CN1234697C - 制备n－取代的2,6－二烷基吗啉的方法 - Google Patents
制备n－取代的2,6－二烷基吗啉的方法 Download PDFInfo
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- CN1234697C CN1234697C CNB028065980A CN02806598A CN1234697C CN 1234697 C CN1234697 C CN 1234697C CN B028065980 A CNB028065980 A CN B028065980A CN 02806598 A CN02806598 A CN 02806598A CN 1234697 C CN1234697 C CN 1234697C
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000002780 morpholines Chemical class 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 150000003335 secondary amines Chemical class 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000002837 carbocyclic group Chemical group 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- JMXKCYUTURMERF-UHFFFAOYSA-N dodemorph Chemical compound C1C(C)OC(C)CN1C1CCCCCCCCCCC1 JMXKCYUTURMERF-UHFFFAOYSA-N 0.000 claims description 2
- -1 platinum group metals Chemical class 0.000 abstract description 31
- 150000004307 14-membered carbocyclic compounds Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000007942 carboxylates Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
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- 150000002736 metal compounds Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- HNVIQLPOGUDBSU-UHFFFAOYSA-N 2,6-dimethylmorpholine Chemical compound CC1CNCC(C)O1 HNVIQLPOGUDBSU-UHFFFAOYSA-N 0.000 description 4
- IMYCBNLQFUEBRK-UHFFFAOYSA-N 4-cyclododecylmorpholine Chemical compound C1COCCN1C1CCCCCCCCCCC1 IMYCBNLQFUEBRK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 239000000377 silicon dioxide Substances 0.000 description 4
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- HNVIQLPOGUDBSU-OLQVQODUSA-N (2s,6r)-2,6-dimethylmorpholine Chemical compound C[C@H]1CNC[C@@H](C)O1 HNVIQLPOGUDBSU-OLQVQODUSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 239000002243 precursor Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- HNVIQLPOGUDBSU-PHDIDXHHSA-N (2r,6r)-2,6-dimethylmorpholine Chemical class C[C@@H]1CNC[C@@H](C)O1 HNVIQLPOGUDBSU-PHDIDXHHSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KQPQBMNTWHMZMO-IAGOWNOFSA-N (2R,6R)-4-(cyclododecen-1-yl)-2,6-dimethylmorpholine Chemical compound C1(=CCCCCCCCCCC1)N1C[C@H](O[C@@H](C1)C)C KQPQBMNTWHMZMO-IAGOWNOFSA-N 0.000 description 1
