CN104837807A - 制备胺类的方法 - Google Patents
制备胺类的方法 Download PDFInfo
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- CN104837807A CN104837807A CN201380064379.6A CN201380064379A CN104837807A CN 104837807 A CN104837807 A CN 104837807A CN 201380064379 A CN201380064379 A CN 201380064379A CN 104837807 A CN104837807 A CN 104837807A
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- alkyl
- aryl
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- 150000001412 amines Chemical class 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- -1 amine compound Chemical class 0.000 claims abstract description 59
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 150000002430 hydrocarbons Chemical group 0.000 claims description 22
- 239000010948 rhodium Substances 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 125000004429 atom Chemical group 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical class 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 150000003283 rhodium Chemical class 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 239000003849 aromatic solvent Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000003284 rhodium compounds Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000006268 reductive amination reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 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
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 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
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical compound [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000006371 dihalo methyl group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 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
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical class C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 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
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000004312 morpholin-2-yl group Chemical group [H]N1C([H])([H])C([H])([H])OC([H])(*)C1([H])[H] 0.000 description 1
- 125000004572 morpholin-3-yl group Chemical group N1C(COCC1)* 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- LIJJGMDKVVOEFT-UHFFFAOYSA-N n-benzyl-4-methoxyaniline Chemical compound C1=CC(OC)=CC=C1NCC1=CC=CC=C1 LIJJGMDKVVOEFT-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical class CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 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
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002206 pyridazin-3-yl group Chemical group [H]C1=C([H])C([H])=C(*)N=N1 0.000 description 1
- 125000004940 pyridazin-4-yl group Chemical group N1=NC=C(C=C1)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D295/027—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及制备胺类的方法,所述方法包括使包含羰基部分的式R1-CO-R2的化合物与式HNR3R4的胺化合物和一氧化碳在催化剂的存在下反应。
Description
本发明涉及新的有机反应和制备和使用这样的反应产物的方法。更具体地,本发明涉及用于还原氨基化的新反应和在无需外部氢源的情况下由该反应产物制备另外的产物的方法。
羰基化合物的还原氨基化是用于生产胺类的关键,且毫无例外地需要氢源,最常用的是氢气(H2)自身。然而,尽管氢不贵且以工业化规模使用,但是它与空气具有宽爆炸范围且可以引起大爆炸。
此外,当今的大部分氢产自化石材料,例如天然气。实现这一目的的主要方法通过包含两步的甲烷蒸汽重整(SMR)法进行。第一步包括使甲烷(CH4)与蒸汽在750-800℃下反应,产生H2和CO。然后使CO-副产物经通道导入第二步,称作水煤气变换(WGS)反应,其中使其与更多蒸汽在催化剂上反应,形成另外的H2和二氧化碳(CO2)。这种方法自身分两个阶段进行,由在350℃下的高温变换和在190-210℃下的低温变换组成。在最终的步骤中,必须从二氧化碳,甲烷,未反应的一氧化碳和水中分离氢。一旦纯化,则将得到的氢供给用于众多应用,包括还原氨基化。
其它的氢源可能经济性较低且昂贵或遇湿气和空气不稳定。
胺类是一类极为有用的和不能代替的化合物。它们不仅用于工业和实验室作为产物(例如药物,染料,气体净化等),而且作为试剂和催化剂。因此,对于用于制备胺类的简便而有效的方法存在需求。
发明人已经研究了几种用于制备胺类的方法。合成胺类的最重要方法之一通过还原亚胺类进行。作为更直接和经济的方法,用胺类对羰基化合物进行还原氨基化避免了亚胺形成的分离步骤。这种方法由此需要更少的纯化步骤并且生成更少的溶剂废物。
发明人研究了几种潜在的均相和多相催化剂系统,并且认为,在工业化应用背景下,使用CO直接作为还原剂可以提供明显的优点,因为作为本领域状态下使用的包括加热至350℃的3个步骤和3种不同催化剂可以被转化成仅使用单一催化剂的单一操作。
一氧化碳与胺-化合物的反应是现有技术中公知的,例如参见Chan Sik Cho,Journal of Heterocyclic Chemistry,1997,1371-1374页。然而,该方法是众所周知的芳基卤与CO的羰基化反应,其与另一种醛的脱氧代-双取代反应组合,由此形成二氢吲哚酮化合物。在该反应中,未进行还原,且由此该方法不是如本发明中的还原氨基化。
发明人还测试了其它均相和多相金属催化剂,且最终,发明人鉴定铑盐例如乙酸铑作为特别有效的催化剂,其用于用对-茴香胺对醛例如苯甲醛在一氧化碳的存在下进行还原氨基化,得到N-苄基-4-甲氧基苯胺。在溶剂筛选时,发现乙酸铑催化的反应有效地在不同溶剂中进行,其中在THF中的反应速率最高。铑源例如Rh(PPh3)3Cl,Rh6(CO)16,[Rh(CO)2Cl]2,[Rh(COD)Cl]2,HRh(PPh3)4,多相铑和钌均显示了不同的催化活性。
因此,本发明涉及新的还原氨基化反应和由它们制备任意另外产物的方法。该反应如方案1中所示。
因此本发明涉及制备胺类的方法,其中使包含式R1-CO-R2的羰基部分的化合物与式HNR3R4的化合物和一氧化碳在催化剂的存在下反应。所述催化剂可以具体地选自多相和/或均相金属催化剂,其选自Pt,Pd,Ir,Rh,Ru,Os,Mo,Ni,Cr,V,Cu,Mn,Zn,Fe,硫,硒及它们的催化活性化合物。该反应可以在溶剂中进行,也可以在无溶剂下进行。
