkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy
Base, imino group, substituted or unsubstituted C1-C20Alkyl imino base, unsubstituted C1-C20Alkyl imino base or such as formula RcRdN- institutes
The group shown；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20It is miscellaneous
Ring group, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom are connected into
Ring；The parent of group that X is represented connection is Y, wherein the part of the connection other end can be each group in itself or group
Various substituents；The parent of group that Y is represented connection is X, wherein the part of the connection other end can be each group in itself,
Can be the various substituents of group；Between can be singly-bound or double bond；
R1For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy, the substituted or unsubstituted C of connection6-C20Fragrant oxygen
The carbonyl of base, the substituted or unsubstituted C of connection6-C20The carbonyl of heterocyclic radical epoxide, substituted or unsubstituted C6-C20Aryl, substitution
Or unsubstituted C6-C20Aryloxy group or substituted or unsubstituted C2-C20Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, substituted or unsubstituted C1-C20Alkyl siloxy, substituted or unsubstituted C2-C20Heterocyclic radical, substitution or
Unsubstituted C6-C20Aryl, C6-C20Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution
Or unsubstituted C6-C20The carbonyl of aryl, the substituted or unsubstituted C of connection2-C20The carbonyl of heterocyclic radical or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently are hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom are connected into
Ring；
R3For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group,
Connect substituted or unsubstituted C1-C20The carbonyl of alkoxy, the substituted or unsubstituted C of connection6-C20The carbonyl of aryloxy group, connection
Substituted or unsubstituted C6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substitution or
Unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkane sulphur
Base, C1-C20Alkane silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, C6-C20Aryl, C6-C20Aryloxy group, connection C1-C20Alkane
The carbonyl of base, connection C6-C20The carbonyl of aryl, connection C2-C20The carbonyl of heterocyclic radical, connection C1-C20The carbonyl of alkoxy, connection
C6-C20The carbonyl of aryloxy group, connection C6-C20The carbonyl of heterocyclic radical epoxide, aminoacyl, connection C1-C20The carbonyl of alkyl amino,
Connect C6-C20The carbonyl of arylamino, connection C2-C20The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C20Alkane
Base urea groups, substituted or unsubstituted C6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20Alkane
The sulfonyl of base amino, connection C6-C20The sulfonyl of arylamino, connection C2-C20The sulfonyl of heterocyclylamino group or such as formula
RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20It is aryl, substituted or unsubstituted
C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution
Or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20
Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or
Person Rc, Rd and N atom connection cyclization；
E1For hydrogen, halogen, nitro, itrile group, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate,
C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, connection C1-C20The carbonyl of alkyl amino
Base, C6-C20Aryl, C6-C20Aryloxy group, sulfoxide group, sulfuryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection replace or not taken
The C in generation6-C20The carbonyl of aryl, the substituted or unsubstituted C of connection2-C20The carbonyl of heterocyclic radical, connection C1-C20The carbonyl of alkoxy
Base, connection C6-C20The carbonyl of arylamino, connection C2-C20The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C20
Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C6-C20Aryl-ureido or substitution do not take
The C in generation2-C20Heterocyclic radical urea groups；
E2For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkyl silicon
Epoxide, aminoacyl, connection C1-C20The carbonyl of alkyl amino, connection C6-C20The carbonyl of arylamino, connection C2-C20Heterocyclic radical
The carbonyl of amino, C6-C20Aryl, C6-C20Aryloxy group, C2-C20Heterocyclic aryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection
C6-C20The carbonyl of aryl, connection C2-C20The carbonyl of heterocyclic radical, connection C1-C20The carbonyl of alkoxy, connection C6-C20Arylamino
Carbonyl, connection C2-C20The carbonyl of heterocyclylamino group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, first
Acyl group, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substitution or unsubstituted
C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Arylsulfonyl
Base or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization；
E3For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkyl siloxy, C6-C20Virtue
Epoxide, C6-C20Aryl, C2-C20Heterocyclic aryl, connection C1-C20The carbonyl of alkoxy, the substituted or unsubstituted C of connection6-C20Virtue
The carbonyl of epoxide, the substituted or unsubstituted C of connection6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substitution do not take
The C in generation1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl first
Acyl group, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substitution do not take
The C in generation6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom are connected into
Ring；
E4、E5、E6And E7Independently be hydrogen, it is halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkane siloxy, take
Generation or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, the substituted or unsubstituted C of connection1-C20Alkane
The carbonyl of base amino, the substituted or unsubstituted C of connection6-C20The carbonyl of arylamino, the substituted or unsubstituted C of connection2-C20It is miscellaneous
The carbonyl of ring group amino, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, the substituted or unsubstituted C of connection6-C20Aryl
Carbonyl, connect substituted or unsubstituted C2-C20The carbonyl of heterocyclic radical, the substituted or unsubstituted C of connection1-C20The carbonyl of alkoxy
Base, the substituted or unsubstituted C of connection6-C20The carbonyl of aryloxy group, the substituted or unsubstituted C of connection6-C20The carbonyl of heterocyclic radical epoxide
Base, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substitution or unsubstituted
C6-C20Aryl-ureido or substituted or unsubstituted C2-C20Heterocyclic radical urea groups, substituted or unsubstituted C6-C20Aryl, substitution or
Unsubstituted C6-C20Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, it is substituted or unsubstituted
C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution do not take
The C in generation1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical first
Acyl group, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substitution do not take
The C in generation2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization.
In the present invention, L is preferably a of following structural III, III b, III c or III d in described IIa, IIb and IIc：
Wherein, R4And R5It independently is C1-C20Alkyl, C6-C20Aryl, C1-C20Heterocyclic radical, aldehyde radical, connection C1-C20Alkyl
Carbonyl, formamido, C1-C20Alkyl amido, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, sulfoamido or
C1-C20Alkylsulfonamido；
R6And R7It independently is hydrogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkane
Base siloxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20Heterocyclic radical, sulfoxide group, sulfuryl, aldehyde radical, connection C1-C20The carbonyl of alkyl
Base, connection C1-C20The carbonyl of alkoxy, formamido, C1-C20Alkyl amido, urea groups, substituted or unsubstituted C1-C20
Alkyl urea groups, sulfoamido, C1-C20Alkylsulfonamido, halogen, nitro or itrile group；
R8And R9It independently is substituted or unsubstituted C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Fragrant oxygen
Base or C2-C20Heterocyclic radical；
In a of formula III, preferably, R4And R5It is aryl；R6And R7It is hydrogen.
More preferably, L structural formula is a of formula III or III d；R4And R5It is 2,4,6- trimethylphenyls；R6And R7It independently is hydrogen
Or III d；R8And R9It is cyclohexyl.
In the another embodiment of the present invention, in the c of II a- of formula II,
Metal (M) is ruthenium；
L1And L2It is chlorion；
L is III a or III d；Wherein R4、R5、R6、R7、R8And R9It is identical 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, L3The pyridine radicals being substituted for one or more of ortho position, meta and contraposition, the nitrogen-atoms of pyridine radicals
Parent is connected, pyridine radicals meta and the substituent aligned are independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C1-C15Alkane
Base, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkyl siloxy, C6-C15Aryloxy group, C1-C15Alkane
Base amido, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic aryl, carbonyl, connection substitution or not
Substituted C1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formamido, C1-C15Alkyl
Formamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, sulfoamido or C1-C15Alkylsulfonamido；
During n=1, p=0, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C15Alkyl, substitution or
Unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15Heterocyclic aryl, carbonyl,
Connect substituted or unsubstituted C1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, imino group,
Substituted or unsubstituted C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substitution
Or unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl,
Substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl is substituted or unsubstituted
C2-C15Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；X1The parent of each group connection represented is Y1, wherein connecting
The part for connecing the other end can be each group in itself or group various substituents；Y1Each group connection represented
Parent is X1, wherein connection the other end part can be each group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group,
Substituted or unsubstituted C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, connection replace or not taken
The C in generation1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15It is the carbonyl of alkoxy, imino group, substituted or unsubstituted
C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-
C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, substitution or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical first
Acyl group；Or Rc, Rd and N atom connection cyclization；In Formulas I a, the parent for the group connection that Y is represented is X, wherein connecting the other end
Part can be each group in itself or group various substituents；In Formulas I b, the parent for the group connection that Y is represented
For aromatic ring, the parent for the group connection that Y is represented in Ic is connection R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C15
Alkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy
Base, substituted or unsubstituted C1-C15Imido grpup；Such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, substitution or
Unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, take
Generation or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-
C15Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；The parent for the group connection that X is represented is Y, wherein connecting another
The part at end can be each group in itself or group various substituents；The parent for the group connection that Y is represented is X, its
It is middle connection the other end part can be each group in itself or group various substituents；Between can be single
Key or double bond；
R1For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, substituted or unsubstituted C6-C15Aryl, take
Generation or unsubstituted C6-C15Aryloxy group or substituted or unsubstituted C2-C15Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, substituted or unsubstituted C2-C15Heterocyclic radical, C6-C15Virtue
Base, C6-C15Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C15
The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, it is formoxyl, substituted or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formyl
Base；Or Rc, Rd and N atom connection cyclization；
R3For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C6-C15Aryl, substitution or unsubstituted
C6-C15Aryloxy group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently are hydrogen, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl
Formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkane sulphur
Base, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, connection C1-C15Alkyl
Carbonyl, connection C6-C15The carbonyl of aryl, connection C2-C15The carbonyl of heterocyclic radical, connection C1-C15The carbonyl of alkoxy, aminoacyl
Base, connection C1-C15The carbonyl of alkyl amino, connection C6-C15The carbonyl of arylamino, connection C2-C15The carbonyl of heterocyclylamino group,
Urea groups, substituted or unsubstituted C1-C15Alkyl urea groups or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Aryl formoxyl, C2-C15Heterocyclic radical
Formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom
Connection cyclization；
E1For hydrogen, halogen, nitro, sulfuryl, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate,
C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, aldehyde radical, connection C1-C15The carbonyl of alkyl, connection
C1-C15The carbonyl of alkoxy, aminoacyl, connection C1-C15The carbonyl of alkyl amino, urea groups, substituted or unsubstituted C1-C15Alkane
Base urea groups, substituted or unsubstituted C1-C15Alkyl, connection C1-C15The sulfonyl of amino or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Virtue
Base formoxyl, C2-C15Heterocyclic radical formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclic radical sulphonyl
Base；Or Rc, Rd and N atom connection cyclization；
E2For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane silica
Base, C6-C15Aryl, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, aldehyde radical, connection C1-C15The carbonyl of alkyl, connection C1-C15Alcoxyl
The carbonyl of base, aminoacyl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl amino or such as formula RcRdGroup shown in N-；
Wherein, Rc and Rd independently are hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E3For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane siloxy, C6-C15Virtue
Base, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, connection C1-C15The carbonyl of alkoxy, aminoacyl, connection C1-C15Alkyl amino
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, substitution
Or unsubstituted C1-C15Alkyl, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15
Aryl formoxyl；Or Rc, Rd and N atom connection cyclization；
E4、E5、E6And E7Independently be hydrogen, it is halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, take
Generation or unsubstituted C2-C15Heterocyclic radical, aminoacyl, connection C1-C15The carbonyl of alkyl amino, connection C6-C15Arylamino
Carbonyl, connection C2-C15The carbonyl of heterocyclylamino group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, connection substitution or not
Substituted C1-C15The carbonyl of alkoxy, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, substituted or unsubstituted C1-C15
Alkylsulfonamido, connection C1-C15The sulphonyl of alkyl amino, substituted or unsubstituted C6-C15It is aryl, substituted or unsubstituted
C6-C15Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C20Virtue
Base, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl, substituted or unsubstituted C1-C15Alkyl sulphonyl, substitution or unsubstituted
C6-C15Aryl sulfonyl or substituted or unsubstituted C2-C15Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization.
More preferably, in the c of II a- of formula II,
M=0 or 1, n=0 or 1；During n=0, p=0 or 1；During n=1, p=0；
During p=1, L3The pyridine radicals being substituted for one or more of ortho position, meta and contraposition, the nitrogen-atoms of pyridine radicals
Parent is connected, pyridine radicals meta and the substituent aligned are independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C1-C8Alkyl,
C1-C8Alkoxy, C1-C8Alkylthio group, C1-C8Alkane silicon substrate, C1-C8Alkyl siloxy, C6-C12Aryloxy group, C1-C8Alkyl amine group, take
Generation or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection1-C8
The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkoxy, formamido, C1-C8Alkyl amido, urea
Base, substituted or unsubstituted C1-C8Alkyl urea groups, sulfoamido or C1-C8Alkylsulfonamido；
During n=1, p=0, X1For oxygen, CH2, substituted or unsubstituted C6-C12Aryl；Y1For oxygen, nitrogen, carbonyl, connection substitution
Or unsubstituted C1-C8The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkoxy, imino group, substitution or not
Substituted C1-C8Imino group；Wherein, X1The parent of each group connection represented is Y1, Y1Represent each group connection parent be
X1；
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkyl, connection replace or not taken
The C in generation1-C8The carbonyl of alkoxy, imino group, substituted or unsubstituted C1-C8Imido grpup or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substitution or
Unsubstituted C1-C8Alkyl；Or Rc, Rd and N atom connection cyclization；In Formulas I a, the parent for the group connection that Y is represented is X, formula
In Ib, the parent of group that Y is represented connection is that the parent of the group connection that Y is represented in aromatic ring, Ic is connection R3Carbon；
During m=1, X is nitrogen, oxygen, methine, methylene, carbonyl；Y is nitrogen, oxygen, substituted or unsubstituted C6-C12Aryl,
Connect substituted or unsubstituted C1-C8The carbonyl of alkyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkoxy, imino group,
Substituted or unsubstituted C1-C8Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substitution
Or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substituted or unsubstituted C1-C8Alkyl；Or Rc,
Rd and N atoms connection cyclization；The parent for the group connection that X is represented is Y, wherein the part of the connection other end can be each group sheet
The various substituents of body or group；The parent of group that Y is represented connection is X, wherein the part of the connection other end can be with
Be each group in itself or group various substituents；Between can be singly-bound or double bond；
R1For hydrogen or substituted or unsubstituted C6-C12Aryl；
R2For methyl, isopropyl, substituted or unsubstituted C1-C8Alkyl or substituted or unsubstituted C6-C12Aryl；
R3For hydrogen, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C1-C8Alkoxy, C6-C12Aryl, C6-
C12Aryloxy group, C2-C12Heterocyclic aryl, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd
It independently is hydrogen, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Aryl formoxyl
Or substituted or unsubstituted C2-C12Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E is hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, connection C1-C8The carbonyl of alkyl, company
Meet C1-C8The carbonyl of alkoxy, connection C1-C8The carbonyl of alkyl amino, connection C1-C8The carbonyl of alkyl amino, connection C6-C12Virtue
The carbonyl of base amino, connection C2-C12The carbonyl of heterocyclylamino group, the substituted or unsubstituted C of connection1-C8The sulphonyl of alkyl amine group
Base；Or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, first
Acyl group, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl
Sulfonyl, substituted or unsubstituted C6-C12Aryl sulfonyl or substituted or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc,
Rd and N atoms connection cyclization；
E1For hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, connection C1-C8The carbonyl of alkyl amino, C6-C12Virtue
Base, C6-C12Aryloxy group, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C8Aryl sulfonyl takes
Generation or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc, Rd and N atom connection cyclization；
E2For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, C2-C12Heterocyclic aryl,
Connect substituted or unsubstituted C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl；Or Rc, Rd and N atom connection cyclization；
E3For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, connection C1-C8Alkoxy
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, substitution
Or unsubstituted C1-C8Alkyl, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Virtue
Base formoxyl；Or Rc, Rd and N atom connection cyclization；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, substituted or unsubstituted C1-C8It is alkyl, substituted or unsubstituted
C1-C8Alkoxy, substituted or unsubstituted C1-C8Alkyl amino, formamido, substituted or unsubstituted C1-C8Alkyl formamides
Base, connection C1-C8The carbonyl of alkyl amino, connection C6-C12The carbonyl of arylamino, connection C2-C12The carbonyl of heterocyclylamino group,
Connect C1-C8The carbonyl of alkoxy, sulfoamido, substituted or unsubstituted C6-C12Aryl, substituted or unsubstituted C6-C12Fragrant oxygen
Base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C12Aryl, C2-C12It is miscellaneous
Ring group, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substitution or
Unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C12Aryl sulfonyl, substituted or unsubstituted C2-C12Heterocycle
Base sulfonyl；Or Rc, Rd and N atom connection cyclization.