- HNVIQLPOGUDBSU-WDSKDSINSA-N (2s,6s)-2,6-dimethylmorpholine Chemical compound C[C@H]1CNC[C@H](C)O1 HNVIQLPOGUDBSU-WDSKDSINSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910003603 H2PdCl4 Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000002538 fungal effect Effects 0.000 description 1
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- 239000000417 fungicide Substances 0.000 description 1
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- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 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
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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- C07—ORGANIC CHEMISTRY
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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Abstract
本发明涉及一种制备通式(I)的N-取代的2，6-二烷基吗啉的方法，其中，R1和R2各自独立地是氢、烷基或环烷基，或R1和R2与和它们连接的碳原子一起是5-14员碳环，和R3和R4各自独立地是烷基或环烷基。本发明的物质通过使至少一种通式(II)的羰基化合物与至少一种通式(III)的吗啉在氢气和至少一种含金属的催化剂存在下反应来制备，该催化剂的活性组分基本上由铂族金属组成，其中R1和R2具有上述含义，R3和R4具有上述含义。
Description
本发明涉及一种通过羰基化合物与仲胺在还原胺化反应中制备N-取代的2，6-二烷基吗啉的方法。
叔胺形成在工业上得到广泛应用的重要的化合物。所以，仍然需要简单可行的方法，允许从容易获得的组分以高产率和对所需目标化合物的高选择性制备叔胺。在杂环叔胺中，例如在作物保护中使用N-取代的四氢-1，4-噁嗪(吗啉)。
K.H.Knig等人在Angewandte Chemie77(1965，327-333页)中描述了N-取代的四氢-1，4-噁嗪及其作为杀霉化合物的用途，具有对农作物的霉菌混乱的良好作用。根据该文献，这些化合物的制备可以例如通过相应的二(2-羟乙基)胺进行脱水环化来进行。
DE-A-25 43 279同样地描述了制备N-取代的四氢-1，4-噁嗪的方法，其中进行N-取代的二(2-羟烷基)胺的单步或两步环化和氢化。
上述方法的缺点在于所用原料的制备方法是复杂的。
DE-A-197 20 475描述了一种在两步合成中制备N-烷基-2，6-二烷基吗啉的方法，包括使相应的醛或酮与仲胺的二醇在酸性离子交换剂的存在下反应来制备噁唑烷，噁唑烷随后在氢气和加氢催化剂的存在下进行反应。
从羰基化合物和特别是从酮和仲胺直接制备叔胺的方法通常是困难的，这是因为通常仅仅以低产率获得目标化合物，它们的分离相应地也是困难的。
DE-A-33 21 712描述了2，6-反式-二甲基吗啉衍生物及其作为杀菌剂的用途。根据该文献，制备N-(环十二烷基)-2，6-二甲基吗啉(环十二烷基吗啉)的方法例如按照两步合成来进行，包括将环十二烷酮与2，6-反式-二甲基吗啉在对甲苯磺酸存在下反应，得到N-环十二碳烯基-2，6-反式-二甲基吗啉和随后在Pd/C催化剂的存在下进行氢化。