在上述式中,
R1和R2各自独立地是氢或烃基,所述烃基可以相同或不同且可以各自选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基,C6-C20芳香烃或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃取代基任选地被一个或多个基团取代,所述基团选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,或C6-C20芳香烃或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基或杂取代基,其中R1和R2的至少一个不是氢,或
R1和R2形成具有4-10个环原子的脂环族或杂脂环族环结构,其任选地包括不饱和键,每个环结构任选地被一个或多个取代基取代,所述取代基选自杂取代基,C1-C20直链、支链或环状脂族烃类,其任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基或C6-C20芳香烃,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃任选地被一个或多个杂取代基取代,且
R3和R4各自独立地是氢或烃基,所述烃基可以相同或不同且可以各自选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基或C6-C20芳香烃或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃取代基任选地被一个或多个基团取代,所述基团选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,或C6-C20芳香烃或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基或杂取代基,其中R3和R4的至少一个不是氢,或
R3和R4形成具有4-10个环原子的脂环族或杂脂环族环结构,其任选地包括不饱和键,每个环结构任选地被一个或多个取代基取代,所述取代基选自杂取代基,C1-C20直链、支链或环状脂族烃类,其任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基或C6-C20芳香烃,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃任选地被一个或多个杂取代基取代。
在上述式中,R1和R2特别地可以各自独立地是氢或取代基,所述取代基选自C1-C20烷基,C2-C20烯基,C2-C20炔基,芳基,优选C6-C14芳基,C1-C20羧酸酯,C1-C20烷氧基,C2-C20烯氧基,C2-C20炔氧基,芳氧基,C2-C20烷氧羰基,C1-C20烷硫基,芳硫基,C1-C20烷基磺酰基,C1-C20烷基亚磺酰基,所述取代基任选地被一个或多个部分取代,所述部分选自C1-C10烷基,C1-C10烷氧基,芳基,优选C6-C14芳基,和一个或多个官能团,所述官能团选自羟基,硫醇,硫醚,酮,醛,酯,醚,胺,亚胺,酰胺,硝基,羧酸,二硫化物,碳酸酯,异氰酸酯,碳二亚胺,烷氧羰基,氨基甲酸酯和卤素,其中R1和R2的至少一个不是氢,且
R3和R4可以各自独立地是氢或取代基,所述取代基选自C1-C20烷基,C2-C20烯基,C2-C20炔基,芳基,优选C6-C14芳基,C1-C20羧酸酯,C1-C20烷氧基,C2-C20烯氧基,C2-C20炔氧基,芳氧基,C2-C20烷氧羰基,C1-C20烷硫基,芳硫基,C1-C20烷基磺酰基,C1-C20烷基亚磺酰基,所述取代基任选地被一个或多个部分取代,所述部分选自C1-C10烷基,C1-C10烷氧基,芳基,优选C6-C14芳基,和一个或多个官能团,所述官能团选自羟基,硫醇,硫醚,酮,醛,酯,醚,胺,亚胺,酰胺,硝基,羧酸,二硫化物,碳酸酯,异氰酸酯,碳二亚胺,烷氧羰基,氨基甲酸酯和卤素,其中R3和R4的至少一个不是氢。
本发明如上述所定义的杂取代基可以选自=O,OH,F,Cl,Br,I,CN,NO2,SO3H,一卤代甲基,二卤代甲基,三卤代甲基,CF(CF3)2,SF5,通过N原子结合的胺,-O-烷基(烷氧基),-O-芳基,-O-SiRS 3,S-RS,S(O)-RS,S(O)2-RS,COOH,CO2-RS,通过C或N原子结合的酰胺,甲酰基,C(O)-RS,COOM,其中M可以是金属,例如Na或K。RS 3可以彼此独立地相同或不同,且可以各自是脂族,杂脂族,芳族或杂芳族基团,它们各自任选地进一步被一个或多个杂取代基,脂族,杂脂族,芳族或杂芳族基团取代。
包括烷基,烯基和炔基的脂族烃类可以包含直链、支链或环状烃类。