In the optimal implementation of the one of the present invention, in the c of II a- of formula II,
M is ruthenium；L isThricyclohexyl phosphorus；L1And L2It is chlorine；
N=0 or 1；
During n=0, p=0 or 1；During n=1, p=0；
During p=1, L3For meta and/or the substituted pyridyl ligands of contraposition, the nitrogen-atoms connection parent of pyridine radicals, pyrrole
The meta of piperidinyl is respectively halogen, C with the substituent aligned1-C3Alkoxy, C1-C6Alkyl amine group, substituted or unsubstituted C6-
C12Aryl；
During n=1, p=0, X1For CH2Or phenyl；Y1For oxygen or carbonyl；
During m=0, Y is C1-C4Alkyl amino or C1-C3Alkoxy；
During m=1, X is carbonyl, CH2, CH or benzyl；Y be nitrogen, NH,C1-C4Alkoxy, C5It is miscellaneous
Epoxy radicals or C1-C3Alkane siloxy；Can be singly-bound or double bond between X and Y；
R1For hydrogen, C6Aryl or the benzyl of nitro substitution；
R2For C1-C3Alkyl or C1-C3Alkoxy；
R3For hydrogen or C6Aryl；
E is halogen, nitro, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkoxy carbonyl, C1-C8Alkyl amino sulfonyl,
C6-C12N-aryl sulfonyl；
E1And E2For independently hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy；E3For hydrogen；
E4、E5And E7Independently to be hydrogen, C1-C4Alkyl or C1-C4Alkoxy；
E6For hydrogen, halogen, C1-C4Alkyl or C1-C6Alkoxy；
In Ia, as n=0, R2For hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy.
The third object of the present invention is to provide a kind of preparation method of metal complex, and it can appointing by following three kinds of methods
One kind is made：
Method one includes following three steps：
The structural formula of above-mentioned metal complex intermediate (Va, Vb, Vc) is as follows：
1) under inert gas shielding, by the substituted or unsubstituted Tosylhydrazone as shown in SM-2 in inorganic strong alkali
Anhydrous organic solvent in generate Cabbeen transition state；Wherein, Ra、Rb、Rc、RdAnd ReAlone for hydrogen, C1-C8Alkyl or C1-C8Alkane
Epoxide；
2) under inert gas shielding, step 1) obtained Cabbeen transition state and ML1L2(PPh)3Reaction, generates metal complex
Thing intermediate compound IV；Wherein, M, L1And L2Definition with described in claim any one of 5-11, but L1And L2It is not RCOO-；
3) under inert gas shielding, step 2) obtained metal complex intermediate and complex ligands Ia, Ib or Ic it is anti-
Metal complex intermediate Va, Vb or Vc should be generated；Wherein, Va, Vb or Vc be in IIa, IIb or IIc L be PPh3When change
Compound, wherein M, L1、L2、Y、Y1、R1、R2、E、E1、E2And E3It is the same as those described above；
Preferably, L1And L2It is chlorine.
Wherein, step 1) in, described Ra、Rb、Rc、RdAnd RePreferably it is hydrogen；Described inorganic strong alkali is preferably
One or more in sodium methoxide, caustic alcohol, sodium tert-butoxide and sodium hydrogen, more preferably caustic alcohol；The use of described inorganic strong alkali
Amount is preferably 1-3 times, more preferably 1.5-2 times of SM-2 moles；Described anhydrous organic solvent is preferably without water beetle
One or more in alcohol, ethanol, the tert-butyl alcohol and tetrahydrofuran, more preferably absolute ethyl alcohol；Described anhydrous organic solvent
Consumption is preferably 5-30 times of SM-2 moles, more preferably 15 times；The temperature of described reaction is preferably 45-75 DEG C,
More preferably 55-65 DEG C；
Step 2) in, the temperature of described reaction is preferably -50 DEG C to -85 DEG C, more preferably -65 DEG C to -75 DEG C；Institute
The ML stated1L2L3Consumption be preferably 0.3-1.0 times, more preferably 0.6-0.7 times of SM-2 moles；Described ML1L2
(PPh)3Preferably RuCl2P(Ph3)3；
Step 3) in, the temperature of described reaction is preferably -50 DEG C to -85 DEG C, more preferably -65 DEG C to -75 DEG C；Institute
Complex ligands Ia, Ib or Ic for stating consumption are preferably 1-3 times of complex intermediate mole, more preferably 1.5-2
Times；
Above-mentioned steps 1)-step 3) in, the time of reaction is untill detecting reaction completely.
Work as ML1L2L is RuCl2P(Ph3)3When, Va, Vb and Vc of generation are as follows：
Method two：By Va, Vb or Vc described in method one under inert gas shielding respectively with except PPh3Outer
Complex ligands L reaction generation following metal complex IIa, IIb or IIc of other electrons, wherein, p=0, M, L, L1、L2、
Y、Y1、R1、R2、E、E1、E2And E3It is as defined above described, but L is not PPh3；
Wherein, preferably, generation metal complex IIa, IIb or IIc in, L be thricyclohexyl phosphorus or
Mes=2,4,6- trimethylphenyls；The temperature of described reaction is preferably 20 DEG C to 75 DEG C, is reacted with complex ligands IIIa
When be more preferably 60 DEG C to 75 DEG C, be more preferably 20 DEG C to 35 DEG C when being reacted with complex ligands IIId；Described IIIa or
IIId consumption is preferably 1-3 times of complex intermediate Va, Vb or Vc mole, more preferably 1.5-2 times；
Method three：By IIa, IIb or IIc under inert gas shielding respectively with addition to thricyclohexyl phosphorus other to electricity
Complex ligands L reaction generation following metal complex IIa, IIb or IIc of son, wherein, as reactant IIa, IIb or
In IIc：P=0, M, L1、L2、Y、Y1、R1、R2、E、E1、E2And E3As defined above described, L is thricyclohexyl phosphorus；It is used as product
IIa, IIb or IIc in：P=0, M, L1、L2、Y、Y1、R1、R2、E、E1、E2And E3It is as defined above described, but L is not three hexamethylenes
Base phosphorus；
Method four：Under inert gas shielding, by product IIa, IIb described in any one of method one to method three
Or the complex ligands L of IIc and electron3Reaction generation IIa, IIb or IIc, wherein, IIa, IIb of the product of this method
Or in IIc：P=1, M, L, L1、L2、L3、Y、Y1、R1、R2、E、E1、E2And E3It is the same as those described above；In method four, the temperature of described reaction
Degree is preferably 20 DEG C to 35 DEG C.
Method one is into method four, preferably, L1And L2It is chlorine.
Here each reaction condition in method three and method four is the normal condition of this two class reaction.
In the present invention, when Z is CH2When, metal complex ligand i a of the invention can be prepared by following reaction：
Wherein, the normal condition that the conditions of the reaction can react for such Suzuki.Similarly, when Z is CH2When, Ib and Ic
Also it can be reacted and prepared by this class.
Wherein Y, Y1、R1、R2、E、E1、E2And E3It is as defined above.
The metal complex of the present invention can also be prepared by other two methods, be prior art, their route is such as
Shown in lower：
Preparation method one：
Each reaction condition 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-s (TsNHN).First from amino-sulfonyl and
The benzaldehyde of the electron-withdrawing groups such as sulfonamide substitution generates Ia, Ib or Ic with tolysulfonyl hydrazine reaction, then in inert gas shielding
Under, Cabbeen is generated in the ethanol solution of caustic alcohol or sodium methoxide, afterwards and RuCl2P(Ph3)3Reaction generation is containing triphenyl phosphorus
Ruthenium complex (Va-Vc), ruthenium complex (Va-Vc) generates part (L) with thricyclohexyl phosphorus reaction again under inert gas shielding
For III d ruthenium complex (IIa-IIc), according to chemism by complex compound (Va-Vc) or complex compound that obtained part is III d
(IIa-IIc) generation part is reacted with five-membered ring part (IIIa) under inert gas shielding more preferable for III a catalytic activity
The c of II a- of complex compound catalyst II.
Preparation method two：
Wherein:L=thricyclohexyls phosphorus or
Thus IIa and IIb route can equally be prepared.Each reaction condition in this route is the routine of this few class reaction
Condition；Wherein, EWG is electron withdraw group, L be thricyclohexyl phosphorus orMes is 2,4,6- trimethylbenzenes
Base.
In above two syntheti c route, M is ruthenium (Ru), L1=L2=Cl；Y、Y1、R1、R2、E、E1、E2And E3Definition it is same
Before.
In the present invention, described heterocyclic radical is preferably heterocyclic aryl.
The fourth object of the present invention is to provide the above-mentioned c of II a- of formula II metal complex in olefin metathesis metathesis reaction
Make the application of catalyst.
Wherein, described olefin metathesis metathesis reaction be preferably intramolecular cyclization olefin metathesis metathesis reaction,
Intermolecular olefin metathesis metathesis reaction (CM) or intermolecular cycloolefin ring opening metathesis polymerzation (ROMP).
The described cycloolefin for olefinic polyreaction (ROMP) is preferably tensioned cycloolefin structure or many
Cycloolefin structure, described cycloolefin structure or polycyclic olefin structure are substituted or non-substituted structure, and they are at one
Or contain F, Cl, Br, N, O, Si, S, P, B, C in multiple rings6-C15Aromatic series and C4-C15One kind in aromatic heterocycle substituent or
It is a variety of.
In the preferred embodiments of the present invention, described cycloolefin structure contains 4 or 5 or 7-16 carbon atom, or
Multiple hetero atoms or heteroatom group；Described polycyclic olefin structure is the polycyclic olefin structure containing 2 to 6 rings；Described
Polycyclic olefin is one or more of cyclopentadiene or its molecule hydrogen by C1-C15Saturation or undersaturated alkyl, substitution or not
Substituted C1-C15Amido, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group, substitution or not
Substituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C6-C15Arylthio, connection
Substituted or unsubstituted C1-C15The carbonyl of alkoxy, formyloxy, formamido, substituted or unsubstituted C1-C15Alkyl
Epoxide, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C6-C15Arylcarbonyloxy or substitution
Or unsubstituted C6-C15The derivative of aryl carboxamides base substitution.
In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIa and VIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution
Or unsubstituted C1-C15The carbonyl of alkoxy, substituted or unsubstituted C1-C15Alkyl amine group, substituted or unsubstituted C1-C15Virtue
Base amido, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C1-C15Aryl carboxamides base or substitution
Or unsubstituted C1-C15Heterocyclic radical formamido；
R10And R11It independently is hydrogen, halogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkane
Epoxide, substituted or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15
Aryl, C2-C15Heterocyclic radical, C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formamido,
Substituted or unsubstituted C1-C15Alkyl amido, C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkane
Base urea groups, ionic liquid monomer, liquid crystal monomer, active drug molecule；In Formula IV a, R10And R11It is not linked to be cyclic structure or company
Circlewise structure.
In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIIa-VIIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution
Or unsubstituted C1-C15The carbonyl of alkoxy, formamido, substituted or unsubstituted C1-C15Alkyl amido, substitution or not
Substituted C1-C15Aryl carboxamides base or substituted or unsubstituted C1-C15Heterocyclic radical formamido；
R12For substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15It is alkoxy, substituted or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15Heterocyclic radical, company
Meet substituted or unsubstituted C1-C15The carbonyl of alkoxy, formamido, substituted or unsubstituted C1-C15Formamido, C1-C15
Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active medicine
Molecule；
R13And R14It independently is substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution
Or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15
Heterocyclic radical, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formamido, substituted or unsubstituted C1-C15Formamide
Base, C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl 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 to prepare high molecular polymerization
The polymerisation of thing material, the organic solvent of reaction is preferably dichloromethane, dichloroethanes, chloroform, toluene, dimethylbenzene, chlorine
One or more in benzene and ionic liquid., can not be added with when the raw material cycloolefin or polycyclic olefin of reaction are liquid
Machine solvent.
It is described as made from intermolecular cycloolefin ring opening metathesis polymerzation in the another preferred embodiments of the present invention
High molecular polymer, is as shown in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD；
Wherein, R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-
C20Alkyl, C1-C20Alkoxy, substituted or unsubstituted C1-C20Aryloxy group, C1-C20Heterocyclic radical epoxide, C1-C20Alkylthio group, C1-
C20Alkane silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, C6-C20Aryloxy group, connection
C1-C20The carbonyl of alkyl, connection C6-C20The carbonyl of aryl, connection C2-C20The carbonyl of heterocyclic radical, connection C6-C20The carbonyl of aryloxy group
Base, connection C6-C20The carbonyl of heterocyclic radical epoxide, the substituted or unsubstituted C of connection1-C20The epoxide carbonyl of saturation or unsaturated alkyl
Base, aminoacyl, the substituted or unsubstituted C of connection1-C20The carbonyl of saturation or unsaturated alkyl amino, connection C6-C20Aryl ammonia
The carbonyl of base, connection C2-C20The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substitution or not
Substituted C6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20The sulfonyl of alkyl amino,
Connect C6-C20The sulfonyl or connection C of arylamino2-C20The sulfonyl of heterocyclylamino group；n1For 102-104；m1For 102-104。
Preferably, above-mentioned high molecular polymer is in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD：
R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-C15Alkane
Base, C1-C15Alkoxy, C1-C15Heterocyclic oxy group, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkyl siloxy, C2-C15It is miscellaneous
Ring group, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, connection C1-C15The carbonyl of alkyl, company
Meet C6-C15The carbonyl of aryl, connection C2-C15The carbonyl of heterocyclic radical, the substituted or unsubstituted C of connection1-C15Saturation or unsaturated hydrocarbons
The Epoxide carbonyl of base, connection C6-C15The carbonyl of aryloxy group, connection C6-C15The carbonyl of heterocyclic radical epoxide, aminoacyl, connection take
Generation or unsubstituted C1-C15The carbonyl of saturation or unsaturated alkyl amino, connection C6-C15The carbonyl of arylamino, connection C2-C15
The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, substituted or unsubstituted C6-C15Aryl ureas
Base, substituted or unsubstituted C2-C15Heterocyclic radical urea groups, connection C1-C15The sulfonyl of alkyl amino, connection C6-C15Arylamino
Sulfonyl, connection C2-C15The sulfonyl of heterocyclylamino group；n1For 102-104；m1For 102-104。
More preferably, described high molecular polymer is in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD：
R10、R11、R12、R13And R14It independently is hydrogen, halogen, substituted or unsubstituted C1-C8Alkyl, C1-C8Alkoxy,
C1-C8Alkylthio group, C1-C8Alkane silicon substrate, C1-C8Alkyl siloxy, C2-C8Heterocyclic radical, substituted or unsubstituted C6-C12Aryl, substitution
Or unsubstituted C6-C12Aryloxy group, connection C1-C8The carbonyl of alkyl, connection C6-C12The carbonyl of aryl, connection C2-C8Heterocyclic radical
Carbonyl, connect substituted or unsubstituted C1-C8Saturation or the Epoxide carbonyl of unsaturated alkyl, connection C6-C12The carbonyl of aryloxy group
Base, connection C6-C8The carbonyl of heterocyclic radical epoxide, aminoacyl, the substituted or unsubstituted C of connection1-C8Saturation or unsaturated alkyl
The carbonyl of amino, connection C6-C12The carbonyl of arylamino, connection C2-C8The carbonyl of heterocyclylamino group, connection C1-C8Alkyl amino
Sulfonyl, connection C6-C12The sulfonyl of arylamino, connection C2-C8The sulfonyl of heterocyclylamino group；n1For 102-104；m1For
102-104。
Optimal, described high molecular polymer is in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD：
In VIc：
A is CH2Or oxygen；
R11And R10Alone for connection C1-C3Saturation or the Epoxide carbonyl of unsaturated alkyl, connect non-substituted or taken by CN
The C in generation6-C12The carbonyl of aryloxy group, connect by C6—C12The C of aryl substitution1-C3The carbonyl of alkoxy, connect by C6—C12Fragrant oxygen
The carbonyl of the alkoxy of base substitution, the C for connecting unsubstituted or CN substitutions6-C12Aryloxy group, connection C1-C3Saturation or unsaturated alkyl
The carbonyl of amino, connect by C6The C of aryl substitution1-C3The carbonyl or connection C of alkyl amino2-C5The carbonyl of heterocyclic radical；
In VIIc：
A is CH2, oxygen；
R12For C1-C5Saturation or undersaturated alkyl, by C1-C3The C of alkoxy substitution1-C3Alkyl, it is optionally substituted by a hydroxyl group
C1-C3Alkyl, by C1-C3The C of alkyl acyloxy substitution1-C3Alkyl, by C6-C12The C of aryl substitution1-C3Alkyl, connected C1-
C3The C of the carbonyl substitution of alkoxy1-C3Alkyl, by C1-C3The C of alkoxy carbonyl group substitution6-C12Aryl, quiltSubstitution
Aryl or C1-C3Alkoxy；
In VIId：
A is CH2Or oxygen；
R14And R13It is C1-C3Alkyl.
The invention further relates to a kind of high molecular polymerization as shown in Formula IV c, VId, VIe, VIIc, VIId and Poly-DCPD
Thing, wherein, R10、R11、R12、R13、R14、n1And m1As described above.