EP-A-0 271 750描述了杀菌性4-取代的环己基胺。这些可以例如在还原剂存在下用仲胺将环己酮还原胺化。合适的还原剂是氢气、甲酸和配合氢化物，例如氰基硼氢化钠。其中没有描述在氢气下进行还原胺化的合适催化剂。该反应方式也没有通过工作实施例来证明。
DE-A-21 18 283描述了一种制备脂族或脂环族的仲胺或叔胺的方法，其中在氢气和加氢催化剂存在下使脂族或脂环族羰基化合物与氨或伯或仲胺反应，其中所用的催化剂是银和钯在烧结载体上的混合物。该方法的缺点是所用的银催化剂的成本高。另外，所得目标化合物的产率和选择性需要改进。
本发明的目的是提供一种制备N-取代的2，6-二烷基吗啉的改进方法。其中，从羰基化合物和仲胺按照单步反应来开始合成。优选的是，该方法应该能以高产率和对目标化合物的高选择性来制备叔胺。
现在，我们惊奇地发现，该目的通过一种制备N-取代的2，6-二烷基吗啉的方法得以实现，其中至少一种羰基化合物与至少一种吗啉衍生物在氢气和至少一种含金属的催化剂存在下按照还原胺化反应，该催化剂的活性组分基本上由铂族金属组成。
本发明因此提供一种制备式I的N-取代的2，6-二烷基吗啉的方法，
其中，
R1和R2各自独立地是氢、烷基或环烷基，或R1和R2与和它们连接的碳原子一起是5-14员碳环，和
R3和R4各自独立地是烷基或环烷基，在该方法中，至少一种式II的羰基化合物与至少一种式III的吗啉在氢气和至少一种含金属的催化剂存在下反应，该催化剂的活性组分基本上由铂族金属组成，
其中R1和R2具有上述含义，
其中R3和R4具有上述含义。
为了本发明的目的，术语“烷基”包括直链和支链烷基。它们优选是直链或支链C1-C20烷基，优选C1-C12烷基，特别优选是C1-C8烷基，和非常特别优选是C1-C4烷基。烷基例如特别是甲基、乙基、丙基、异丙基、正丁基、2-丁基、仲丁基、叔丁基、正戊基、2-戊基、2-甲基丁基、3-甲基丁基、1，2-二甲基丙基、1，1-二甲基丙基、2，2-二甲基丙基、1-乙基丙基、正己基、2-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1，2-二甲基丁基、1，3-二甲基丁基、2，3-二甲基丁基、1，1-二甲基丁基、2，2-二甲基丁基、3，3-二甲基丁基、1，1，2-三甲基丙基、1，2，2-三甲基丙基、1-乙基丁基、2-乙基丁基、1-乙基-2-甲基丙基、正庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、辛基、壬基、癸基。
取代的烷基基团优选具有1、2、3、4或5个取代基，特别是1、2或3个取代基。这些取代基选自例如环烷基、芳基、杂芳基、卤素、OH、SH、烷氧基、烷硫基、NE1E2、(NE1E2E3)+、羧基、羧酸根、-SO3H、磺酸根、硝基和氰基。
环烷基基团优选是C6-C12环烷基基团，例如环己基、环庚基、环辛基、环癸基或环十二烷基。特别优选环己基和环十二烷基。
如果环烷基是被取代的，则它优选具有1、2、3、4或5个取代基，特别是1、2或3个取代基。这些取代基选自例如烷基、烷氧基、烷硫基、OH、SH、环烷基、环烷基烷基、硝基、氰基或卤素。
芳基优选是苯基、甲苯基、二甲苯基、基、萘基、蒽基、菲基、并四苯基，特别是苯基或萘基。
取代的芳基优选具有1、2、3、4或5个取代基，特别是1、2或3个取代基。这些取代基选自例如烷基、烷氧基、羧基、羧酸根、三氟甲基、-SO3H、磺酸根、NE1E2、亚烷基-NE1E2、硝基、氰基或卤素。
杂芳基优选是吡咯基、吡唑基、咪唑基、吲哚基、咔唑基、吡啶基、喹啉基、吖啶基、哒嗪基、嘧啶基或吡嗪基。
取代的杂芳基优选具有1、2、3个取代基，选自烷基、烷氧基、羧基、羧酸根、-SO3H、磺酸根、NE1E2、亚烷基-NE1E2、三氟甲基或卤素。
上述关于烷基基团的叙述也适合于烷氧基和烷硫基基团。
基团NE1E2优选是N，N-二甲基、N，N-二乙基、N，N-二丙基、N，N-二异丙基、N，N-二正丁基、N，N-二叔丁基、N，N-二环己基或N，N-二苯基。
卤素是氟、氯、溴和碘，优选氟、氯和溴。
为了本发明的目的，羧酸根和磺酸根优选是羧酸官能的衍生物或磺酸官能的衍生物，特别是金属羧酸盐或金属磺酸盐，羧酸酯或磺酸酯官能的衍生物，或者羧酰胺或磺酰胺官能的衍生物。
根据本发明使用的活性组分基本上由铂族金属组成，即Ru、Rh、Pd、Os、Ir、Pt和其混合物。
优选使用其活性组分基本不含银的催化剂。
优选使用其活性组分包含以下物质的催化剂：
-1-100重量％、优选10-99重量％的Pd，
-0-60重量％、优选1-55重量％的Pt，和
-0-50重量％、例如0.1-40重量％的至少一种其它金属，其特别选自
Ru、Rh、Os、Ir、Ce、La和其混合物。