杂脂族基团(heteroaliphatic)是具有1-20个碳原子的烃,包括烷基,烯基和炔基,其可以包含直链、支链和环状烃类,其中一个或多个碳原子被杂原子替代或取代。
更具体地,C1-C20-烷基可以是直链或支链的且具有1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19或20个碳原子。烷基可以是C1-C6-烷基,特别是甲基,乙基,丙基,异丙基,丁基,异丁基,仲-丁基或叔-丁基,同样是戊基,1-,2-或3-甲基丙基,1,1-,1,2-或2,2-二甲基丙基,1-乙基丙基,己基,1-,2-,3-或4-甲基戊基,1,1-,1,2-,1,3-,2,2-,2,3-或3,3-二甲基丁基,1-或2-乙基丁基,1-乙基-1-甲基丙基,1-乙基-2-甲基丙基,1,1,2-或1,2,2-三甲基丙基。取代的烷基是三氟甲基,五氟乙基和1,1,1-三氟乙基。
环烷基可以是环丙基,环丁基,环戊基,环己基或环庚基。
烯基可以是C2-C20烯基。炔基可以是C2-C20炔基。
卤素是F,Cl,Br或I。
烷氧基优选是C2-C10烷氧基,例如甲氧基,乙氧基,丙氧基,叔-丁氧基等。
具有一个或多个选自N、O和S的杂原子的C3-C8-杂环烷基优选是2,3-二氢-2-,-3-,-4-或-5-呋喃基,2,5-二氢-2-,-3-,-4-或-5-呋喃基,四氢-2-或-3-呋喃基,1,3-二氧戊环-4-基,四氢-2-或-3-噻吩基,2,3-二氢-1-,-2-,-3-,-4-或-5-吡咯基,2,5-二氢-1-,-2-,-3-,-4-或-5-吡咯基,1-,2-或3-吡咯烷基,四氢-1-,-2-或-4-咪唑基,2,3-二氢-1-,-2-,-3-,-4-或-5-吡唑基,四氢-1-,-3-或-4-吡唑基,1,4-二氢-1-,-2-,-3-或-4-吡啶基,1,2,3,4-四氢-1-,-2-,-3-,-4-,-5-或-6-吡啶基,1-,2-,3-或4-哌啶基,2-,3-或4-吗啉基,四氢-2-,-3-或-4-吡喃基,1,4-二噁烷基,1,3-二噁烷-2-,-4-或-5-基,六氢-1-,-3-或-4-哒嗪基,六氢-1-,-2-,-4-或-5-嘧啶基,1-,2-或3-哌嗪基,1,2,3,4-四氢-1-,-2-,-3-,-4-,-5-,-6-,-7-或-8-喹啉基,1,2,3,4-四氢-1-,-2-,-3-,-4-,-5-,-6-,-7-或-8-异喹啉基,2-,3-,5-,6-,7-或8-3,4-二氢-2H-苯并-1,4-噁嗪基。
任选取代的是指未取代或单取代,二取代,三取代,四取代,五取代的,乃至对于烃上的每个氢进一步被取代的。
芳基可以是苯基,萘基或联苯基。
芳基烷基可以是苄基。
具有一个或多个选自N、O和S的杂原子的杂芳基优选是2-或3-呋喃基,2-或3-噻吩基,1-,2-或3-吡咯基,1-,2-,4-或5-咪唑基,1-,3-,4-或5-吡唑基,2-,4-或5-噁唑基,3-,4-或5-异噁唑基,2-,4-或5-噻唑基,3-,4-或5-异噻唑基,2-,3-或4-吡啶基,2-,4-,5-或6-嘧啶基,还优选1,2,3-三唑-1-,-4-或-5-基,1,2,4-三唑-1-,-3-或-5-基,1-或5-四唑基,1,2,3-噁二唑-4-或-5-基,1,2,4-噁二唑-3-或-5-基,1,3,4-噻二唑-2-或-5-基,1,2,4-噻二唑-3-或-5-基,1,2,3-噻二唑-4-或-5-基,3-或4-哒嗪基,吡嗪基,1-,2-,3-,4-,5-,6-或7-吲哚基,4-或5-异吲哚基,1-,2-,4-或5-苯并咪唑基,1-,3-,4-,5-,6-或7-苯并吡唑基,2-,4-,5-,6-或7-苯并噁唑基,3-,4-,5-,6-或7-苯并异噁唑基,2-,4-,5-,6-或7-苯并噻唑基,2-,4-,5-,6-或7-苯并异噻唑基,4-,5-,6-或7-苯并-2,1,3-噁二唑基,2-,3-,4-,5-,6-,7-或8-喹啉基,1-,3-,4-,5-,6-,7-或8-异喹啉基,3-,4-,5-,6-,7-或8-噌啉基,2-,4-,5-,6-,7-或8-喹唑啉基,5-或6-喹喔啉基,2-,3-,5-,6-,7-或8-2H-苯并-1,4-噁嗪基,还优选1,3-苯并间二氧杂环戊烯-5-基,1,4-苯并二噁烷-6-基,2,1,3-苯并噻二唑-4-或-5-基或2,1,3-苯并噁二唑-5-基。
还原剂是提供于反应室中作为气体的一氧化碳,其可以包含另外的气体作为杂质,例如氮,甲烷,氢,氧,二氧化碳,水,氯,氩,氦,氖,氙等,含量至多为占全部气体混合物的90%.b.w.。
本发明的反应一般在1-200巴,优选在50-150且更优选在80-120巴的反应压力下进行。
根据溶剂的不同,本发明的反应一般在50°-350℃,优选80-160°的升高的温度下进行,反应时间为2-20小时,优选4-15小时。
该反应可以在有任意的溶剂或没有溶剂的存在下进行,且可以任选地包括形成助剂。已知的助剂包括防电剂,抗氧化剂,粘着促进剂,增粘剂,光稳定剂,增塑剂,染料,色素,填充剂,强化纤维,润滑剂和脱模增强剂。