Described high molecular polymer can be made by any of following two methods：
Method one：When raw material monomer is liquid, it comprises the following steps：
Under inert gas shielding, the metal complex catalyst of raw material monomer and the present invention carry out heating response, you can system
Obtain VIc, VId, VIe, VIIc, VIId or Poly-DCPD.
Method two：When raw material monomer is solid or liquid, it comprises the following steps：
Under inert gas shielding, in anhydrous organic solvent, the metal complex catalyst of raw material monomer and the present invention are from 20
DEG C progressively it is warming up to 75 DEG C of reactions, you can VIc, VId, VIe, VIIc, VIId or Poly-DCPD is made.
In described method one：The consumption of catalyst is preferably the 0.5%-10% of raw material monomer mole, heating
The temperature of reaction is preferably 30-120 DEG C；In described method two：The consumption of catalyst is preferably raw material monomer mole
The 0.01%-5% of amount, anhydrous organic solvent is preferably dichloroethanes (DCE).
When high molecular polymer is Poly-DCPD, it can be made by method one, and step is as follows：
Wherein, n1For 102-104；m1For 102-104。
Argon gas is passed through in liquid bicyclopentadiene monomer (DCPD) to rush oxygen, then rapidly joins this project etc. filters out
Ruthenium catalyst (0.1-5 ‰), reaction solution gradually becomes viscous and exothermic after heating response a few minutes between 30-120 degree, finally gathers
Conjunction obtains the luxuriant diene polymeric solid product (Poly-DCPD) of poly bis ring.Polymer P oly-DCPD solids have good hardness
(>80Gpa), bending modulus (>20Gpa) and heat distortion temperature (>200℃).
When high molecular polymer is VIc, it can be made by method two, and step is as follows：
1) under inert gas shielding, olefinic monomer raw material VIa is dissolved in anhydrous solvent (such as dichloroethanes DCE), filled
Argon catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. is filtered out, and reaction, which progressively heats up (20-75 DEG C), to be added
Thermal response, reaction solution gradually becomes viscous；
2) reaction solution is slowly toppled over after reaction overnight and be precipitated out in ethanol, produced filtering and drying to obtain polymer solids
Thing (VIc), yield is 80-98%；Wherein, R10、R11、n1It is as defined above.
The invention further relates to high molecular polymer prepare the explosion-proof lamp of high intensity and high rigidity, tire material,
Effective carrier, tooth patching material, Liquid Crystalline Polymeric Materials, conductive polymer new material, film or the spinning of macromolecule medicament prodrug
Application in wire material.
In the present invention, described alkyl is to include the saturated aliphatic hydrocarbon with specified carbon number purpose side chain or straight chain
Base；Such as in " C1-C10Have 1,2,3,4,5,6,7,8,9 or 10 defined in alkyl " to be included in straight chain or branched structure
The group of individual carbon atom.For example, " C1-C10Alkyl " specifically include methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group,
Isobutyl group, amyl group, hexyl, heptyl, octyl group, nonyl and decyl etc..
Described " alkoxy " represent alkyl be connected with oxygen atom after generation group, i.e., " RO- ", R is alkyl.
Described " aryl " refers to the monocyclic or bicyclic carbocyclic that 7 atoms are may be up in each ring of any stabilization, its
In at least one ring be aromatic rings；The example of above-mentioned aryl unit include phenyl, naphthyl, tetralyl, indanyl,
Xenyl, phenanthryl, anthryl or acenaphthenyl (acenaphthyl).It is appreciated that be two ring substituents in aryl substituent, and its
In in the case of a ring is non-aromatic ring, connection is carried out by aromatic ring.
What " heterocyclic aryl " represented in each ring up to 7 atoms stablizes monocyclic or two rings, and wherein at least one ring is
Aromatic rings and contain the hetero atoms that 1-4 is selected from O, N and S；Heterocyclic aryl within the range defined herein includes but is not limited to：
Acridinyl, carbazyl, cinnolines base, quinoxalinyl, pyrazolyl, indyl, BTA base, furyl, thienyl, benzothiophene
It is base, benzofuranyl, quinolyl, isoquinolyl, oxazolyl, isoxazolyls, indyl, pyrazinyl, pyridazinyl, pyridine radicals, phonetic
Piperidinyl, pyrrole radicals, tetrahydroquinoline.As the definition of following heterocycle, " heterocyclic aryl " is it should also be understood that be to include any contain
The N- oxide derivatives of azepine aryl.Heterocyclic aryl substituent is two ring substituents wherein and a ring is non-aromatic ring
Or not comprising in the case of heteroatomic, it will be understood that connection by aromatic ring or passes through the hetero atom comprising ring and carried out respectively.
" alkylthio group " represent alkyl be connected with sulphur atom after generation group, i.e., " RS- ", R is alkyl.
" aryloxy group " represent aryl be connected with oxygen atom after generation group, i.e., " RO- ", R is aryl.
" fragrant amino " refers to " NH3" in a hydrogen be substituted with aryl after amino.
" alkyl imino " refers to the imino group for being connected with alkyl, and alkyl can be connected on the carbon of imino group or on nitrogen；" substitution
Alkyl imino " refer to one or more of alkyl imino hydrogen it is substituted after group.
" substituted amino " is " NH3" in any one or more hydrogen it is substituted after group.Substituent can be C6-
C20Aryl, formoxyl, C1-C20Alkyl acyl, the C of substitution1-C20Alkyl acyl, alkyl sulphonyl, the C of substitution1-C20Alkyl sulphur
Acyl group etc..
Wherein, " alkyl sulphonyl " is connected with the group of alkyl, " substituted alkyl sulphonyl " for the sulphur atom on sulfonyl
Group after being substituted with a substituent for one or more of alkyl sulphonyl hydrogen；" alkyl acyl " be acyl group in carbon atom or
Nitrogen-atoms is connected to the acyl group of alkyl, and " substituted alkyl acyl " is that any one or more hydrogen in alkyl acyl are substituted base
Group after substitution.
" heterocyclic radical " be fragrance or nonaromatic heterocycles containing one or more of the hetero atom selected from O, N and S, and
And including bicyclic groups.Therefore, " heterocyclic radical " includes above-mentioned heterocyclic aryl and its dihydro or tetrahydrochysene analog." heterocyclic radical "
Other examples include but is not limited to it is following：Benzimidazolyl, benzofuranyl, benzopyrazoles base, BTA base, benzo thiophene
It is fen base, benzoxazolyl, carboline base, furyl, imidazole radicals, indolinyl, indyl, indazolyl, isobenzofuran-base, different
Indyl, isoquinolyl, isothiazolyl, isoxazolyl, oxazolyl, oxazoline, isoxazolines, oxygen cyclobutyl, pyranose, pyrrole
Piperazine base, pyrazolyl, pyridazinyl, pyridopyridine base, pyridazinyl, pyridine radicals, pyrimidine radicals, pyrrole radicals, quinazolyl, quinolyl,
Quinoxalinyl, THP trtrahydropyranyl, thiadiazolyl group, thiazolyl, thienyl, triazolyl, azetidinyl, 1,4- alkyl dioxins,
Hexahydro azatropylidene base, piperazinyl, piperidyl, pyrrolidinyl, morpholinyl, thio-morpholinyl, dihydrobenzo imidazole radicals, dihydrobenzo
Furyl, dihydrobenzo thienyl, Er hydrogen benzoxazolyl, dihydrofuran base, glyoxalidine base, indolinyl, dihydro are different
Oxazolyl, dihydro isothiazolyl, Er Qing oxadiazolyls, dihydro-oxazole base, dihydro pyrazine base, pyrazoline base, dihydropyridine base,
Dihydro-pyrimidin base, pyrrolin base, EEDQ base, dihydro tetrazole radical, thiodiazoline base, dihydro-thiazolyl, dihydro-thiophene
Base, dihydro triazolyl, dihydro azetidinyl, methylenedioxyphenyl formoxyl, tetrahydrofuran base and tetrahydro-thienyl and
Its N- oxide.Heterocyclic radical can be attached through carbon atom or hetero atom with central element.
" substituted heterocyclic radical " be heterocyclic radical in any one or more hydrogen be substituted with a substituent after group.
" alkyl amido " is that carbon or nitrogen in formamido is ined succession the group of alkyl, " substituted alkyl amido "
Group after being substituted with a substituent for any one or more hydrogen in alkyl amido.
" siloxy " is that structural formula is R1R2R3SiO- group；" alkyl siloxy " is R1R2R3R in SiO-1、R2And R3In
At least one is alkyl, and remaining is the group of hydrogen；" substituted alkyl siloxy " is one or more of alkyl siloxy
Group after hydrogen is substituted.
" alkyl amido " is the generation group after the hydrogen on carbon or the hydrogen on nitrogen are replaced by alkyl in formamido；
" substituted alkyl amido " is the group after one or more of alkyl amido hydrogen is substituted with a substituent.
" alkane silicon substrate " is structure R1R2R3In Si-, R1、R2And R3In at least one be alkyl, remaining be hydrogen group.
" aminoacyl " is that structural formula isGroup.
" carbonyl of connection alkyl amino " is that the nitrogen in aminoacyl connects the group formed after alkyl；" substituted connection
Group of the carbonyl of alkyl amino " for one or more of the carbonyl of connection alkyl amino hydrogen after substituted.
" alkyl urea groups " is the group after one or more hydrogen in urea groups on nitrogen are replaced by alkyl；" substituted ureine
Base " is the group after one or more of alkyl urea groups hydrogen is substituted.
Raw material involved in the present invention and reagent are commercially available unless otherwise specified.
The present invention positive effect be：
1st, the present invention is fully ground by designing and synthesizing metal complex part and corresponding metal especially ruthenium complex
Study carefully the influence of the substituent and its position of substitution of different ligands to the catalytic activity and stability of catalyst, as a result show the present invention
Metal complex catalyst have higher olefin metathesis metathesis reaction catalytic activity, and with amino-sulfonyl,
The adjacent alkoxystyrene complex ligands of the electron-withdrawing groups such as sulfoamido, carbonyl, chlorine substitution significantly improve respective metal complexing
The catalytic activity and stability of thing.The present invention metal complex catalyst can be effectively used for intramolecular alkene ring closure reaction,
Intermolecular cycloolefin ring-opening polymerization etc., is new chemical materialses and pharmaceutical synthesis etc. with extensive industry application value
Field provides a kind of new synthetic method by olefin metathesis metathesis reaction.
2nd, the novel metal complexes structural formula of present invention design synthesis is the c of II a- of formula II, its chemical catalysis performance and thing
Rationality energy and its various Sexual behavior mode of application increase significantly and improved compared with Grubbs-Hoveyda catalyst, and optimize gold
Belong to the preparation method of complex compound, largely reduce preparation cost, be the industry metaplasia of the catalytic reaction of metal complex
Production provides an effective practical new method.
3rd, the present invention have developed by being prepared under the conditions of different monomer process by the catalyzed ring opening polymerization reaction of cycloolefin
The high molecular polymer new material of different performance and preparation method thereof.
4th, the main application of high molecular polymer new material prepared by the present invention is the explosion-proof green wood of high intensity and high rigidity
Material, tire new material, effective new support of macromolecule medicament prodrug, tooth patching material, Liquid Crystalline Polymeric Materials, conductive polymer
Deng new material, it can also be used to which film and spinning prepare new material.It can provide more for the development of human society in field of new materials
More preferable new product.
Embodiment:
The present invention according to researched and developed about olefin metathesis reaction catalyst data (patent US20070043180A1,
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 not
The complexing of the complex ligands (3a-3cz, 5a-5z, 7a-7t, 9a-9j, 11a-11j) and ruthenium complex intermediate of same type is anti-
Different types of metal ruthenium complex (4a-4u, 6a-6v, 8a-8e, 10a-10e, 12a-12f) should be prepared for, and is passed through respectively
The catalytic cyclization and ring-opening polymerization of alkene have studied the structure and substituent effect of different type complex ligands to its phase
The influence of metal complex catalytic activity is answered, and it is poly- by alkene open loop to have extensively studied different type metal complex catalyst
The macromolecular material that reaction prepares different performance is closed, and further research and development optimize different types of new complex compound for preparing
High molecular polymer new material of different performance and preparation method thereof and multiple use.
The following is according to relevant documents and materials ruthenium complex 4a-4cz is synthesized using complex ligands (3a-3cz)：
It is complex compound 4a-4cz structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
It is ruthenium complex 4a-4cz synthesis below:
The ruthenium complex 4a of embodiment 1 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3a (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4a, yield：32%.
After testing, ruthenium complex (4a)1HNMR(400MHz,CDCl3):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,
NCH2),4.14-3.90(m,4H,NCH2CH2N),3.85(s,3H,OCH3), 3.47 (d, J=12.8Hz, 1H, NCH2),2.89-
1.62(m,18H,aromatic CH3).
The ruthenium complex 4b of embodiment 2 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3b (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4b, yield：35%.
After testing, ruthenium complex (4b)1HNMR(400MHz,CDCl3):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, NCH2), 3.85 (d, J=
12.4Hz,1H,NCH2),3.80(s,3H,OCH3),2.28-1.24(m,33H,PCy3).
The ruthenium complex 4c of embodiment 3 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3c (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4c, yield：14%.
After testing, ruthenium complex (4c)1HNMR(400MHz,CDCl3):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, NHCH2),4.19-3.58(m,8H,NHCH2,NCH2CH2N, NCH3),2.52-2.37(m,
18H,aromatic CH3).
The ruthenium complex 4d of embodiment 4 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3d (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4d, yield：13%.
After testing, ruthenium complex (4d)1HNMR(400MHz,CDCl3):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, OCH3), 3.70 (d, J=12.4Hz, 1H, NH),
2.57(s,3H,OCH3),2.29-1.21(m,33H,PCy3).
The ruthenium complex 4e of embodiment 5 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3e (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4e, yield：13%.
After testing, ruthenium complex (4e)1HNMR(400MHz,CDCl3):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,
NHCH2),4.19-3.55(m,8H,NHCH2,NCH2CH2N, NCH3),2.86-2.10(m,18H,aromatic CH3).
The ruthenium complex 4f of embodiment 6 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3f (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4f, yield：28%.
After testing, ruthenium complex (4f)1HNMR(400MHz,CDCl3):δ7.69-7.60(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,
NCH2), 3.87 (d, J=12.4Hz, 1H, NCH2),3.78(s,3H,OCH3),2.38-1.13(m,33H,PCy3).
The ruthenium complex 4g of embodiment 7 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3g (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4g, yield：7%.
After testing, ruthenium complex (4a)1HNMR(400MHz,CDCl3):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,NCH2),4.4-3.89(m,4H,NCH2CH2N),3.83(s,3H,OCH3), 3.45 (d, J=12Hz, 1H,
NCH2),2.86-1.56(m,21H,NCH3,aromatic CH3).
The ruthenium complex 4h of embodiment 8 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3h (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4h, yield：29%.
After testing, ruthenium complex (4h)1HNMR(400MHz,CDCl3):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, NCH2),3.71(s,3H,
OCH3), 3.62 (d, J=12Hz, 1H, NCH2),2.51(s,3H,NCH3),2.22-1.13(m,33H,PCy3).
The ruthenium complex 4j of embodiment 9 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3j (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4j, yield：37%.
After testing, ruthenium complex (4j)1HNMR(400MHz,CDCl3):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, NHCH2,NCH2CH2N, OCH3),
2.62-2.08(m,18H,aromatic CH3).
The ruthenium complex 4k of embodiment 10 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3k (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4k, yield：52%.
After testing, ruthenium complex (4k)1HNMR(400MHz,CDCl3):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,
NCH2), 5.27 (t, J=6Hz, 1H, NH), 3.93 (d, J=12Hz, 1H, NCH2),3.88(s,3H,OCH3),2.33-1.24
(m,33H,PCy3).
The ruthenium complex 4m of embodiment 11 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3m (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4m, yield：84%.
After testing, ruthenium complex (4m)1HNMR(400MHz,CDCl3):δ 18.89 (s, Ru=CH), 7.60-6.45 (m,
11H,aromatic H),5.13-3.52(m,8H,NHCH2,NCH2CH2N, OCH), 2.95-2.10 (m, 18H, aromatic
CH3), 0.95 (d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4n of embodiment 12 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3n (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4n, yield：58%.
After testing, ruthenium complex (4n)1HNMR(400MHz,CDCl3):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,
NCH2), 5.13 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.90 (d, J=12Hz, 1H, NCH2),2.30-1.25(m,
39H,PCy3).
The ruthenium complex 4p of embodiment 13 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3p (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4p, yield：10%.
