JP6080774B2 - 四座アミノ/イミノ−チオエーテルベースのルテニウム錯体によるエステル基又はカルボニル基の水素化 - Google Patents
四座アミノ/イミノ−チオエーテルベースのルテニウム錯体によるエステル基又はカルボニル基の水素化 Download PDFInfo
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- JP6080774B2 JP6080774B2 JP2013545259A JP2013545259A JP6080774B2 JP 6080774 B2 JP6080774 B2 JP 6080774B2 JP 2013545259 A JP2013545259 A JP 2013545259A JP 2013545259 A JP2013545259 A JP 2013545259A JP 6080774 B2 JP6080774 B2 JP 6080774B2
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 27
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title description 6
- 150000003303 ruthenium Chemical class 0.000 title description 5
- 150000002148 esters Chemical class 0.000 title description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title description 4
- GLBQVJGBPFPMMV-UHFFFAOYSA-N sulfilimine Chemical compound S=N GLBQVJGBPFPMMV-UHFFFAOYSA-N 0.000 title 1
- 239000003446 ligand Substances 0.000 claims description 48
- 239000002585 base Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 150000002576 ketones Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001299 aldehydes Chemical group 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 239000012041 precatalyst Substances 0.000 claims description 10
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 8
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 7
- 239000012327 Ruthenium complex Substances 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910010276 inorganic hydride Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 description 35
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 29
- -1 metal hydride salts Chemical class 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 23
- 125000004429 atom Chemical group 0.000 description 21
- 150000002430 hydrocarbons Chemical group 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 125000003342 alkenyl group Chemical group 0.000 description 20
- 125000003545 alkoxy group Chemical group 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 14
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 0 CCCC1*C(C)*C1 Chemical compound CCCC1*C(C)*C1 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BRTDDLTZIGWMNW-DNQXCXABSA-N 1-(2-tert-butylsulfanylphenyl)-N-[(1R,2R)-2-[(2-tert-butylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound CC(C)(C)SC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)SC(C)(C)C)CCCC1 BRTDDLTZIGWMNW-DNQXCXABSA-N 0.000 description 4
- LKUDRIXVPKCDBB-UHFFFAOYSA-N 1-(2-tert-butylsulfanylphenyl)-N-[2-[(2-tert-butylsulfanylphenyl)methylideneamino]ethyl]methanimine Chemical compound CC(C)(C)SC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1SC(C)(C)C LKUDRIXVPKCDBB-UHFFFAOYSA-N 0.000 description 4
- CATPSSFGOWLZEH-LJQANCHMSA-N 1-(2-tert-butylsulfanylphenyl)-n-[(2r)-2-[(2-tert-butylsulfanylphenyl)methylideneamino]propyl]methanimine Chemical compound C([C@@H](C)N=CC=1C(=CC=CC=1)SC(C)(C)C)N=CC1=CC=CC=C1SC(C)(C)C CATPSSFGOWLZEH-LJQANCHMSA-N 0.000 description 4
- KGLMJKLZEVCRGR-UHFFFAOYSA-N 1-(2-tert-butylsulfanylphenyl)-n-[3-[(2-tert-butylsulfanylphenyl)methylideneamino]propyl]methanimine Chemical compound CC(C)(C)SC1=CC=CC=C1C=NCCCN=CC1=CC=CC=C1SC(C)(C)C KGLMJKLZEVCRGR-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 description 4
- 150000004820 halides Chemical group 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FALSJIFEWOQXMB-LOYHVIPDSA-N (1R,2R)-1-N,2-N-bis[(2-phenylsulfanylphenyl)methyl]cyclohexane-1,2-diamine Chemical compound N([C@@H]1CCCC[C@H]1NCC=1C(=CC=CC=1)SC=1C=CC=CC=1)CC1=CC=CC=C1SC1=CC=CC=C1 FALSJIFEWOQXMB-LOYHVIPDSA-N 0.000 description 3