用于本发明方法的溶剂可以选自脂族,脂环族或芳族溶剂,酯类,醚类或其混合物,例如己烷,苯,甲苯,脂族醇类,例如THF,MeOH,DMSO,AcOH,乙酸乙酯或乙醚,其中优选THF。
作为催化剂,可以使用任意的金属催化剂,且可以具体地选自多相和/或均相金属催化剂,其选自Pt,Pd,Ir,Rh,Ru,Os,Mo,Ni,Cr,V,Cu,Mn,Zn,Fe,硫,硒及它们的催化活性化合物。铑化合物例如铑盐如乙酸铑,Rh(PPh3)3Cl,Rh6(CO)16,[Rh(CO)2Cl]2,[Rh(COD)Cl]2,HRh(PPh3)4可以有利地用于本发明的方法,其中乙酸铑是最有前景的。相对于反应物的摩尔比,所述催化剂可以以0,1-5,0mol%的催化量使用。
如上所述,本发明一般涉及使用一氧化碳对羰基化合物进行还原氨基化且进一步由如下实施例示例。
实施例1
放入0.2mg Rh2(OAc)4。然后加入27.6mg对-茴香胺。将反应小瓶抽真空,加入一氧化碳。加入0.1mL THF(3.7ppm水)。加入20μL 2-丁酮。给高压釜脱气,此后,加入一氧化碳。建立20巴的CO-压力。将高压釜加热至120℃。4h后,将该反应混合物冷却至室温,释放压力。分离定量收率的产物。
1H NMR(500MHz,CDCl3)ppm 6.79(d,J=8.9Hz,2H),6.57(d,J=8.9Hz,2H),3.75(s,3H),3.38-3.28(m,1H),3.18(br s,1H),1.55-1.67(m,1H),1.40-1.51(m,1H),1.16(d,J=6.3Hz,3H),0.96(t,J=7.4Hz,3H)。
13C NMR(125MHz,CDCl3)ppm 10.3,20.1,29.5,50.7,55.7,114.6,114.8,141.9,151.7。
实施例2
将8.8mg(0.2mol%)Rh2(OAc)4放入36ml高压釜。然后加入1.21g对-茴香胺。给高压釜脱气,加入一氧化碳。加入2mL THF。加入1mL苯甲醛。CO压力为20巴。将高压釜加热至120℃。6h后,将该反应混合物冷却至室温,释放压力。分离产物,收率为97%。
1H NMR(500MHz,CDCl3)ppm 7.35-7.45(m,4H),7.31(t,J=7.0Hz,1H),6.82(d,J=8.9Hz,2H),6.64(d,J=8.9Hz,2H),4.32(s,2H),3.78(s,3H),3.70(br s,1H)。13C NMR(125MHz,CDCl3)ppm 49.1,55.7,114.0,114.8,127.1,127.5,128.5,139.6,142.4,152.1。
实施例3
放入0.31mg(0.21mol%)Rh2(OAc)4。然后加入28μL(100mol%)吡咯烷。加入0.2mL THF(18.1ppm水)。加入35μL苯甲醛。CO压力为20巴。将高压釜加热至120℃。4h后,将该反应混合物冷却至室温,释放压力。收率为85%。
1H NMR(500MHz,CDCl3)ppm 7.20-7.45(m,5H),3.66(s,2H),2.50-2.60(m,4H),1.75-1.87(m,4H)。
13C NMR(125MHz,CDCl3)ppm 23.4,54.1,60.7,126.8,128.1,128.8,139.3。
实施例4
放入0.44mg Rh2(OAc)4。然后加入56.9mg(100mol%)对-茴香胺。加入0.1mL THF(19.7ppm水)。加入50μL新戊醛。CO压力为20巴。将高压釜加热至120℃。4h后,将该反应混合物冷却至室温,释放压力。定量收率。
1H NMR(500MHz,CDCl3)ppm 6.82(d,J=8.9Hz,2H),6.63(d,J=8.9Hz,2H),3.77(s,3H),3.40(br s,1H),2.88(s,2H),1.03(s,9H)。
13C NMR(125MHz,CDCl3)ppm 27.6,31.7,55.7,59.9,113.8,114.8,143.4,151.7。
实施例5
放入0.40mg Rh2(OAc)4。然后加入21μL N-甲基-N-苄胺。加入0.1mL THF(5.7ppm水)。加入18μL苯甲醛。CO压力为20巴。将高压釜加热至140℃。12h后,将该反应混合物冷却至室温,释放压力。收率为93%。
1H NMR(500MHz,CDCl3)ppm 7.10-7.33(m,10H),3.44(s,4H),2.10(s,3H)。
13C NMR(125MHz,CDCl3)ppm 42.2,61.8,126.9,128.2,128.9,139.2。
实施例6
放入23mg 10%Rh/C。然后加入40μL苯胺。加入0.1mL THF(21.3ppm水)。加入44μL苯甲醛。CO压力为20巴。将高压釜加热至140℃。42h后,将该反应混合物冷却至室温,释放压力。收率为50%。