After testing, ruthenium complex (4p)1HNMR(400MHz,CDCl3):δ 18.97 (s, Ru=CH), 7.50-6.58 (m,
11H,aromatic H),5.26-3.52(m,8H,NHCH2,NCH2CH2N, OCH), 3.48-2.07 (m, 18H, aromatic
CH3), 1.23 (d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4n of embodiment 14 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3q (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4q, yield：31%.
After testing, ruthenium complex (4q)1HNMR(400MHz,CDCl3):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,
NCH2), 5.22 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.95 (d, J=12Hz, 1H, NCH2),2.34-0.87(m,
39H,PCy3).
The ruthenium complex 4r of embodiment 15 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3r (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4r, yield：14%.
After testing, ruthenium complex (4n)1HNMR(400MHz,CDCl3):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, NHCH2,NCH2CH2N,OCH3),
2.56-1.78(m,18H,aromatic CH3).
The ruthenium complex 4s of embodiment 16 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3s (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4s, yield：37%.
After testing, ruthenium complex (4s)1HNMR(400MHz,CDCl3):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,
NCH2), 5.35 (t, J=6Hz, 1H, NH), 3.96 (d, J=12Hz, 1H, NCH2),3.91(s,3H,OCH3),2.34-1.22
(m,33H,PCy3).
The ruthenium complex 4t of embodiment 17 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3t (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid 4t, impure, thick yield：21%, nothing1HNMR analysis knots
Really.
The ruthenium complex 4u of embodiment 18 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3u (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid 4u, impure, thick yield：7%, nothing1HNMR analysis knots
Really.
The ruthenium complex 4v of embodiment 19 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3v (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4v, yield：45%.
After testing, ruthenium complex (4v)1HNMR(400MHz,CDCl3):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, NCH2),4.180-3.857(m,6H,NCH2CH2N,OCH2), 3.549 (d, J=11.2Hz,
1H,NCH2),2.790-2.000(m,18H,aromatic CH3),1.19(m,OCH2CH3).
The ruthenium complex 4w of embodiment 20 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3w (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4w, yield：7%.
After testing, ruthenium complex (4w)1HNMR(400MHz,CDCl3):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,NCH2,NCH2CH2N),3.884(s,3H,OCH3),2.645(s,3H,NCH3),2.495(s,
12H,aromatic CH3),2.347(s,6H,18H,aromatic CH3),0.912(m,6H,OCH(CH3)2).
The ruthenium complex 4x of embodiment 21 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3x (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4x, yield：40%.
After testing, ruthenium complex (4x)1HNMR(400MHz,CDCl3):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,NCH2),4.180(s,4H,NCH2CH2N),3.887(s,6H,OCH3),2.494(s,12H,
aromatic CH3),2.402(s,6H,aromatic CH3).
The ruthenium complex 4y of embodiment 22 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3y (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4y, yield：50%.
After testing, ruthenium complex (4y)1HNMR(400MHz,CDCl3):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, NCH2),4.451(m,1H,OCH3),4.202-4.051(m,4H,
NCH2CH2), N 3.615 (d, J=12Hz, 1H, NCH2),2.692-2.026(m,18H,aromatic CH3), 1.177 (d, J=
5.6Hz,6H,OCH(CH3)2).
The ruthenium complex 4z of embodiment 23 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3z (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 4z, yield：49%.
After testing, ruthenium complex (4z)1HNMR(400MHz,CDCl3):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,NCH2),4.179(s,4H,NCH2CH2N),
3.886(s,3H,OCH3),2.493(s,12H,aromatic CH3),2.399(s,6H,18H,aromatic CH3),0.931
(m,6H,OCH(CH3)2).
The ruthenium complex 4aa of embodiment 24 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3aa (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4aa, yield：55%.
After testing, ruthenium complex (4aa)1H-NMR(400MHz,CDCl3):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,NCH2),5.225(m,1H,NH),
4.159-3.942(m,3H,NCH2,OCH2),2.358-0.812(m,36H,PCy3,OCH2CH3).
The ruthenium complex 4ab of embodiment 25 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ab (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ab, yield：8%.
After testing, ruthenium complex (4ab)1H-NMR(400MHz,CDCl3):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,NCH2), 4.226 (d, J=13.2Hz, 1H, NCH2),4.104(s,3H,OCH3),3.800(s,4H,
NCH2CH2), N 3.686 (d, J=13.2Hz, 1H, NCH2),2.646-2.075(m,18H,aromatic CH3).
The ruthenium complex 4ac of embodiment 26 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ac (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ac, yield：63%.
After testing, ruthenium complex (4ac)1H-NMR(400MHz,CDCl3):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,NCH2),
4.334(s,3H,OCH3),3.896(s,3H,OCH3),2.345-1.272(m,33H,18H,PCy3).
The ruthenium complex 4ad of embodiment 27 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ad (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ad, yield：3%.
After testing, ruthenium complex (4ad)1H-NMR(400MHz,CDCl3):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,
NCH2), 4.152 (d, J=13.2Hz, 1H, NCH2),4.083-3.769(m,7H,NCH2CH2N,OCH3),3.195(s,3H,
NCH3),2.409(m,18H,aromatic CH3).
The ruthenium complex 4ae of embodiment 28 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ae (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ae, yield：50%.
After testing, ruthenium complex (4ae)1H-NMR(400MHz,CDCl3):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, NCH2),4.451(m,1H,OCH3),4.202-
4.051(m,4H,NCH2CH2), N 3.615 (d, J=12Hz, 1H, NCH2),2.692-2.026(m,18H,aromatic CH3),
1.177 (d, J=5.6Hz, 6H, OCH (CH3)2).
The ruthenium complex 4af of embodiment 29 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3af (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4af, yield：15%.
After testing, ruthenium complex (4af)1H-NMR(400MHz,CDCl3):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, NCH2), 5.393 (d, J=13.2Hz, 1H, NCH2),4.074-3.770
(m,7H,NCH2CH2N,OCH3),3.518(s,3H,NCH3),2.648-2.303(m,18H,aromaticCH3).
The ruthenium complex 4ag of embodiment 30 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ag (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ag, yield：4%.
After testing, ruthenium complex (4ag)1H-NMR(400MHz,CDCl3):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, NCH2),4.044(s,4H,
NCH2CH2), N 3.612 (d, J=12.9Hz, 1H, NCH2),2.452(s,12H,aromatic CH3),2.332(s,6H,
aromatic CH3).
The ruthenium complex 4ah of embodiment 31 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ah (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ah, yield：5%.
After testing, ruthenium complex (4ah)1H-NMR(400MHz,CDCl3):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, NCH2),4.043(s,4H,
NCH2CH2), N 3.586 (d, J=12.9Hz, 1H, NCH2),2.445(s,12H,aromatic CH3),2.371(s,6H,
aromatic CH3).
The ruthenium complex 4am of embodiment 32 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3am (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4am, yield：40%.
After testing, ruthenium complex (4am)1H-NMR(400MHz,CDCl3):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, NHCH2,NCH2CH2N,
OCH3),2.62-2.05(m,18H,aromatic CH3).
The ruthenium complex 4an of embodiment 33 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3an (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4an, yield：51%.
After testing, ruthenium complex (4an)1H-NMR(400MHz,CDCl3):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, NCH2),4.05(s,
4H,NCH2CH2N),3.53(s,3H,OCH3), 3.43 (d, J=12Hz, 1H, NCH2),2.56-2.13(m,21H,aromatic
CH3).
The ruthenium complex 4ap of embodiment 34 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ap (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ap, yield：50%.
After testing, ruthenium complex (4ap)1H-NMR(400MHz,CDCl3):δ 18.90 (s, 1H, Ru=CH), 7.38-
6.37(m,9H,aromatic H),4.85(m,2H,NH,NCH2),3.99(s,4H,NCH2CH2N), 3.80 (d, J=12Hz,
1H,NCH2),3.31(s,3H,OCH3),2.69-0.85(m,38H,C(CH3)3,aromatic CH3).
The ruthenium complex 4aq of embodiment 35 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3aq (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4aq, yield：37%.
After testing, ruthenium complex (4aq)1H-NMR(400MHz,CDCl3):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,NCH2),4.02(s,4H,NCH2CH2N),
3.41(m,1H,NCH2),2.53-2.31(m,18H,aromatic CH3),1.29(s,9H,C(CH3)3),0.89-0.87(m,
6H,OCH(CH3)2).
The ruthenium complex 4ar of embodiment 36 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ar (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ar, yield：54%.
After testing, ruthenium complex (4ar)1H-NMR(400MHz,CDCl3):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, NCH2),4.39-4.33(m,
2H,OCH),4.15-4.02(m,4H,NCH2CH2N),3.65(m,1H,NCH2),2.66-2.05(m,18H,aromatic
CH3),1.55(m,6H,OCH(CH3)2),1.38(m,6H,OCH(CH3)2).
The ruthenium complex 4as of embodiment 37 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3as (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4as, yield：46%.
After testing, ruthenium complex (4as)1H-NMR(400MHz,CDCl3):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, NCH2),
4.36(m,1H,OCH),4.06(brs,4H,NCH2CH2), N 3.42 (d, J=13.2Hz, 1H, NCH2),2.63-2.09(m,
21H,aromatic CH3),1.09(m,6H,OCH(CH3)2).
The ruthenium complex 4at of embodiment 38 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3at (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4at, yield：37%.
After testing, ruthenium complex (4at)1H-NMR(400MHz,CDCl3):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,NCH2),3.79(s,3H,OCH3),3.76(s,3H,OCH3),2.26-1.25(m,33H,PCy3).
The ruthenium complex 4aw of embodiment 39 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3aw (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4aw, yield：8%.
After testing, ruthenium complex (4aw)1H-NMR(400MHz,CDCl3):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,NCH2),3.72(m,1H,NCH2),2.26-1.24(m,48H,PCy3,C(CH3)3,OCH(CH3)2).
The ruthenium complex 4az of embodiment 40 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3az (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4az, yield：31%.
After testing, ruthenium complex (4az)1H-NMR(400MHz,CDCl3):δ 18.53 (s, 1H, Ru=CH), 7.26-
5.75 (m, 10H, aromatic H), 4.88 (d, J=11.2Hz, 1H, NCH2),4.52-4.43(m,2H,OCH),4.14-
3.88(m,5H,NCH2,NCH2CH2N),2.98-1.39(m,27H,NCH3,aromatic CH3,OCH(CH3)2).
The ruthenium complex 4ba of embodiment 41 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ba (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ba, yield：44%.
After testing, ruthenium complex (4ba)1H-NMR(400MHz,CDCl3):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,NCH2,NCH2CH2N),3.72(d,J
=13.2Hz, 1H, NCH2),2.48-2.34(m,19H,C(CH3)3,aromatic CH3),1.45-0.95(m,21H,OCH
(CH3)2,C(CH3)3).
The ruthenium complex 4bb of embodiment 42 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bb (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bb, yield：42%.
After testing, ruthenium complex (4bb)1H-NMR(400MHz,CDCl3):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,NCH2,NCH2CH2NH),3.7(s,3H,OCH3), 3.54 (d, J=13.2Hz, 1H, NCH2),2.48-2.18(m,
24H,aromatic CH3).
The ruthenium complex 4be of embodiment 43 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3be (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4be, yield：48%.
After testing, ruthenium complex (4be)1H-NMR(400MHz,CDCl3):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, NCH2,NCH2CH2N),
4.01 (d, J=13.2Hz, 1H, NCH2),2.75-2.00(m,19H,CH(CH3)2,aromatic CH3),1.01-0.90(m,
6H,CH(CH3)2).
The ruthenium complex 4bg of embodiment 44 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bg (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bg, yield：52%.
After testing, ruthenium complex (4bg)1H-NMR(400MHz,CDCl3):δ 18.95 (s, 1H, Ru=CH), 7.43-
6.36(m,10H,aromatic H),4.00(m,6H,NCH2,NCH2CH2N),2.67-2.06(m,20H,CH(CH3)2,
aromatic CH3),0.90-0.83(m,12H,CH(CH3)2).
The ruthenium complex 4bj of embodiment 45 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bj (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bj, yield：64%.
After testing, ruthenium complex (4bj)1H-NMR(400MHz,CDCl3):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, NCH2,NCH2CH2N),
2.77-1.90(m,27H,aromatic CH3).
The ruthenium complex 4bk of embodiment 46 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bk (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bk, yield：26%.
After testing, ruthenium complex (4bk)1H-NMR(400MHz,CDCl3):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, NCH2,NCH2CH2N),
3.44 (d, J=13.2Hz, 1H, NCH2),2.46-2.00(m,21H,aromatic CH3).
The ruthenium complex 4bn of embodiment 47 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bn (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bn, yield：38%.
After testing, ruthenium complex (4bn)1H-NMR(400MHz,CDCl3):δ 18.75 (s, 1H, Ru=CH), 7.26-
6.21(m,9H,aromatic H),4.05-3.85(m,5H,NCH2,NCH2CH2N),3.72(s,3H,OCH3), 3.34 (d, J=
13.2Hz,1H,NCH2),2.82-0.95(m,30H,NCH3,aromatic CH3).
The ruthenium complex 4br of embodiment 48 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3br (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4br, yield：14%.
After testing, ruthenium complex (4br)1H-NMR(400MHz,CDCl3):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, NCH2,
NCH2CH2), N 3.46 (d, J=11.3Hz, 1H, NCH2),2.62-1.00(m,21H,aromatic CH3).
The ruthenium complex 4bs of embodiment 49 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bs (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bs, yield：17%.
After testing, ruthenium complex (4bs)1H-NMR(400MHz,CDCl3):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, NCH2), 3.72 (d, J=11.3Hz, 1H, NCH2),2.29-0.95(m,
36H,PCy3,aromatic CH3,).
The ruthenium complex 4bv of embodiment 50 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bv (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bv, yield：90%.
After testing, ruthenium complex (4bv)1H-NMR(400MHz,CDCl3):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, NCH2),4.16-4.04(m,4H,NCH2CH2N),3.59(s,3H,OCH3), 3.48 (d, J=13.2Hz,
1H,NCH2),2.62-2.32(m,18H,aromatic CH3).
The ruthenium complex 4bw of embodiment 51 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bw (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bw, yield：49%.
After testing, ruthenium complex (4bw)1H-NMR(400MHz,CDCl3):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,
aromaticH),5.47(m,1H,NH),5.24(m,1H,NCH2), 3.92 (d, J=13.6Hz, 1H, NCH2),3.80(s,3H,
OCH3),2.30-0.87(m,33H,PCy3).
The ruthenium complex 4bx of embodiment 52 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bx (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4bx, yield：65%.
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,NHCH2),4.40-4.15(m,4H,NCH2CH2N),3.48-3.45(m,1H,NHCH2),2.64-2.04(m,
18H,aromatic CH3), 1.10 (d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4cc of embodiment 53 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cc (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cc, yield：23%.
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,NCH2CH2N),2.63-1.75(m,22H,NHCH2,aromatic CH3), 0.92 (d, J=7.6Hz, OCH (CH3)2),
0.83 (d, J=7.6Hz, OCH (CH3)2).
The ruthenium complex 4cd of embodiment 54 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cd (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cd, yield：42%.
After testing, ruthenium complex (4cd)1H-NMR(400MHz,CDCl3):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,NCH2),4.16-4.01(m,4H,
NCH2CH2N),3.58-3.54(m,4H,NCH2,OCH3),2.75(s,6H,NCH3),2.73-1.98(m,18H,aromatic
CH3).
The ruthenium complex 4cf of embodiment 55 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cf (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cf, yield：32%.
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,NHCH2),4.00(s,4H,
NCH2CH2N),2.51-2.49(m,1H,NHCH2),2.51-2.32(m,18H,aromatic CH3), 1.12 (d, J=7.6Hz,
OCH(CH3)2), 1.04 (d, J=7.6Hz, OCH (CH3)2).
The ruthenium complex 4cg of embodiment 56 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cg (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cg, yield：51%.
After testing,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), 7.29 (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,NHCH2),4.45-4.42
(m,1H,OCH),4.14-4.01(m,4H,NCH2CH2N),3.56-3.53(m,1H,NHCH2),3.12-3.07(m,4H,
NCH2),2.67-2.36(m,18H,aromatic CH3),1.99-1.00(m,24H,CH2CH2CH2CH3,OCH(CH3)2).
The ruthenium complex 4ch of embodiment 57 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ch (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ch, yield：74%.
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,
aromaticH),5.27-5.20(m,1H,NH),4.64-4.61(m,1H,NHCH2),4.46-4.44(m,1H,OCH),4.14-
4.01(m,4H,NCH2CH2N),3.59-3.56(m,1H,NHCH2),3.12-3.07(m,4H,NCH2),2.75(s,6H,NCH3),
2.67-2.36(m,18H,aromatic CH3), 1.13 (d, J=6.0Hz, 6H, OCH (CH3)2).
The ruthenium complex 4cj of embodiment 58 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cj (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cj, yield：77%.