在本发明方法中，优选使用含有载体的催化剂。合适的载体是本领域技术人员熟知的常用载体材料。这些载体包括例如含碳的载体材料，例如活性炭，碳化硅，聚合物载体，金属载体(例如由不锈钢制成)，氧化铝，二氧化硅，硅酸盐，硅铝酸盐，例如沸石，浮石，硅藻土，硅胶，水滑石，二氧化钛，二氧化锆，氧化锌，氧化镁和其混合物。在适宜时，载体材料可以用碱金属和/或碱土金属氧化物掺杂。特别优选使用α-Al2O3、γ-Al2O3、SiO2、TiO2、ZrO2和其混合物。特别优选ZrO2。载体通常具有常规的形状，可以例如作为挤出物(成股的形式)、粒料、珠粒、片料、环、鞍形物、织造织物、编织物、整料、球形、粉末等。对于非连续方法，优选以粉末形式使用。
所用的催化剂可以通过常规公知的方法制备，例如用含所用金属的化合物或配合物的溶液浸渍载体。合适的金属化合物(前体)是例如金属盐，例如硝酸盐、硝酰基硝酸盐、卤化物、碳酸盐、羧酸盐；金属配合物，例如乙酰丙酮化物；卤素配合物，例如含氯配合物，胺配合物等。金属化合物可以被涂布在载体上，例如通过常规的沉淀或浸渍进行。如果使用两种或多种金属化合物，则这些化合物可以同时涂布或依次涂布。在本申请中，活性组分的涂布顺序通常不是重要的。合适的用于通过浸渍制备催化剂的溶剂是水和有机溶剂，例如醇类，例如甲醇和乙醇；芳族化合物，例如苯和甲苯；脂族溶剂，例如己烷、庚烷等；脂环族溶剂，例如环己烷等。
含钯的担载催化剂的制备优选通过用Pd(NO3)2、PdCl2、H2PdCl4、乙酰丙酮化钯等的溶液浸渍载体来进行。
在浸渍之后，载体优选进行干燥。此时的温度通常是约50-200℃，优选100-150℃。在干燥后，如果需要的话，载体可以进行煅烧。为此，温度通常是约200-600℃，优选400-500℃。煅烧时间可以在宽范围内变化，和例如是约1-10小时，优选1.5-5小时。为了将前体转化成活性组分，催化剂可以用常规的还原剂例如氢气处理。在该处理过程中，如果需要的话，惰性气体例如氮气或氩气可以与还原剂混合。在还原期间的温度优选是约100-500℃，特别优选约200-300℃。如果为了制备本发明的催化剂而将易于热分解的金属化合物用作前体，则这些化合物通常已经在煅烧条件下被分解成元素金属或氧化性金属化合物，这意味着随后的还原通常是不需要的。
干燥和/或煅烧和/或还原之后，可以进行至少一个其它处理步骤。这些处理包括例如惰化，例如用氧气进行，其中如果合适的话，在氧气中可以混合至少一种惰性气体。钝化优选用于制备这样的催化剂，这些催化剂以那些其金属氧化物已经具有催化活性的金属为基础。
制备可以根据本发明使用的催化剂的其它方法是本领域技术人员公知的，包括例如蒸气沉积、溅射、离子交换法等。
根据合适的实施方案，催化剂在现场被氢气还原，并转化成活性形式。
催化剂的表面积、孔体积和孔尺寸分布不是关键的，可以在宽范围内。
在本发明方法中，特别优选使用这样的催化剂，基于活性组分和载体的重量计，该催化剂含有0.1-10重量％的Pd。该催化剂优选含有0-5重量％、例如0.1-4重量％的Pt。特别优选仅仅含有Pd作为活性组分的催化剂。
本发明方法以有利的方式允许单步制备N-取代的2，6-二烷基吗啉。在本发明中，目标化合物通常以高产率和高选择性获得。即使在高的原料进料速率的情况下，本发明方法也有利地制备N-取代的2，6-二烷基吗啉，即通常达到良好的时空产率。本发明方法的另一个优点是使得有可能以异构纯的方式制备N-取代的2，6-二烷基吗啉。
优选，对于制备N-取代的2，6-二烷基吗啉，使用式II的酮，其中R1和R2与和它们连接的碳原子一起形成6-12员碳环，该碳环可以具有1、2或3个取代基，这些取代基独立地选自烷基、烷氧基、烷硫基、环烷基和环烷基烷基。式II的化合物特别优选是环十二烷酮。
优选，式III中的基团R3和R4各自独立地是C1-C4烷基。特别优选，R3和R4都是甲基。
本发明方法特别适合于制备N-(环十二烷基)-2，6-二甲基吗啉(环十二烷基吗啉)。
反应温度优选是100-300℃。
反应压力优选是5-300巴，特别优选10-250巴。
本发明方法可以在存在或不存在溶剂的情况下进行。合适的溶剂是水；醇类，例如甲醇和乙醇；醚类，例如甲基叔丁基醚；环醚，例如四氢呋喃；酮类，例如丙酮和甲基乙基酮等。用作原料的吗啉特别优选用作溶剂。在这方面，吗啉可以以相对于胺组分计至多100倍摩尔过量来使用。
本发明方法可以以间歇或连续的方式进行。优选连续的方式。
用于进行本发明方法的合适的反应器是本领域技术人员公知的在高压下操作的常规设备，例如高压釜或管式反应器。催化剂优选以固定床或其它合适的插入形式来使用。反应空间优选以立式方式排列。
该反应优选在从上至下流经催化剂床时或在从下至上流经催化剂床时进行。在这方面，原料优选以这样的方式引入，使得整个催化剂层基本上连续地被液体覆盖。