1H NMR(500MHz,CDCl3)ppm 7.26-7.44(m,5H),7.17-7.22(m,2H),6.72-6.78(m,1H),6.63-6.79(m,2H),4.35(s,2H)。
13C NMR(125MHz,CDCl3)ppm 48.2,112.8,117.5,127.1,127.4,128.5,129.2,139.4,148.1。
实施例7
将1.28mg Ru3(CO)12放入36ml高压釜。然后加入27.1mg对-茴香胺。给高压釜脱气,加入一氧化碳。加入0.15mL THF(11.0ppm水)。加入20μL苯甲醛。CO压力为95巴。将高压釜加热至100℃。6h后,将该反应混合物冷却至室温,释放压力。分离产物,收率为2%。
1H NMR(500MHz,CDCl3)ppm 7.35-7.45(m,4H),7.31(t,J=7.0Hz,1H),6.82(d,J=8.9Hz,2H),6.64(d,J=8.9Hz,2H),4.32(s,2H),3.78(s,3H),3.70(br s,1H)。13C NMR(125MHz,CDCl3)ppm 49.1,55.7,114.0,114.8,127.1,127.5,128.5,139.6,142.4,152.1。
如上所述,本发明提供了用于制备胺类的简便而有效的方法,以直接方式通过利用一氧化碳作为还原剂进行。本发明的这种新方法具有安全的优点,且显示具有经济价值。因此发明人发现了有效、稳定和通用的催化还原氨基化方法,其无需外部氢源,而是利用现存的底物的氢原子和一氧化碳(CO)作为终端还原剂。
除一氧化碳是极为有用的C-1结构单元且已知作为还原剂起作用外(大部分通过水煤气变换反应进行),本发明的发明人已经证实,一氧化碳还可以用作还原氨基化中的还原剂,而无需任何外部氢源,该方法是完全未知的。
Claims (6)
1.制备胺类的方法,包括使包含羰基部分的式R1-CO-R2的化合物与式HNR3R4的胺化合物和一氧化碳在催化剂的存在下反应:
其中:
R1和R2各自独立地是氢或烃基,所述烃基可以相同或不同且可以各自选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基或C6-C20芳香烃类或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃取代基任选地被一个或多个基团取代,所述基团选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,或C6-C20芳香烃类或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基或杂取代基,其中R1和R2的至少一个不是氢,或
R1和R2形成具有4-10个环原子的脂环族或杂脂环族环结构,其任选地包括不饱和键,每个环结构任选地被一个或多个取代基取代,所述取代基选自杂取代基,C1-C20直链、支链或环状脂族烃类,其任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基或C6-C20芳香烃,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃任选地被一个或多个杂取代基取代,且
R3和R4各自独立地是氢或烃基,所述烃基可以相同或不同且可以各自选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基或C6-C20芳香烃或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃取代基任选地被一个或多个基团取代,所述基团选自C1-C20直链、支链或环状脂族烃类,其任选地包括杂原子和/或任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,或C6-C20芳香烃或部分芳烃-氢化形式,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基或杂取代基,其中R3和R4的至少一个不是氢,或
R3和R4形成具有4-10个环原子的脂环族或杂脂环族环结构,其任选地包括不饱和键,每个环结构任选地被一个或多个取代基取代,所述取代基选自杂取代基,C1-C20直链、支链或环状脂族烃类,其任选地具有一个或多个不饱和键,例如C1-C20-烷基,C2-C20-烯基或C2-C20-炔基,C3-C8-杂环烷基或C6-C20芳香烃,例如芳基,芳基-(C1-C6)-烷基,杂芳基-(C1-C6)-烷基,每个烃任选地被一个或多个杂取代基取代。
2.权利要求1的方法,其中所述反应在溶剂中进行,所述溶剂选自脂族,脂环族或芳族溶剂,酯类,醚类或其混合物,例如己烷,苯,甲苯,脂族醇类,优选THF。
3.权利要求1或2的方法,其中所述催化剂选自多相和/或均相金属催化剂,其选自Pt,Pd,Ir,Rh,Ru,Os,Mo,Ni,Cr,V,Cu,Mn,Zn和Fe,硫,硒及它们的催化活性化合物。