After testing, ruthenium complex (4cj)1H-NMR(400MHz,CDCl3):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,NCH2),4.62-4.56(m,1H,OCH),3.99-3.96(m,1H,NCH2),2.80(s,6H,NCH3),2.30-1.24(m,
39H,PCy3,OCH(CH3)2).
The ruthenium complex 4ck of embodiment 59 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ck (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ck, yield：47%.
After testing, ruthenium complex (4ck)1H-NMR(400MHz,CDCl3):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,NCH2),4.16-4.12(m,4H,
NCH2CH2N),3.61(s,3H,OCH3),3.56-3.52(m,4H,NCH2),3.10-3.06(m,4H,NCH2),2.63-2.05
(m,18H,aromatic CH3),1.37-0.98(m,14H,CH2CH2CH3).
The ruthenium complex 4cm of embodiment 60 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cm (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cm, yield：27%.
After testing, ruthenium complex (4cm)1H-NMR(400MHz,CDCl3):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,NCH2),4.64-4.42(m,2H,OCH,NH),4.15-4.02(m,4H,NCH2CH2N),3.16(m,1H,NCH2),
3.17(m,1H,NCH),2.67-2.00(m,18H,aromatic CH3),1.85-1.00(m,16H,CH2CH2,OCH(CH3)2).
The ruthenium complex 4cn of embodiment 61 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cn (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cn, yield：26%.
After testing, ruthenium complex (4cn)1H-NMR(400MHz,CDCl3):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,NCH2),4.38-4.37(m,1H,NH),4.14-4.03(m,4H,NCH2CH2N),3.60(s,3H,OCH3),3.56-
3.53(m,1H,NCH2),3.14-3.13(m,1H,NCH),2.66-1.27(m,34H,aromatic CH3,CH2CH2,OCH
(CH3)2).
The ruthenium complex 4cp of embodiment 62 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cp (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cp, yield：68%.
After testing, ruthenium complex (4cp)1H-NMR(400MHz,CDCl3):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,NCH2,NCH2CH2), N 3.25 (d, J=13.6Hz, NCH2),2.76-1.27(m,24H,aromatic
CH3).
The ruthenium complex 4cr of embodiment 63 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cr (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cr, yield：59%.
After testing, ruthenium complex (4cr)1H-NMR(400MHz,CDCl3):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,NHCH2),4.41(m,1H,OCH),
3.96(m,4H,NCH2CH2N),3.55-3.52(m,1H,NHCH2),2.66-2.33(m,18H,aromatic CH3),1.14
(d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4cs of embodiment 64 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cs (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cs, yield：82%.
After testing, ruthenium complex (4cs)1H-NMR(400MHz,CDCl3):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,NCH2,NCH2CH2N,OCH2),3.55(m,
1H,NCH2),2.44-1.00(m,7H,aromatic CH3).
The ruthenium complex 4ct of embodiment 65 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ct (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4ct, yield：57%.
After testing, ruthenium complex (4ct)1H-NMR(400MHz,CDCl3):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,NCH2),3.96-
3.83(m,3H,OCH2,NCH2),2.28-1.00(m,40H,PCy3,CH2CH2CH3).
The ruthenium complex 4cu of embodiment 66 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cu (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cu, yield：65%.
After testing, ruthenium complex (4cu)1H-NMR(400MHz,CDCl3):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, NCH2,OCH2),
4.71-4.01(m,5H,NH,NCH2CH2), N 3.58 (d, J=12.8Hz, 1H, NCH2),2.89-1.29(m,21H,OCH2CH3,
aromatic CH3).
The ruthenium complex 4cw of embodiment 67 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cw (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cw, yield：85%.
After testing, ruthenium complex (4cw)1H-NMR(400MHz,CDCl3):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, NCH2),4.06-
3.93(m,7H,NH,NCH2CH2N,OCH2), 3.57 (d, J=12.8Hz, 1H, NCH2),2.89-1.29(m,29H,CH2CH3,
aromatic CH3).
The ruthenium complex 4cy of embodiment 68 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cy (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cy, yield：70%.
After testing, ruthenium complex (4cy)1H-NMR(400MHz,CDCl3):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, NCH2),4.52-
4.06(m,6H,NH,NCH2CH2N, OCH), 3.57 (d, J=12.8Hz, 1H, NCH2),2.89-1.29(m,24H,CH2CH3,
aromatic CH3).
The ruthenium complex 4cz of embodiment 69 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cz (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 4cz, yield：64%.
After testing, ruthenium complex (4cz)1H-NMR(400MHz,CDCl3):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, NCH2),4.50(m,1H,OCH),
3.90-3.86(m,1H,NCH2),2.30-1.21(m,39H,CH2CH3,PCy3).
The following is according to relevant documents and materials ruthenium complex 6a-6z is synthesized using complex ligands (5a-5z)：
It is complex compound 6a-6z structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 6a of embodiment 70 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5a (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6a, yield：79%.
After testing, ruthenium complex (6a)1HNMR(400MHz,CDCl3):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, NCH2CH2N),2.50(s,12H,
aromatic CH3),2.42(s,6H,aromatic CH3).
The ruthenium complex 6b of embodiment 71 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5b (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6b, yield：77%.
After testing, ruthenium complex (6a)1HNMR(400MHz,CDCl3):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,PCy3).
The ruthenium complex 6c of embodiment 72 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5c (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6c, yield：96%.
After testing, ruthenium complex (6c)1HNMR(400MHz,CDCl3):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, NCH2CH2N),3.837
(s,3H,OCH3),2.514(m,18H,aromatic CH3).
The ruthenium complex 6d of embodiment 73 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5d (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6d, yield：65%.
After testing, ruthenium complex (6d)1HNMR(400MHz,CDCl3):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,OCH3),2.310-1.074(m,33H,
PCy3).
The ruthenium complex 6e of embodiment 74 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5e (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6e, yield：31%.
After testing, ruthenium complex (6e)1HNMR(400MHz,CDCl3):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,NCH2CH2N),3.810(s,3H,OCH3),2.493(m,18H,aromatic
CH3).
The ruthenium complex 6f of embodiment 75 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5f (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6f, yield：7%.
After testing, ruthenium complex (6f)1HNMR(400MHz,CDCl3):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,OCH3),2.496-1.275(m,33H,PCy3).
The ruthenium complex 6g of embodiment 76 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5g (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6g, yield：24%.
After testing, ruthenium complex (6g)1HNMR(400MHz,CDCl3):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, NCH2CH2N),2.495(m,18H,aromatic CH3).
The ruthenium complex 6h of embodiment 77 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5h (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6h, yield：27%.
After testing, ruthenium complex (6h)1HNMR(400MHz,CDCl3):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,
PCy3).
The ruthenium complex 6j of embodiment 78 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5j (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6j, yield：38%.
After testing, ruthenium complex (6j)1HNMR(400MHz,CDCl3):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, NCH2CH2N), 2.490 (m, 18H,
aromatic CH3).
The ruthenium complex 6k of embodiment 79 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5k (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6k, yield：15%.
After testing, ruthenium complex (6k)1HNMR(400MHz,CDCl3):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,
PCy3).
The ruthenium complex 6m of embodiment 80 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5m (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6m, yield：17%.
After testing, ruthenium complex (6m)1HNMR(400MHz,CDCl3):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,NCH2CH2N),3.845(s,3H,OCH3),2.519(m,18H,
aromatic CH3).
The ruthenium complex 6n of embodiment 81 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5n (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6n, yield：40%.
After testing, ruthenium complex (6n)1HNMR(400MHz,CDCl3):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,NCH2CH2N),2.517(m,18H,aromatic CH3).
The ruthenium complex 6p of embodiment 82 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5p (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6p, yield：47%.
After testing, ruthenium complex (6p)1HNMR(400MHz,CDCl3):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,PCy3).
The ruthenium complex 6q of embodiment 83 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5q (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6q, yield：33%.
After testing, ruthenium complex (6q)1HNMR(400MHz,CDCl3):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,NCH2CH2N),2.510(m,18H,aromatic CH3).
The ruthenium complex 6r of embodiment 84 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5r (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6r, yield：8%.
After testing, ruthenium complex (6r)1HNMR(400MHz,CDCl3):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,PCy3).
The ruthenium complex 6s of embodiment 85 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5s (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6s, yield：37%.
After testing, ruthenium complex (6s)1HNMR(400MHz,CDCl3):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,NCH2CH2N),3.947(s,3H,OCH3),3.87(s,3H,OCH3),2.49(s,12H,
aromatic CH3),2.48(s,6H,aromatic CH3).
The ruthenium complex 6t of embodiment 86 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5t (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains greenish yellow solid product 6t, yield：-- %.
After testing, ruthenium complex (6t)1HNMR(400MHz,CDCl3):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,OCH3),3.86(s,3H,OCH3),2.33-1.30(m,33H,PCy3).
The ruthenium complex 6u of embodiment 87 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5u (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains gray solid product 6u, yield：17%.
After testing, ruthenium complex (6u)1HNMR(400MHz,CDCl3):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,OCH3),2.31-0.82(m,33H,PCy3).
The ruthenium complex 6v of embodiment 88 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5v (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains red solid product 6v, yield：28%.Product be not it is very stable, very
Difficult purification assays ruthenium complex 6v's1H-NMR structures, but its impure ruthenium complex 6v can be directly used for olefin metathesis double decomposition
Catalytic reaction.
The ruthenium complex 6w of embodiment 89 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5w (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 6w, yield：22%.
After testing, ruthenium complex (6w)1H-NMR(400MHz,CDCl3):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,NCH2CH2N),3.805(s,3H,OCH3),2.493(m,18H,aromatic
CH3).
The ruthenium complex 6y of embodiment 90 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5y (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 6y, yield：9%.
After testing, ruthenium complex (6y)1H-NMR(400MHz,CDCl3):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,NCH2CH2N),2.67-2.28(m,20H,aromatic CH,aromatic CH3), 0.92 (d, J=7.6Hz, OCH
(CH3)2), 0.83 (d, J=7.6Hz, OCH (CH3)2).
The ruthenium complex 6z of embodiment 91 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5z (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 6z, yield：9%.
After testing, ruthenium complex (6z)1H-NMR(400MHz,CDCl3):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,NCH2CH2N),2.48-2.31(m,27H,aromatic CH3).
The following is according to relevant information ruthenium complex 8a-8t is synthesized using complex ligands (7a-7t)：
It is complex compound 8a-8t structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 8a of embodiment 92 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7a (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8a, yield：32%.
After testing, ruthenium complex (8a)1HNMR(400MHz,CDCl3):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,NCH2CH2N),2.69(s,6H,NCH3),2.49(s,(s,12H,aromatic CH3),2.42(s,6H,aromatic
CH3).
The ruthenium complex 8b of embodiment 93 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7b (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8b, yield：79%.
After testing, ruthenium complex (8b)1HNMR(400MHz,CDCl3):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, NCH2),3.876-3.846(m,4H,NCH2CH2N),3.519(s,3H,OCH3),3.438
(d, J=11.6Hz, 1H, NCH2),2.85-1.50(m,21H,NCH3,aromatic CH3).
The ruthenium complex 8c of embodiment 94 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7c (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8c, yield：9%.
After testing, ruthenium complex (8c)1HNMR(400MHz,CDCl3):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,NCH2CH2N),2.567(s,6H,N
(CH3)2,2.473(s,12H,aromatic CH3),2.390(s,6H,aromatic CH3).
The ruthenium complex 8d of embodiment 95 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7d (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8d, yield：24%.
After testing, ruthenium complex (8d)1HNMR(400MHz,CDCl3):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,NCH3,aromatic CH3), 0.574 (t, J=6.8Hz, 3H, CH2CH3).
The ruthenium complex 8e of embodiment 96 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7e (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8e, yield：74%.
After testing, ruthenium complex (8e)1HNMR(400MHz,CDCl3):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, NCH2),4.210-3.959(m,4H,NCH2CH2N),3.559
(s,3H,OCH3), 3.535 (d, J=11.2Hz, 1H, NCH2),2.938-0.923(m,21H,NCH3,aromatic CH3)。
The ruthenium complex 8f of embodiment 97 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7f (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8f, yield：8%.
After testing, ruthenium complex (8f)1HNMR(400MHz,CDCl3):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, NCH2CH2N),3.262(s,3H,
OCH3),2.734(s,3H,NCH3),2.572-2.260(m,18H,aromatic CH3).
The ruthenium complex 8g of embodiment 98 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7g (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8g, yield：9%.
After testing, ruthenium complex (8g)1H-NMR(400MHz,CDCl3):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, NCH2), 3.978 (d, J=13.2Hz, 1H, NCH2),3.646(s,3H,OCH3),2.836
(s,3H,NCH3),2.412-0.837(m,33H,PCy3).
The ruthenium complex 8h of embodiment 99 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7h (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8h, yield：37%.
After testing, ruthenium complex (8h)1H-NMR(400MHz,CDCl3):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,NCH2CH2), N 3.846 (d, J=14.0Hz, 1H, NCH2), 3.094 (d, J=14.0Hz,
1H,NCH2),2.737(s,3H,NCH3),2.429-2.278(m,18H,aromatic CH3), 1.095 (d, J=6Hz, 6H,
OCH(CH3)2).
The ruthenium complex 8j of embodiment 100 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7h (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8j, yield：48%.
After testing, ruthenium complex (8j)1H-NMR(400MHz,CDCl3):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, NCH2), 4.500-4.470 (m, 1H, OCH), 4.049 (d, J=
12.8Hz,1H,NCH2),2.704(s,3H,NCH3),2.384-0.780(m,39H,PCy3,OCH(CH3)2).
The ruthenium complex 8k of embodiment 101 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7k (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8k, yield：77%.
After testing, ruthenium complex (8k)1H-NMR(400MHz,CDCl3):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, NCH2),4.477-4.432(m,1H,
OCH),4.015-3.983(m,5H,NCH2CH2N,NCH2),2.535-2.304(m,18H,aromatic CH3),2.246(s,
3H,NCH3), 1.285 (d, J=6Hz, 6H, OCH (CH3)2).
The ruthenium complex 8m of embodiment 102 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7m (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8m, yield：23%.
After testing, ruthenium complex (8m)1H-NMR(400MHz,CDCl3):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, NCH2),4.588-4.543(m,1H,OCH),4.245-4.207(m,1H,NCH2),
2.639(s,3H,NCH3),2.418-0.810(m,39H,PCy3,OCH(CH3)2).
The ruthenium complex 8q of embodiment 103 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7q (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8q, yield：59%.
After testing, ruthenium complex (8g)1H-NMR(400MHz,CDCl3):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,NCH2CH2N),3.91(s,3H,COOCH3),
2.58(s,6H,N(CH3)2,2.47(s,12H,aromatic CH3),2.43(s,6H,aromatic CH3).
The ruthenium complex 8s of embodiment 104 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7s (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8s, yield：43%.
After testing, ruthenium complex (8s)1H-NMR(400MHz,CDCl3):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, NCH2),4.84-4.83(m,1H,OCH),4.14-3.93(m,4H,
NCH2CH2), N 3.45 (d, J=11.2Hz, 1H, NCH2),2.89-1.19(m,27H,NCH3,aromatic CH3,OCH
(CH3)2).
The ruthenium complex 8t of embodiment 105 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7t (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 8t, yield：87%.
After testing, ruthenium complex (8t)1H-NMR(400MHz,CDCl3):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,NCH2CH2N),3.95-3.92(m,1H,NH,NCH2),3.74(s,3H,OCH3),2.50-2.37(m,18H,
aromatic CH3), 0.96 (d, J=6.4Hz, 1H, CH3).
The following is according to relevant information ruthenium complex 10a-10j is synthesized using complex ligands (9a-9j)：
It is complex compound 10a-10j structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 10a of embodiment 106 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9a (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 10a, yield：19%.Product be not it is very stable,
It is difficult to purification assays ruthenium complex 10a1HNMR structures, but its impure ruthenium complex 10a can be directly used for olefin metathesis answer
Decompose catalytic reaction.
The ruthenium complex 10b of embodiment 107 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9b (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 10b, yield：15%.Product be not it is very stable,
It is difficult to purification assays ruthenium complex 10b1HNMR structures, but its impure ruthenium complex 10b can be directly used for olefin metathesis answer
Decompose catalytic reaction.
The ruthenium complex 10c of embodiment 108 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9c (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains red brown solid product 10c, yield：4%.
After testing, ruthenium complex (10c)1HNMR(400MHz,CDCl3):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,NCH2CH2N),3.973(s,3H,
OCH3),2.481(s,12H,aromatic CH3),2.459(s,6H,aromatic CH3).
The ruthenium complex 10d of embodiment 109 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9d (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains yellow solid product 10d, yield：34%.
After testing, ruthenium complex (10d)1HNMR(400MHz,CDCl3):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(CH3)2),4.13(s,4H,NCH2CH2N),
2.46(m,18H,aromatic CH3), 1.24 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10e of embodiment 110 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9e (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 10e, yield：34%.