本发明进一步提供上述催化剂用于制备叔胺的用途，其中使至少一种羰基化合物与至少一种仲胺在氢气的存在下反应。
下面参考非限制性实施例更详细地描述本发明。
实施例
实施例1(对比Pd/Ag催化剂)：
将500ml的在SiO2载体上含5％Ag2O和0.4％PdO的催化剂加入立式管式反应器中。在220℃的温度和100巴的氢气压力下，将已加热到220℃的1份顺式-2，6-二甲基吗啉、1份反式-2，6-二甲基吗啉和0.39份环十二酮的混合物以360ml/h的进料速率从下面泵入。
在减压下除去2，6-二甲基吗啉之后，该反应混合物含有89.6％的环十二烷基吗啉和2.3％的环十二酮。这相应于97.3％的转化率和91％的选择性。
实施例2(Pd/ZrO2催化剂)：
进行实施例1的工序，但是使用纯的顺式-2，6-二甲基吗啉和Pd/ZrO2催化剂(钯含量0.9％)。在相同的温度和进料速率下和除去2，6-二甲基吗啉的情况下，反应混合物含有94.4％的环十二烷基吗啉和0.7％的环十二酮。这相应于99.3％的转化率和95％的选择性。
实施例3(Pd/ZrO2催化剂)：
进行实施例2的工序，但是使用双倍进料速率(720ml/h)和240℃的温度。在除去2，6-二甲基吗啉之后，反应混合物含有92.2％的环十二烷基吗啉和2.6％的环十二酮。这相应于97.4％的转化率和95％的选择性。
实施例4(Pd/Pt，ZrO2催化剂)：
进行实施例1的工序，但是使用纯的顺式-2，6-二甲基吗啉和Pd/Pt/ZrO2催化剂(钯含量0.4％，铂含量0.4％)。在230℃的温度和180ml/h的进料速率下和除去2，6-二甲基吗啉之后，反应混合物含有95.6％的顺式环十二烷基吗啉，且不含环十二酮。这相应于100％的转化率和95％的选择性。
Claims (9)
1.一种制备式I的N-取代的2，6-二烷基吗啉的方法，
其中，
R1和R2各自独立地是氢、C1-C20烷基或C6-C12环烷基，或R1和R2与和它们连接的碳原子一起是5-14员碳环，和
R3和R4各自独立地是C1-C20烷基或C6-C12环烷基，
在该方法中，至少一种式II的羰基化合物与至少一种式III的吗啉在氢气和至少一种含金属的催化剂存在下反应，
其中R1和R2具有上述含义，
其中R3和R4具有上述含义，
其中使用其活性组分包含以下物质的催化剂：
-1-100重量％的Pd，
-0-60重量％的Pt，和
-0-50重量％的至少一种其它金属，选自Ru、Rh、Os、Ir、Ce、La和其混合物。
2.根据权利要求1的方法，其中使用含有载体的催化剂。
3.根据权利要求2的方法，其中所用的载体是ZrO2。
4.根据权利要求2或3的方法，其中使用含有0.1-10重量％的Pd和0-5重量％的Pt的含载体的催化剂，所述重量％是基于活性组分和载体的重量计。
5.根据权利要求1的方法，其中R1和R2与和它们连接的碳原子一起形成6-12员碳环，该碳环可以具有1、2或3个取代基，这些取代基独立地选自C1-C20烷基、C1-C20烷氧基、C1-C20烷硫基、C6-C12环烷基和C6-C12环烷基-C1-C20烷基。
6.根据权利要求1的方法，其中R3和R4各自独立地是C1-C4烷基。
7.根据权利要求1的方法，其中R3和R4都是甲基。
8.根据权利要求1的方法，其中式I的化合物是N-(环十二烷基)-2，6-二甲基吗啉。
9.其活性组分包含以下物质的催化剂用于制备叔胺的用途，
-1-100重量％的Pd，
-0-60重量％的Pt，和
-0-50重量％的至少一种其它金属，选自Ru、Rh、Os、Ir、Ce、La和其混合物，
其中使至少一种羰基化合物与至少一种仲胺在氢气的存在下反应。
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| EP1868616A2 (en) * | 2005-03-29 | 2007-12-26 | The University of Maryland, Baltimore | Inhibitors for extracellular signal-regulated kinase docking domains and uses therefor |
| DE102005019540A1 (de) * | 2005-04-27 | 2006-11-09 | Basf Ag | Verfahren zur Herstellung eines Amins |
| ATE545626T1 (de) * | 2006-03-21 | 2012-03-15 | Basf Se | Verfahren zur herstellung eines amins |