4.权利要求1或2的方法,其中所述催化剂包含铑化合物,例如铑盐,如乙酸铑,Rh(PPh3)3Cl,Rh6(CO)16,[Rh(CO)2Cl]2,[Rh(COD)Cl]2,HRh(PPh3)4,优选乙酸铑。
5.上述权利要求任一项的方法,其中所述反应在1-200巴,优选20-150巴且更优选80-120巴的反应压力下进行。
6.上述权利要求任一项的方法,其中所述反应在50°-350℃的升温下进行。
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EP12196518.0A EP2743250A1 (en) | 2012-12-11 | 2012-12-11 | Process for preparing amines |
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PCT/EP2013/076093 WO2014090806A1 (en) | 2012-12-11 | 2013-12-10 | Process for preparing amines |
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US3091641A (en) * | 1959-12-28 | 1963-05-28 | Texaco Inc | Preparation of tertiary amines |
US3947458A (en) * | 1970-12-22 | 1976-03-30 | Monsanto Company | Preparation of amines |
JPS5238530B2 (zh) * | 1974-04-26 | 1977-09-29 | ||
JPS5822468B2 (ja) * | 1975-03-25 | 1983-05-09 | 住友化学工業株式会社 | ニキユウアミンカゴウブツノセイゾウホウ |
JPS5543008A (en) * | 1978-09-21 | 1980-03-26 | Agency Of Ind Science & Technol | Preparation of tertiary amine |
US4831159A (en) * | 1986-06-20 | 1989-05-16 | Texaco Inc. | Process for hydroformylation of n-vinyl-2-pyrrolidinone |
DE19737053A1 (de) * | 1997-08-26 | 1999-03-04 | Hoechst Ag | Einstufiges Verfahren zur Herstellung von Aminen |
DE10012251A1 (de) * | 1999-06-25 | 2000-12-28 | Degussa | Verfahren zur Herstellung von N-Acylaminosäuren |
DE10138140A1 (de) * | 2001-08-09 | 2003-02-20 | Degussa | Verfahren zur Herstellung von Aminen durch reduktive Aminierung von Carbonylverbindungen unter Transfer-Hydrierungsbedingungen |
JP4970958B2 (ja) * | 2004-02-10 | 2012-07-11 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | オレフィンのヒドロアミノメチル化 |
DE102004052040A1 (de) * | 2004-10-26 | 2006-04-27 | Basf Ag | Liganden zur asymmetrischen Hydroformylierung |
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L. MARKÓ ET AL.: "Homogeneous Reductive Amination with Cobalt and Rhodium Carbonyls as Catalysts", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
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KR20150095839A (ko) | 2015-08-21 |
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