After testing, ruthenium complex (10e)1HNMR(400MHz,CDCl3):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 (CH3)2),4.114(s,4H,
NCH2CH2N),2.451(m,18H,aromatic CH3), 1.281 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10f of embodiment 111 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9f (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains yellow solid product 10f, yield：41%.
After testing, ruthenium complex (10f)1HNMR(400MHz,CDCl3):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,OCH2),4.529(m,1H,OCH(CH3)2),4.151(s,4H,
NCH2CH2N),2.511(m,18H,aromatic CH3), 1.395 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10g of embodiment 112 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9g (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 10g, yield：53%.
After testing, ruthenium complex (10g)1HNMR(400MHz,CDCl3):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, OCH2),4.515(m,1H,OCH
(CH3)2),4.159(s,4H,NCH2CH2N),2.514(s,12H,aromatic CH3),2.482(s,6H,aromatic
CH3), 1.277 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10h of embodiment 113 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9h (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 10h, yield：23%.
After testing, ruthenium complex (10h)1HNMR(400MHz,CDCl3):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,
OCH2),4.560(m,1H,OCH(CH3)2),4.158(s,4H,NCH2CH2N),2.712(s,12H,aromatic CH3),
2.515(s,6H,aromatic CH3), 1.315 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10j of embodiment 114 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9j (10mmol), CuCl (30mmol, 3eq) and
30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, is then washed with methanol or pentane-DCM and obtains green solid product 10j, yield：37%.
After testing, ruthenium complex (10j)1H-NMR(400MHz,CDCl3):1H-NMR(400MHz,CDCl3):δ18.74
(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 (CH3)2),5.25
(m,1H,OCH(CH3)2),4.13(s,4H,NCH2CH2N),2.47(m,18H,aromatic CH3), 1.43 (d, J=6Hz, CH
(CH3)2), 1.24 (d, 6H, J=6Hz, CH (CH3)2).
The following is according to relevant information ruthenium complex 12a-12j is synthesized using complex ligands (11a-11j)：
It is complex compound 12a-12j structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 12a of embodiment 115 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1a (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12a, yield：75%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12a structure, but its impure ruthenium complex 12a can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12b of embodiment 116 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1b (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12b, yield：57%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12b structure, but its impure ruthenium complex 12b can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12c of embodiment 117 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1c (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12c, yield：40%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12c structure, but its impure ruthenium complex 12c can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12d of embodiment 118 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1d (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12d, yield：42%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12d structure, but its impure ruthenium complex 12d can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12e of embodiment 119 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1e (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12e, yield：69%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12e structure, but its impure ruthenium complex 12e can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12f of embodiment 120 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1f (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12f, yield：63%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12f structure, but its impure ruthenium complex 12f can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12g of embodiment 121 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1g (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12g, yield：69%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12g structure, but its impure ruthenium complex 12g can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12h of embodiment 122 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1h (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12h, yield：61%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12h structure, but its impure ruthenium complex 12h can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12j of embodiment 123 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1j (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
With 30mL dry DCM, then with argon gas replace three times after with argon gas ball protect enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed with methanol or pentane-DCM and obtain green solid product 12j, yield：46%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12j structure, but its impure ruthenium complex 12j can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
Ruthenium complex 13a-13ag is synthesized using ruthenium complex (13-SM) the following is according to relevant information：
It is ruthenium complex 13a-13ag structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 13a of embodiment 124 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13a, yield are obtained after filtering：47%.
After testing, ruthenium complex (13a)1H-NMR(400MHz,CDCl3):δ17.33(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 ruthenium complex 13b of embodiment 125 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13b, yield are obtained after filtering：48%.
After testing, ruthenium complex (13b)1H-NMR(400MHz,CDCl3):δ16.49(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 ruthenium complex 13d of embodiment 126 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13d, yield are obtained after filtering：42%.
After testing, ruthenium complex (13d)1H-NMR(400MHz,CDCl3):δ17.33(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 ruthenium complex 13e of embodiment 127 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13e, yield are obtained after filtering：95%.
After testing, ruthenium complex (13e)1H-NMR(400MHz,CDCl3):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 ruthenium complex 13g of embodiment 128 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13g, yield are obtained after filtering：52%.
After testing, ruthenium complex (13g)1H-NMR(400MHz,CDCl3):δ16.49(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), (d, J=4.4Hz, the 6H) of 4.19 (s, 4H), 2.48-2.41 (m, 18H), 1.26
The ruthenium complex 13h of embodiment 129 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13h, yield are obtained after filtering：59%.
After testing, ruthenium complex (13h)1H-NMR(400MHz,CDCl3):δ16.52(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 ruthenium complex 13j of embodiment 130 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13j, yield are obtained after filtering：81%.
After testing, ruthenium complex (13j)1H-NMR(400MHz,CDCl3):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 ruthenium complex 13k of embodiment 131 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13k, yield are obtained after filtering：36%.
After testing, ruthenium complex (13k)1H-NMR(400MHz,CDCl3):δ17.39(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 ruthenium complex 13m of embodiment 132 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13m, yield are obtained after filtering：35%.
After testing, ruthenium complex (13m)1H-NMR(400MHz,CDCl3):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 ruthenium complex 13n of embodiment 133 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13n, yield are obtained after filtering：49%.
After testing, ruthenium complex (13n)1H-NMR(400MHz,CDCl3):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 ruthenium complex 13p of embodiment 134 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13p, yield are obtained after filtering：52%.
After testing, ruthenium complex (13p)1H-NMR(400MHz,CDCl3):δ17.39(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 ruthenium complex 13q of embodiment 135 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13q, yield are obtained after filtering：81%.
After testing, ruthenium complex (13q)1H-NMR(400MHz,CDCl3):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 ruthenium complex 13r of embodiment 136 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13r, yield are obtained after filtering：37%.
After testing, ruthenium complex (13r)1H-NMR(400MHz,CDCl3):δ18.67(s,1H),8.40(m,1H),
(d, J=4.0Hz, the 6H) of 7.47-6.91 (m, 13H), 6.58 (m, 1H), 4.12 (m, 6H), 2.63-2.27 (m, 19H), 1.00
The ruthenium complex 13s of embodiment 137 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13s, yield are obtained after filtering：73%.
After testing,1H-NMR(400MHz,CDCl3):δ18.67(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 ruthenium complex 13t of embodiment 138 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13t, yield are obtained after filtering：55%.
After testing, ruthenium complex (13t)1H-NMR(400MHz,CDCl3):δ18.69(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 ruthenium complex 13u of embodiment 139 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13u, yield are obtained after filtering：63%.
After testing, ruthenium complex (13u)1H-NMR(400MHz,CDCl3):δ18.69(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 ruthenium complex 13v of embodiment 140 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13v, yield are obtained after filtering：90%.
After testing,1H-NMR(400MHz,CDCl3):δ18.69(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 ruthenium complex 13w of embodiment 141 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13w, yield are obtained after filtering：49%.
After testing, ruthenium complex (13w)1H-NMR(400MHz,CDCl3):δ18.67(s,1H),8.40(m,1H),
(d, J=4.0Hz, the 6H) of 7.69-6.90 (m, 13H), 6.60 (m, 1H), 4.12 (m, 6H), 2.62-2.17 (m, 19H), 1.00
The ruthenium complex 13x of embodiment 142 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13x, yield are obtained after filtering：97%.
After testing, ruthenium complex (13x)1H-NMR(400MHz,CDCl3):δ16.57(s,1H),7.63-6.69(m,
11H), (d, J=4.0Hz, the 6H) of 4.83-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 21H), 1.24
The ruthenium complex 13y of embodiment 143 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13y, yield are obtained after filtering：81%.
After testing, ruthenium complex (13y)1H-NMR(400MHz,CDCl3):δ16.85(s,1H),8.40-6.83(m,
15H), (d, J=4.4Hz, the 6H) of 4.95 (m, 1H), 4.16 (s, 3H), 3.80 (s, 4H), 2.46-2.23 (m, 18H), 1.29
The ruthenium complex 13z of embodiment 144 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13z, yield are obtained after filtering：78%.
After testing, ruthenium complex (13z)1H-NMR(400MHz,CDCl3):δ16.85(s,1H),8.42-7.07(m,
15H), (d, J=4.4Hz, the 6H) of 4.95 (m, 1H), 4.19 (s, 4H), 2.45-2.29 (m, 18H), 1.29
The ruthenium complex 13aa of embodiment 145 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13aa, yield are obtained after filtering：85%.
After testing, ruthenium complex (13aa)1H-NMR(400MHz,CDCl3):δ16.85(s,1H),8.47-6.85(m,
16H), (d, J=4.4Hz, the 6H) of 4.94 (m, 1H), 4.19 (s, 4H), 2.40-2.29 (m, 18H), 1.29
The ruthenium complex 13ab of embodiment 146 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ab, yield are obtained after filtering：96%.
After testing, ruthenium complex (13ab)1H-NMR(400MHz,CDCl3):δ17.00(s,1H),8.47-6.82(m,
11H), (d, J=4.4Hz, the 6H) of 4.90 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26
The ruthenium complex 13ac of embodiment 147 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ac, yield are obtained after filtering：95%.
After testing, ruthenium complex (13ac)1H-NMR(400MHz,CDCl3):δ17.00(s,1H),8.47-6.83(m,
11H), (d, J=4.4Hz, the 6H) of 4.91 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26
The ruthenium complex 13ad of embodiment 148 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ad, yield are obtained after filtering：33%.
After testing, ruthenium complex (13ad)1H-NMR(400MHz,CDCl3):δ18.65(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 ruthenium complex 13ae of embodiment 149 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ae, yield are obtained after filtering：68%.
After testing, ruthenium complex (13ae)1H-NMR(400MHz,CDCl3):δ18.65(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 ruthenium complex 13af of embodiment 150 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13af, yield are obtained after filtering：59%.
After testing, ruthenium complex (13af)1H-NMR(400MHz,CDCl3):δ18.65(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 ruthenium complex 13ag of embodiment 151 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used after being replaced three times with argon gas
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ag, yield are obtained after filtering：69%.
After testing, ruthenium complex (13ag)1H-NMR(400MHz,CDCl3):δ18.65(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).
Substantially effectively to optimize the synthetic method of all kinds of ruthenium catalysts, cost and resource consumption are reduced, the present invention is to several
Class ruthenium catalyst employs different synthetic routes.When raw material 4-SM generates Cabbeen intermediate in the presence of caustic alcohol, then directly
Connect and RuCl2(PPh3)3The unstable ruthenium complex intermediate 4-1 of reaction generation；Intermediate 4-1 triphenyl phosphorus part can quilt
Another part PCy3The stable ruthenium complex 4bf of (4-2) generation.Ruthenium complex intermediate 4-1 or 4bf and part H2IMes(4-3)
The directly more stable and higher catalytic activity ruthenium catalyst 4be of substitution generation.Ruthenium complex 4be and part 4- chloropyridines (4-4)
Reaction directly complexing generation 13s:
It is ruthenium complex intermediate 4-1, ruthenium catalyst 4be, 4bf and 13s an easy synthetic route below：
The ruthenium complex 4bf of embodiment 152 synthesis
One 500mL there-necked flask sequentially adds ligand stock 4-SM (33g, 100mmol, 1.0eq.) after being replaced with argon gas
It is dissolved in 300mL ethanol, NaOEt (400mmol, 4.0eq.) is rapidly added under stirring, is heated to 60 DEG C of reaction half an hour.30 points
120mL water is added after clock, with extraction into heptane (200mL × 3).Combining extraction liquid, (150mL is washed with saturated sodium carbonate solution
× 2), saturated common salt water washing (150mL × 2) is concentrated into about 50mL after anhydrous sodium sulfate drying at 0 DEG C.Yield presses 50%
Next step reaction is calculated to feed intake.
By RuCl2(PPh3)3(29g, 20mmol) is dissolved in 250mL dichloromethane, is cooled to -78 DEG C, adds -70 DEG C
Above-mentioned diazonium pentane solution (~60mL).After 5 minutes, reaction temperature is slowly increased to room temperature, add CuCl (14.7g,
100mmol).After 15 minutes, filtering.After filtrate concentration, column chromatography purifying, with gradient elution agent (2: 1 n-hexanes/dichloromethane
To absolute dichloromethane).Product section is concentrated, n-hexane washing, vacuum drying is obtained in the middle of the unstable ruthenium complexs of 12.3g
Body 4-1.
Intermediate 4-1 (15.0mmol) is dissolved in dichloromethane (30mL), adds three rings phosphorus (PCy3,30mmol,
2.0eq.), after 20 DEG C are reacted half an hour, with dark green solid is obtained after chromatography column separating purification product, with methanol and just oneself
Alkane washing obtains green solid product 4bf, thick yield after drying：53%.Product 4bf is not very stable, it is difficult to purification assays ruthenium
Complex compound 4bf's1H-NMR structures, but its impure ruthenium complex 4bf can be directly used for preparation 4be or olefin metathesis double decomposition
Catalytic reaction.
The ruthenium complex 4be of embodiment 153 synthesis
One 50mL, two mouthfuls of flasks sequentially add ruthenium complex 4bf (5.0mmol) and H after being replaced with argon gas2IMes(H)
(CCl3) (4-3,10.0mmol, 2.0eq.) be dissolved in 30mL drying be dissolved in toluene, then with argon gas replace three times after use argon gas
Ball protects enclosed system, is heated to 80 DEG C, reaction in 1.5 hours terminates rear crystallisation by cooling filtering, and silica gel is added in filtrate after filtering
Dark green solid crude product is obtained after column chromatography, the green solid product stablized then is washed with methanol or pentane-DCM
4be, yield：59%.
After testing, ruthenium complex (4be)1H-NMR(400MHz,CDCl3):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, NCH2,NCH2CH2N),
4.01 (d, J=13.2Hz, 1H, NCH2),2.75-2.00(m,19H,CH(CH3)2,aromatic CH3),1.01-0.90(m,
6H,CH(CH3)2).
Ruthenium complex 13s preparation is by above-mentioned ruthenium complex 4be and part 4- chloropyridines (4-4) reaction directly complexing
Into about preparing experiment and the synthesis of the ruthenium complex 13s described in analysis result detailed in Example 137.
Application Example of the ruthenium complex catalyst in olefin metathesis double decomposition cyclization：
There is generation in another patent (US20070043180A1) delivered before making the present invention below for the present inventor
Complex compound 14a, 14b of table and other four representational catalyst 14c, 14d, 14e, 14f structural formula：
Some ruthenium complex catalysts in these ruthenium catalysts (14a-14f) and the present invention are selectively used for following
The catalytic cyclization reaction and ring-opening polymerization of cycloolefin prepare the experiment of the high molecular polymer new material of difference in functionality, and with
The catalytic effect contrast for the similar catalyst that the present invention is listed is discussed.
Ruthenium complex catalysed olefin metathesis reaction experimental procedure：50mg substrate is placed in bis- mouthfuls of round-bottomed flasks of 25mL
In, addition 1mL newly steams after being replaced 5 times with argon gas dichloromethane and 5mg catalyst.Under argon gas protection, reactant mixture
It is stirred at room temperature complete to reaction.The conversion ratio of reaction is obtained by HPLC monitorings.The following is ruthenium complex in different alkene
Catalytic activity research in transposition metathesis reaction：
Effect example 1:
In order to contrast the catalytic activity of the ruthenium complex containing different substituents, now the different rutheniums that embodiment is synthesized are complexed
The catalytic activity and relative catalytic activity of thing metathesis reaction are compared.
Metathesis cyclization reaction experiment in olefin hydrocarbon molecules：50mg reaction substrates 15 are separately added into the necks of 25ml bis- bottle, with three
Logical displacement makes inside be full of argon gas, adds 1.0ml dichloromethane with syringe, is stirred at room temperature after making to be completely dissolved, is separately added into
2mol% above-mentioned ruthenium complex catalyst (4a-4cz, 6a-6z, 8a-8t, 10a-10j).Respectively at 10min, 30min,
1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr are sampled, and are reacted with HPLC and LC-MS tracking.Calculated and produced with normalized method
The conversion ratio of thing, reaction result is shown in Table 2.
Olefin metathesis double decomposition cyclisation product (16)1HNMR(400MHz,CDCl3):δ=7.78 (d, 2H, J=
8.21Hz), (s, 3H) the molecular weight of 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (M+H+)：
M/z calculated values are 300.1, and test value is 300.2.
The Intra-molecular condensation catalyst 4a-4cz of table 1-1. alkene 15 Activity Assessment
Except more than ten new catalyst listed in above-mentioned table 1-1 has preferable activity in ruthenium catalyst 4a-4cz, its
Remaining listed ruthenium catalyst it is active poor, it can be seen that the ruthenium complex that the substituent electronic effect of Novel Ligands is formed to it
Catalytic activity have significant influence.