| US8507704B2 (en) * | 2009-09-08 | 2013-08-13 | Air Products And Chemicals, Inc. | Liquid composition containing aminoether for deposition of metal-containing films |
| CN108484529B (zh) * | 2018-06-06 | 2019-11-05 | 南通江天化学股份有限公司 | 一种n,n’-亚甲基双吗啉的合成方法 |
| EP3611570A1 (en) * | 2018-08-16 | 2020-02-19 | ASML Netherlands B.V. | Method for controlling a manufacturing process and associated apparatuses |
| CN110713469A (zh) * | 2019-09-26 | 2020-01-21 | 宿州亿帆药业有限公司 | 一种十三吗啉的合成工艺 |
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| US2779789A (en) | 1953-10-28 | 1957-01-29 | Universal Oil Prod Co | Reductive alkylation process |
| DE1014547B (de) * | 1953-10-28 | 1957-08-29 | Universal Oil Prod Co | Verfahren zur reduktiven Alkylierung von Amino- und Nitroverbindungen |
| BE790119A (fr) * | 1971-04-15 | 1973-04-13 | Basf Ag | Procede de preparation d'amines aliphatiques et cycloaliphatiques secondaires ou tertiaires. |
| DE2118963C3 (de) | 1971-04-20 | 1974-01-17 | A. Ahlstroem Oy, Helsinki | Verfahren und Vorrichtung zum kontinuierlichen Aufwickeln von Materialbahnen in Einzelrollen und Vorrichtung zur Durchführung des Verfahrens |
| DE2543279A1 (de) * | 1975-09-27 | 1977-04-07 | Basf Ag | Verfahren zur herstellung von n-substituierten tetrahydro-1.4-oxazinen |
| DE2657476A1 (de) | 1976-12-18 | 1978-06-22 | Basf Ag | Morpholinderivate |
| DE2830999A1 (de) * | 1978-07-14 | 1980-01-31 | Basf Ag | Verfahren zur herstellung von stereoisomeren n-aralkyl-2,6-dimethylmorpholinen |
| US4283534A (en) * | 1979-04-11 | 1981-08-11 | Basf Aktiengesellschaft | Reductive alkylation of nitrogen heterocycles |
| EP0111928A1 (en) | 1982-12-20 | 1984-06-27 | Air Products And Chemicals, Inc. | Catalysis of condensation reactions |
| DE3321712A1 (de) * | 1983-06-16 | 1984-12-20 | Basf Ag, 6700 Ludwigshafen | 2,6-trans-dimethylmorpholinderivate und diese enthaltende fungizide und verfahren zur bekaempfung von pilzen |
| DE3643009A1 (de) * | 1986-12-17 | 1988-06-30 | Basf Ag | Fungizide cyclohexylamine |
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