The Intra-molecular condensation catalyst 6a-6z of table 1-2. alkene 15 Activity Assessment
Except tri- new catalysts of 6s, 6t and 6v listed in above-mentioned table 1-2 have preferable work in ruthenium catalyst 6a-6z
Property, catalytic activity is substantially better than the similar catalyst 14f that oneself knows.Remaining ruthenium catalyst it is active very poor, it can be seen that it is new
The catalytic activity for the ruthenium complex that the substituent electronic effect of part is formed on it has significant influence.
The Intra-molecular condensation catalyst 8a-8t of table 1-3. alkene 15 Activity Assessment
Except tri- new catalysts of 8c, 8e and 8h listed in above-mentioned table 1-3 have preferable work in ruthenium catalyst 8a-8t
Property, catalytic activity is substantially better than the similar catalyst 14d that oneself knows.Ruthenium catalyst listed by remaining it is active poor, it can be seen that
The catalytic activity for the ruthenium complex that the substituent electronic effect of Novel Ligands is formed on it has significant influence.
The Intra-molecular condensation catalyst 10a-10j of table 1-4. alkene 15 Activity Assessment
Urged in ruthenium catalyst 10a-10j except listed in above-mentioned table 1-4 10c, 10d, 10e, 10f and 10g five is new
Agent has preferable activity, and catalytic activity is substantially better than the similar catalyst 14e that oneself knows.Remaining ruthenium catalyst activity compared with
Difference, it can be seen that the catalytic activity for the ruthenium complex that the substituent electronic effect of Novel Ligands is formed to it has significant shadow
Ring.
The Intra-molecular condensation catalyst 13a-13ag of table 1-5. alkene 15 Activity Assessment
Except four new catalysts listed in above-mentioned table 1-5 have poor activity in ruthenium catalyst 13a-13ag, its
The cyclisation activity of remaining ruthenium catalyst is very poor, it can be seen that the ruthenium complex that the substituent electronic effect of Novel Ligands is formed to it
Catalytic activity have significant influence.But it is anti-that some of which catalyst 13a-13ag can be effectively used for cycloolefin ring-opening polymerisation
Should.
Except the several catalyst for having a preferable activity listed in above-mentioned each table in above-mentioned all kinds of new ruthenium catalysts, remaining
Cyclization (RCM) activity of the ruthenium catalyst of preparation is very poor, as a result shows do not have substituent on new complex ligands phenyl ring
Ruthenium complex (14f) and substituted base ruthenium complex (such as 6g and 6m) catalytic activity it is very low, it is impossible to trigger urging for alkene
Change cyclization (RCM).As can be seen here the present invention in new oxygen-containing or nitrogen coordination atom part substituent electronic effect to it
The catalytic activity of the ruthenium complex of formation has significant influence.Table 1-1,1-2,1-3,1-4,1-5 result shows, of the invention
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 are good to the expression activitiy of alkene 15, and ring closure reaction is most of to be terminated in 1.5-3hr, are catalysis in the current field
The good new olefin double decomposition cyclization catalyst of expression activitiy.
Effect example 2:
In order to contrast the catalytic activity of all kinds of ruthenium complexs containing different substituents, now to having in above-described embodiment preferably
The catalytic activity and relative catalytic activity of the ruthenium complex catalyst of activity are compared.
Olefin hydrocarbon molecules intramolecular cyclization reaction is tested：50mg reaction substrates 17 are separately added into the necks of 25ml bis- bottle, are put with threeway
Changing makes inside be full of argon gas, adds 1.0ml dichloromethane with syringe, is stirred at room temperature after making to be completely dissolved, is separately added into 2mol%
The good ruthenium complex catalyst of above-mentioned expression activitiy.Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr,
15.0hr is sampled, and is reacted with HPLC and LC-MS tracking.The conversion ratio of product is calculated with normalized method, reaction result is shown in Table
2。
Olefin metathesis double decomposition cyclisation product (12)1HNMR(400MHz,CDCl3):δ=7.78 (d, 2H, J=8.21Hz),
(s, 3H) the molecular weight of 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (M+H+)：M/z theory meters
Calculation value is 300.1, and test value is 300.2.
The Activity Assessment of all kinds of catalyst of Intra-molecular condensation of the alkene 17 of table 2.
The result of table 2 shows, the work of all kinds of new catalyst 4c, 4t, 4x, 4af, 6s, 8e, 10d of the invention to alkene 17
Property it is relatively good, ring closure reaction is most of to be terminated in 1.5-3hr, is the relatively good new olefin of catalytic activity in the current field
Double decomposition cyclization catalyst.
Effect example 3:
In order to preferably determine the difference between different high activated catalysts, this patent devises one existing two and inhales electricity
There are two methyl substituted substrates 19 on sub- fluoro, alkene again, substrate 19, which imitates the difficult characteristic for occurring transposition double decomposition cyclisation, makes catalysis
Activity difference between agent (11a-j) is determined obviously to be come.
Metathesis cyclization reaction experiment in olefin hydrocarbon molecules：50mg reaction substrate Multi substituted benzenes are separately added into the necks of 25ml bis- bottle
Vinethene alkene 19, makes inside be full of argon gas, 1.0ml dichloromethane is added with syringe, being stirred at room temperature makes completely with threeway displacement
After dissolving, 3mol% above-mentioned ruthenium complex catalyst (12a-12h) is separately added into.Respectively at 10min, 30min, 1.0hr,
3.0hr, 5.0hr, 8.0hr, 15.0hr are sampled, and are reacted with HPLC and LC-MS tracking.Turning for product is calculated with normalized method
Rate, dependent dynamics result is listed in table 3.
Olefin metathesis double decomposition cyclisation product (20)1HNMR(CDCl3：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 values are 200.99, and test value is 201.1.
The Intra-molecular condensation catalytic activity of the alkene 19 of table 3. is assessed
The result of table 3 shows, new catalyst 12a, 12b, 12d, 12e, 12g, 12h of the invention to the activity of alkene 19 very
Good, ring closure reaction is most of to be terminated in 30 minutes, was that the best class of catalytic activity is new in the current catalytic cyclization field
Olefin metathesis cyclization catalyst.
Application Example of the ruthenium complex catalyst in alkene ring-opening polymerization：
In order to further research and develop the machinery of more effective alkene ring-opening polymerization catalyst and its high molecular polymer new material
Performance, preferably determines the difference between different high activated catalysts, is implemented by the effect of following alkene ring-opening polymerization
The mechanicalnesses such as intensity and modulus of the example 4-7 to research and develop contrast raising olefin metathesis reaction catalyst and high molecular polymer product
Energy.
Effect example 4:
Method one；Alkene ring-opening polymerization tests (catalytic polymerization in solvent)：Cyclo-octene (21) raw material monomer is dissolved in
In the anhydrous solvent (such as dichloroethanes DCE) of 20 times of amounts (20x), argon filling catches up with oxygen, then rapidly joins the ruthenium that this project etc. is filtered out
Catalyst (0.1 ‰ -5%), reacts (20-75 DEG C) heating response that preferably progressively heats up, and reaction solution gradually becomes viscous.Reaction is stayed overnight
Reaction solution is slowly toppled over afterwards and is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain polymer solids product (22), production
Rate is 70%-98%.
Method two；Alkene ring-opening polymerization tests (solvent-free catalytic polymerization)：Lead in Breakup of Liquid Ring octene monomers (21)
Enter argon gas to rush oxygen, then rapidly join the ruthenium catalyst (0.1-5 ‰) that this project etc. is filtered out, heated between 20-120 degree
Reaction solution gradually becomes viscous and exothermic after reaction a few minutes, and finally polymerization obtains open loop high molecular polymer solid product (22).
As a result show, new catalyst 8c, 8d, 4j, 4m, 4p, 4r, 4c, 8c, 8e of the invention polymerize to cyclo-octene (21)
The expression activitiy of reaction is good, catalytic polymerate (22) have preferable tensile strength and modulus (>1.5Gpa), it is the current neck
The relatively good new olefin metathesis polymerization catalysts of catalytic activity in domain.Open loop high molecular polymer (22) heating can melt
Change and be dissolved in weak polar solvent (such as petroleum ether, paraffin oil), be processed further the explosion-proof lamp that can be used for preparing high intensity
Or spinning processing high-strength products.
Effect example 5:
Method one；Alkene ring-opening polymerization tests (catalytic polymerization in solvent)：ENB (23) raw material monomer is molten
In the anhydrous solvent (such as dichloroethanes DCE) of 20 times of amounts (20x), argon filling catches up with oxygen, then rapidly joins what this project etc. was filtered out
Ruthenium catalyst (0.1 ‰ -5%), reacts (20-75 DEG C) heating response that preferably progressively heats up, and reaction solution gradually becomes viscous.Reacted
Reaction solution is slowly toppled over after night and is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain polynorbornene solid product
(24), yield is 75%-98%.
Method two；Alkene ring-opening polymerization tests (solvent-free catalytic polymerization)：In liquid norbornene monomer (23)
Be passed through argon gas to rush oxygen, then rapidly join the ruthenium catalyst (0.1-5 ‰) that this project etc. is filtered out, between 25-100 DEG C plus
Reaction solution gradually becomes viscous and exothermic after thermal response a few minutes, finally obtains polynorbornene solid product (24).
As a result show, new catalyst 4c, 4h, 4j, 4m, 4p, 4r, 8c, 8d, 8e of the invention is to ENB (23)
Expression activitiy is good, and catalytic polymerization terminates in 10-60min, and polynorbornene product (24) has preferable intensity, hardness
And stretch modulus, it is the relatively good new olefin metathesis polymerization catalysts of catalytic activity in the current field.Open loop is high
Molecularly Imprinted Polymer (24) is processed further the explosion-proof lamp or spinning material that can be used for preparing high intensity.
Effect example 6:
Method one；Alkene ring-opening polymerization tests (catalytic polymerization in solvent)：By bicyclic luxuriant diene (DCPD, 25) monomer
Raw material is dissolved in the anhydrous solvent of 20 times of amounts (20x) (such as dichloroethanes DCE), and argon filling catches up with oxygen, then rapidly joins the sieve such as this project
The ruthenium catalyst (0.1 ‰ -5%) selected, reacts (20-75 DEG C) heating response that preferably progressively heats up, and reaction solution gradually becomes viscous.
Reaction solution is slowly toppled over after reaction overnight and is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain the luxuriant diene of poly bis ring
(Poly-DCPD) solid product (26), yield is 75%-98%.
Method two；Alkene ring-opening polymerization tests (solvent-free catalytic polymerization)：In liquid bicyclopentadiene monomer
Argon gas is passed through in (DCPD, 25) to rush oxygen, then rapidly joins the ruthenium catalyst (0.1-5 ‰) that this project etc. is filtered out, in 30-
Reaction solution gradually becomes viscous and exothermic after heating response a few minutes between 120 degree, and finally polymerization obtains the luxuriant diene (Poly- of poly bis ring
DCPD) polymeric solid product (26).
Catalytic result shows, new catalyst 4c of the invention, 4h, 4j, 4m, 4p, 4am, 4be, 4bg, 4bx, 4cg, 8a,
8b, 8c, 8d, 8e, 8h, 8q are preferable to alkene DCPD (25) polymerization catalytic activity, are homogeneous catalysis activity in the current field
Relatively good new olefin metathesis polymerization catalysts.Polymerisation is carried out preferably, under the conditions of differential responses at 40-60 DEG C
Catalytic polymerization terminates in 10-60min.It is especially with 4c, 4am, 4be, 4cg or anti-with the polymerization of the new catalyst such as 8h
The luxuriant diene product (26) of poly bis ring that should be obtained has good intensity, hardness and bending modulus.
Polymer (26) the performance test results show that Poly-DCPD solid polymers prepared by solvent-free catalytic polymerization have
Have good hardness (>80Gpa), bending modulus (>20Gpa) and heat distortion temperature (>200 DEG C), main performance index is better than mesh
Luxuriant diene (Poly-DCPD) product of similar poly bis ring of preceding U.S. Materia companies and Nippon Zeon.Add during catalytic polymerization
Plus the copolymer such as the antioxidant or crosslinking agent of (0.1-5%) can improve luxuriant diene product (26) hardness of poly bis ring and modulus on a small quantity
Etc. physical property, different high intensity can be made up of injection moulding processing technology (ROMP-RIM) from now on, high rigidity, resistance to low
Luxuriant diene (26) product of poly bis ring of temperature, acid and alkali-resistance, has in industry and life and has been widely used.
Effect example 7:
Alkene ring-opening polymerization is tested：Olefinic monomer (27) raw material is dissolved in the anhydrous solvent (such as two of 15 times of amounts (15x)
Chloroethanes DCE) in, argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. is filtered out, and reacts best
Progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly toppled in ethanol after reaction overnight
It is precipitated out, ethanol immersion, filtering and drying to obtain white polymer solid product (28), yield is 80-98%.Open loop macromolecule
Polymer (28) is processed further the spinning material that can be used for preparing high intensity.
Effect example 8:
" Linker " is the group for connecting cycloolefin monomers and functional group " G ", including but not limited to O, S, C1-C15Saturation or
Undersaturated alkyl, substituted or unsubstituted C1-C15Amido, substituted or unsubstituted C1-C15It is alkoxy, substituted or unsubstituted
C6-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, substitution do not take
The C in generation6-C15Arylthio, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formyloxy, formamido, substitution or
Unsubstituted C1-C15Alkyl carbonyloxy, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C6-C15
Arylcarbonyloxy, substituted or unsubstituted C6-C15Aryl carboxamides base；
" G " is the compound with property or purposes, the small molecule liquid crystal that can be such as connected with " Linker " (29d,
29e, 29f) and the material such as small-molecule drug (29g, " G " is medicine " Lipitor "), being generated after the monomer ring-opening polymerisation of connection has
The prodrug (30g) of property or purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix.
Following is the structure of high molecular polymer (30) prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Alkene ring-opening polymerization is tested：Olefinic monomer raw material (29) is dissolved in the anhydrous solvent (such as two of 20 times of amounts (20x)
Chloroethanes DCE) in, argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. is filtered out, and reacts best
Progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly toppled in ethanol after reaction overnight
It is precipitated out, ethanol immersion, filtering and drying to obtain polymer solids product (30), yield is 80%-98%.
Relevant preferable polymerization results are summarized and are listed as follows (table 4)：
The result of table 4 shows, small molecule liquid crystal or medicine the monomer energy under the New Ruthenium catalyst action that this project screening goes out
Polymerization generation have specific characteristics can or purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix prodrug (30g).It is living
Property test result shows, the work of new catalyst 4a, 4c, 4e, 4g, 6e, 6e and 13a of the invention to olefinic monomer (29a-g)
Property it is relatively good, polymerisation terminates in 5-15hr, under the conditions of the catalytic polymerization of optimization, yield be higher than 90%.Polymerization test
As a result show, different types of ruthenium catalyst is solvent-free and have the catalysis polymerizeing to different monomers under solvent condition in the present invention
Activity has obvious difference, especially some new ruthenium catalysts (such as 4a, 6e) catalytic activity is very low in cyclization, but
Then there is good catalytic activity, thus in cyclisation (RCM) and the reaction of the class of ring-opening polymerisation (ROMP) two in solvent in polymerisation
In show good selectivity and catalytic activity.
Effect example 9:
Alkene ring-opening polymerization is tested：Olefinic monomer raw material is dissolved in anhydrous solvent (such as two chloroethenes of 20 times of amounts (20x)
Alkane DCE) in, argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (4a or 6e, 0.1 ‰ -5%) that this project etc. is filtered out, and reaction is most
Good (20-75 DEG C) heating response that progressively heats up, reaction solution gradually becomes viscous.Reaction solution is slowly poured over ethanol after reaction overnight
In be precipitated out, ethanol immersion, filtering and drying to obtain polymer solids, yield is 60%-98%.
Following is the structure of high molecular polymer 32 (VIc) prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Relevant preferable polymerization results are summarized and are listed as follows (table 5)：
The result of table 5 shows that the small molecule monomer (31a-31s) rolled into a ball containing difference in functionality is urged in the New Ruthenium that this project screening goes out
Can polymerize generation under agent effect has higher-strength and the high molecular polymer of modulus, wherein polymer 32a, 32b, 32n, 32q
The modulus and tensile strength tested after processing film forming are respectively 0.5-3.0Gpa and 20-40MPa, available for spinning processing.
Effect example 10:
Alkene ring-opening polymerization is tested：Olefinic monomer raw material 33 (VIIa) is dissolved in the anhydrous solvent of 20 times of amounts (20x)
In (such as dichloroethanes DCE), argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. is filtered out, reaction
Preferably progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly poured over second after reaction overnight
It is precipitated out in alcohol, ethanol immersion, filtering and drying to obtain polymer solids, yield is about 60%-98%.
Following is high molecular polymer 34 (VIIc) structure prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Relevant preferable polymerization results are summarized and are listed as follows (table 6)：
The result of table 6 shows that the small molecule monomer (33a-33s) rolled into a ball containing difference in functionality is urged in the New Ruthenium that this project screening goes out
Agent effect is lower, which to be polymerize to generate, higher-strength and the high molecular polymer of modulus (34), wherein polymer 34a, 34b, 34c,
The modulus and tensile strength tested after 34v, 34w, 34x processing film forming are respectively 1.0-16Gpa and 30-50MPa, wherein polymer
34c and 34x (modulus of film forming test is up to 16Gpa) process high-strength products more suitable for spinning, are to be opened at present by alkene
The best family macromolecule polymer architecture of modulus in the product that cyclopolymerization (ROMP) is obtained.
Effect example 11:
Alkene ring-opening polymerization is tested：Olefinic monomer raw material 35 (VIIb) is dissolved in the anhydrous solvent of 20 times of amounts (20x)
In (such as dichloroethanes DCE), argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. is filtered out, reaction
Preferably progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly poured over second after reaction overnight
It is precipitated out in alcohol, ethanol immersion, filtering and drying to obtain polymer solids 36 (VIId), yield is about 85-98%.
Following is high molecular polymer (VIId) structure prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Test result shows that polymer 36a-36d modulus and tensile strength is relatively low, respectively less than 0.5GPa and 10MPa,
Processing characteristics is not so good as 34c and 34x.
Effect example 12:
By two or more cycloolefin monomers raw materials (such as 21,23,25,27,29,31,33 in the effect above embodiment 5-11
Or 35) mixing is dissolved in anhydrous solvent (such as dichloroethanes DCE), the new ruthenium catalyst heating that this project screening goes out is added anti-
Should, the high-molecular copolymer of different performance can be prepared, specific copolyreaction is as follows：
Alkene ring-opening polymerization is tested：Two or more cycloolefin monomers raw materials are dissolved in the anhydrous of 20 times of amounts (20x)
In solvent (such as dichloroethanes DCE), argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. is filtered out,
(20-75 DEG C) heating response that preferably progressively heats up is reacted, reaction solution gradually becomes viscous.Reaction solution is slowly toppled over after reaction overnight
It is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain polymer solids, yield is about 65%-98%.
Two or more above-mentioned cycloolefin monomers can by copolyreaction under some catalyst actions of this Project-developing
Different high-molecular copolymer new materials are prepared, the structure about each analog copolymer is as follows：
Test result shows that polymer 37j and 37u process the modulus tested after film forming and tensile strength respectively 2.0-
10Gpa and 40-70MPa, available for film forming or spinning processing high-strength products.
The effect above embodiment 7-11 results show that (film forming modulus is up to the high molecular polymer that structure is 34c and 34x
16Gpa) it is the best class ROMP polymer architectures of modulus in the product that obtains at present by alkene ring-opening polymerisation (ROMP).Urge
Agent 4a and 6e have preferable activity and selectivity.
The instrument and raw material that are related in embodiment are described as follows below：
Ir data is the Fourier Transform AVATAR using Thermo Nicolet companiesTM
360E.S.PTMRadar stealthy materials analysis is obtained, with cm-1Represented for unit.
Proton nmr spectra is that the analysis of Varian Mercury Plus 400 (400MHz) nuclear magnetic resonance spectrometer is obtained.Chemical shift
Recorded by internal standard of tetramethylsilane, (CHCl is represented in units of ppm3：δ=7.26ppm).The data message of record is such as
Under：Chemical shift and its split point and coupling constant (s:Singlet；d:Doublet；t:Triplet；q:Quartet；br:Broad peak；m:
Multiplet).
Mass spectrometric data needs except other, is all divided using Finnigan Finnigan LCQ Advantage LC-MS instrument
Analysis, all reactions are all operated under the conditions of the anhydrous and oxygen-free that dry argon gas is protected.Solid metal-organic compound is in argon gas
Stored in protection drying box.
All column chromatography silica gels (200-300 mesh) are bought from Haiyang Chemical Plant, Qingdao.
Tetrahydrofuran and ether are obtained by distillation, add metallic sodium and benzophenone during distillation wherein.Dichloromethane
Alkane, pentane and hexane are handled with calcium hydride.Cl2Ru=CHPh (PCy3)(H2IMes) it is (the Jason that is prepared according to document
S.Kingsbury,Joseph P.A.Harrity,Peter J.Bonitatebus,Jr.,Amir H.Hoveyda*,
J.Am.Chem.Soc.1999,121,791；American Chemical Society's magazine 1999 year 121 volume page 791).Other all chemical reagent from
Shanghai Reagent Company buys.
Claims (22)
1. structural formula is Formula II c metal complex：
Wherein, M is metal Ru；
L is IMes or PCy3；
L1And L2It is halogen；
M=0 or 1；N=0 or 1；P=0；
During n=1, X1For CH2；Y1For oxygen, nitrogen or carbonyl；Wherein, X1The parent of each group connection represented is Y1, Y1What is represented is each
The parent of group connection is X1；
During m=0, Y is oxygen, nitrogen, C1-C4Alkyl amino or C1-C3Alkoxy；
During m=1, X is carbonyl, CH2Or benzyl；Y is oxygen, nitrogen, C1-C4Alkoxy, C5Heterocyclic oxy group or C1-C3Alkane silica
Base；X and Y is singly-bound；
R1For hydrogen, C6Aryl or the phenyl of nitro substitution；
R2For C1-C3Alkyl or C1-C3Alkoxy；
R3For hydrogen, C1Alkyl or C6-C12Aryl.
2. metal complex according to claim 1, it is characterised in that：In Formula II c,
L1And L2It is chlorion.
3. metal complex according to claim 1, it is characterised in that：In Formula II c,
During n=1, X1For CH2；Y1For oxygen or carbonyl；
R3For hydrogen or C6Aryl.
4. a kind of metal complex, it is following any structure,
5. the preparation method of the metal complex described in claim any one of 1-4, it is characterised in that：It comprises the steps：
The structural formula of above-mentioned metal complex intermediate (Vc) is as follows：
1) under inert gas shielding, by the substituted or unsubstituted Tosylhydrazone as shown in SM-2 inorganic strong alkali nothing
Cabbeen transition state is generated in water organic solvent；Wherein, Ra、Rb、Rc、RdAnd ReAlone for hydrogen, C1-C8Alkyl or C1-C8Alcoxyl
Base；2) under inert gas shielding, step 1) obtained Cabbeen transition state and ML1L2(PPh3)3In reaction, generation metal complex
Mesosome IV；3) under inert gas shielding, step 2) obtained metal complex intermediate and complex ligands Ic reaction generation gold
Belong to complex intermediate Vc；Wherein, complex ligands Ic structure is as follows；4) by described Vc under inert gas shielding with network
Compound ligand L reaction generation metal complex IIc；Wherein, p=0, Z are CH2Orm、n、M、L、L1、L2、X1、
X、Y、Y1、R1、R2And R3Definition with described in claim any one of 1-4；
6. the preparation method of metal complex as claimed in claim 5, it is characterised in that：
In step 1) in, described Ra、Rb、Rc、RdAnd ReIt is hydrogen；Described inorganic strong alkali is sodium methoxide, caustic alcohol, the tert-butyl alcohol
One or more in sodium and sodium hydrogen；The consumption of described inorganic strong alkali is 1-3 times of SM-2 moles；Described is anhydrous organic
Solvent is the one or more in absolute methanol, ethanol, the tert-butyl alcohol and tetrahydrofuran；The consumption of described anhydrous organic solvent is
5-30 times of SM-2 moles；The temperature of described reaction is 45-75 DEG C；
In step 2) in, described ML1L2(PPh3)3For RuCl2(PPh3)3；The temperature of described reaction is -50 DEG C to -85 DEG C；
Described ML1L2(PPh3)3Consumption be 0.3-1.0 times of SM-2 moles；
In step 3) in, the temperature of described reaction is -50 DEG C to -85 DEG C；Described complex ligands Ic consumption is complexing
1-3 times of thing intermediate mole；
In step 4) in, the temperature of described reaction is 20 DEG C to 75 DEG C, is 60 DEG C to 75 when being reacted with complex ligands IMes
DEG C, with complex ligands PCy3It is 20 DEG C to 35 DEG C during reaction；Described IMes or PCy3Consumption rubbed for complex intermediate Vc
1-3 times of that amount；
In step 1) to step 4) in, the time of reaction is untill detecting reaction completely.
7. the metal complex described in claim any one of 1-4 makees the application of catalyst in olefin metathesis metathesis reaction.
8. application according to claim 7, it is characterised in that：Described olefin metathesis metathesis reaction is intramolecular cyclization
Olefin metathesis metathesis reaction, intermolecular olefin metathesis metathesis reaction or intermolecular cycloolefin ring opening metathesis polymerization
Reaction.
9. application according to claim 8, it is characterised in that：The described cycloolefin for polymerisation is tensioned
Cycloolefin structure or polycyclic olefin structure；They are substituted or non-substituted structures, and they contain in one or more rings
F、Cl、Br、N、O、Si、S、P、B、C6-C15Aromatic series and C4-C15One or more in aromatic heterocycle substituent.
10. application according to claim 9, it is characterised in that：Described cycloolefin structure contains 4 or 5 or 7-
16 carbon atoms, or multiple hetero atoms or heteroatom group.
11. application according to claim 9, it is characterised in that：Described polycyclic olefin structure is containing 2 to 6 rings
Polycyclic olefin structure.
12. the application according to claim 9, it is characterised in that：Described polycyclic olefin is cyclopentadiene or its molecule
One or more of hydrogen by C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Amido, substitution do not take
The C in generation1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substitution or
Unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C6-C15Arylthio, the substituted or unsubstituted C of connection1-C15Alkoxy
Carbonyl, formyloxy, formamido, substituted or unsubstituted C1-C15Alkyl carbonyloxy, substituted or unsubstituted C1-C15Alkane
Base formamido, substituted or unsubstituted C6-C15Arylcarbonyloxy or substituted or unsubstituted C6-C15Aryl carboxamides
The derivative of base substitution.
13. the application according to claim 11, it is characterised in that：Described polycyclic olefin is following polycyclic olefin structure
VIa and VIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C1-
C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution do not take
The C in generation1-C15The carbonyl of alkoxy, substituted or unsubstituted C1-C15Alkyl amine group, substituted or unsubstituted C1-C15Arylamine
Base, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C1-C15Aryl carboxamides base or substitution or not
Substituted C1-C15Heterocyclic radical formamido；
R10And R11It independently is hydrogen, halogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy,
Substituted or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl,
C2-C15Heterocyclic radical, C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formamido, substitution or
Unsubstituted C1-C15Alkyl amido, C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups,
Ionic liquid monomer, liquid crystal monomer, active drug molecule；In Formula IV a, R10And R11It is not linked to be cyclic structure or is linked to be ring-type
Structure.
14. the application according to claim 11, it is characterised in that：Described polycyclic olefin is following polycyclic olefin knot
Structure VIIa-VIIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C1-
C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution do not take
The C in generation1-C15The carbonyl of alkoxy, formamido, substituted or unsubstituted C1-C15It is alkyl amido, substituted or unsubstituted
C1-C15Aryl carboxamides base or substituted or unsubstituted C1-C15Heterocyclic radical formamido；
R12For substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C1-C15
Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15Heterocyclic radical, connection substitution
Or unsubstituted C1-C15The carbonyl of alkoxy, formamido, substituted or unsubstituted C1-C15Formamido, C1-C15Alkyl sulphur
Amide groups, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule；
R13And R14It independently is substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or not
Substituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15Heterocycle
Base, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formamido, substituted or unsubstituted C1-C15Formamido,
C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or work
Property drug molecule.
15. application according to claim 8, it is characterised in that：Described intermolecular cycloolefin ring opening metathesis polymerization
React to prepare the polymerisation of macromolecule polymer material.
16. application according to claim 15, it is characterised in that：The described polymerization for preparing macromolecule polymer material is anti-
The organic solvent answered is one kind or many in dichloromethane, dichloroethanes, chloroform, toluene, dimethylbenzene, chlorobenzene and ionic liquid
Kind.
17. application according to claim 15, it is characterised in that：Described intermolecular cycloolefin ring opening metathesis polymerization
In reaction, when raw material cycloolefin or polycyclic olefin are liquid, organic solvent is not added with.
18. application according to claim 15, it is characterised in that：Described high molecular polymer be as Formula IV c, VId,
Shown in VIe, VIIc, VIId, Poly-DCPD；
Wherein, R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-C20Alkane
Base, C1-C20Alkoxy, substituted or unsubstituted C1-C20Aryloxy group, C1-C20Heterocyclic radical epoxide, C1-C20Alkylthio group, C1-C20Alkane
Silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, C6-C20Aryloxy group, connection C1-
C20The carbonyl of alkyl, connection C6-C20The carbonyl of aryl, connection C2-C20The carbonyl of heterocyclic radical, connection C6-C20The carbonyl of aryloxy group,
Connect C6-C20The carbonyl of heterocyclic radical epoxide, the substituted or unsubstituted C of connection1-C20Saturation or the Epoxide carbonyl of unsaturated alkyl,
Aminoacyl, the substituted or unsubstituted C of connection1-C20The carbonyl of saturation or unsaturated alkyl amino, connection C6-C20Arylamino
Carbonyl, connection C2-C20The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substitution do not take
The C in generation6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20The sulfonyl of alkyl amino, company
Meet C6-C20The sulfonyl or connection C of arylamino2-C20The sulfonyl of heterocyclylamino group；n1For 102-104；m1For 102-104。
19. application according to claim 18, it is characterised in that：In Formula IV c, VId, VIe, VIIc, VIId, Poly-
In DCPD,
R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-C15Alkyl,
C1-C15Alkoxy, C1-C15Heterocyclic oxy group, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkyl siloxy, C2-C15Heterocycle
Base, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, connection C1-C15The carbonyl of alkyl, connection
C6-C15The carbonyl of aryl, connection C2-C15The carbonyl of heterocyclic radical, the substituted or unsubstituted C of connection1-C15Saturation or unsaturated alkyl
Epoxide carbonyl, connection C6-C15The carbonyl of heterocyclic radical epoxide, aminoacyl, the substituted or unsubstituted C of connection1-C15Saturation or not
The carbonyl of saturated hydrocarbyl amino, connection C2-C15The carbonyl of heterocyclylamino group, urea groups, substituted or unsubstituted C1-C15Ureine
Base, substituted or unsubstituted C6-C15Aryl-ureido, substituted or unsubstituted C2-C15Heterocyclic radical urea groups, connection C1-C15Alkyl ammonia
The sulfonyl of base, connection C6-C15The sulfonyl of arylamino, connection C2-C15The sulfonyl of heterocyclylamino group；n1For 102-104；
m1For 102-104。
20. application according to claim 19, it is characterised in that：In Formula IV c, VId, VIe, VIIc, VIId, Poly-
In DCPD,
R10、R11、R12、R13And R14It independently is connection C6-C15The carbonyl or connection C of aryloxy group6-C15The carbonyl of arylamino.
21. application according to claim 19, it is characterised in that：In Formula IV c, VId, VIe, VIIc, VIId, Poly-
In DCPD,
R10、R11、R12、R13And R14It independently is hydrogen, halogen, substituted or unsubstituted C1-C8Alkyl, C1-C8Alkoxy, C1-C8Alkane
Sulfenyl, C1-C8Alkane silicon substrate, C1-C8Alkyl siloxy, C2-C8Heterocyclic radical, substituted or unsubstituted C6-C12Aryl, substitution do not take
The C in generation6-C12Aryloxy group, connection C1-C8The carbonyl of alkyl, connection C6-C12The carbonyl of aryl, connection C2-C8The carbonyl of heterocyclic radical,
Connect substituted or unsubstituted C1-C8Saturation or the Epoxide carbonyl of unsaturated alkyl, connection C6-C8The carbonyl of heterocyclic radical epoxide, ammonia
Base acyl group, the substituted or unsubstituted C of connection1-C8The carbonyl of saturation or unsaturated alkyl amino, connection C2-C8Heterocyclylamino group
Carbonyl, connection C1-C8The sulfonyl of alkyl amino, connection C6-C12The sulfonyl of arylamino, connection C2-C8Heterocyclylamino group
Sulfonyl；n1For 102-104；m1For 102-104。
22. application according to claim 21, it is characterised in that：In Formula IV c, VId, VIe, VIIc, VIId, Poly-
In DCPD,
R10、R11、R12、R13And R14It independently is connection C6-C12The carbonyl or connection C of aryloxy group6-C12The carbonyl of arylamino.
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| CN104262590B (en) | 2018-10-09 |
| 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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