- OYDZTRAZLSCZKY-DNQXCXABSA-N (1R,2R)-1-N,2-N-bis[(2-tert-butylsulfanylphenyl)methyl]cyclohexane-1,2-diamine Chemical compound CC(C)(C)SC1=CC=CC=C1CN[C@H]1[C@H](NCC=2C(=CC=CC=2)SC(C)(C)C)CCCC1 OYDZTRAZLSCZKY-DNQXCXABSA-N 0.000 description 3
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 description 3
- BENSHBXJCKSVFA-LOYHVIPDSA-N 1-(2-cyclohexylsulfanylphenyl)-N-[(1R,2R)-2-[(2-cyclohexylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound C1CCCCC1SC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)SC2CCCCC2)CCCC1 BENSHBXJCKSVFA-LOYHVIPDSA-N 0.000 description 3
- WIDAQWYJAXDSRF-DNQXCXABSA-N 1-(2-propan-2-ylsulfanylphenyl)-N-[(1R,2R)-2-[(2-propan-2-ylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound CC(C)SC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)SC(C)C)CCCC1 WIDAQWYJAXDSRF-DNQXCXABSA-N 0.000 description 3
- JHQGAXBMKKWADH-UHFFFAOYSA-N 1-(2-propan-2-ylsulfanylphenyl)-N-[2-[(2-propan-2-ylsulfanylphenyl)methylideneamino]ethyl]methanimine Chemical compound CC(C)SC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1SC(C)C JHQGAXBMKKWADH-UHFFFAOYSA-N 0.000 description 3
- YXVLCHXSFPZYEH-DNQXCXABSA-N 1-(2-tert-butylsulfanyl-4,5-dimethoxyphenyl)-N-[(1R,2R)-2-[(2-tert-butylsulfanyl-4,5-dimethoxyphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound C1=C(OC)C(OC)=CC(SC(C)(C)C)=C1C=N[C@H]1[C@H](N=CC=2C(=CC(OC)=C(OC)C=2)SC(C)(C)C)CCCC1 YXVLCHXSFPZYEH-DNQXCXABSA-N 0.000 description 3
- PEDCYLRBQSTEHH-LQFQNGICSA-N 1-(2-tert-butylsulfanyl-4-phenylphenyl)-N-[(1R,2R)-2-[(2-tert-butylsulfanyl-4-phenylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound N([C@@H]1CCCC[C@H]1N=CC1=CC=C(C=C1SC(C)(C)C)C=1C=CC=CC=1)=CC(C(=C1)SC(C)(C)C)=CC=C1C1=CC=CC=C1 PEDCYLRBQSTEHH-LQFQNGICSA-N 0.000 description 3
- ALAYLKBYPZDDCV-DNQXCXABSA-N 1-(2-tert-butylsulfanyl-5-nitrophenyl)-N-[(1R,2R)-2-[(2-tert-butylsulfanyl-5-nitrophenyl)methylideneamino]cyclohexyl]methanimine Chemical compound CC(C)(C)SC1=CC=C([N+]([O-])=O)C=C1C=N[C@H]1[C@H](N=CC=2C(=CC=C(C=2)[N+]([O-])=O)SC(C)(C)C)CCCC1 ALAYLKBYPZDDCV-DNQXCXABSA-N 0.000 description 3
- BZMCMDHHWIKDBR-UHFFFAOYSA-N 1-(2-tert-butylsulfanylphenyl)-n-[3-[(2-tert-butylsulfanylphenyl)methylideneamino]-2,2-dimethylpropyl]methanimine Chemical compound CC(C)(C)SC1=CC=CC=C1C=NCC(C)(C)CN=CC1=CC=CC=C1SC(C)(C)C BZMCMDHHWIKDBR-UHFFFAOYSA-N 0.000 description 3
- WSHZNOMDEAPHCA-DNQXCXABSA-N 1-(4-bromo-2-tert-butylsulfanylphenyl)-N-[(1R,2R)-2-[(4-bromo-2-tert-butylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound CC(C)(C)SC1=CC(Br)=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC(Br)=CC=2)SC(C)(C)C)CCCC1 WSHZNOMDEAPHCA-DNQXCXABSA-N 0.000 description 3
- PFBRITPHXGGORJ-LOYHVIPDSA-N 1-(4-tert-butyl-2-tert-butylsulfanylphenyl)-N-[(1R,2R)-2-[(4-tert-butyl-2-tert-butylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound CC(C)(C)SC1=CC(C(C)(C)C)=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC(=CC=2)C(C)(C)C)SC(C)(C)C)CCCC1 PFBRITPHXGGORJ-LOYHVIPDSA-N 0.000 description 3
- IEBXJKJTZVKBID-VSGBNLITSA-N 1-[2,6-bis(tert-butylsulfanyl)phenyl]-N-[(1R,2R)-2-[[2,6-bis(tert-butylsulfanyl)phenyl]methylideneamino]cyclohexyl]methanimine Chemical compound CC(C)(C)SC1=CC=CC(SC(C)(C)C)=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2SC(C)(C)C)SC(C)(C)C)CCCC1 IEBXJKJTZVKBID-VSGBNLITSA-N 0.000 description 3
- IUMLGNVGPLPOCC-LOYHVIPDSA-N 1-[2-(4-fluorophenyl)sulfanylphenyl]-N-[(1R,2R)-2-[[2-(4-fluorophenyl)sulfanylphenyl]methylideneamino]cyclohexyl]methanimine Chemical compound C1=CC(F)=CC=C1SC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)SC=2C=CC(F)=CC=2)CCCC1 IUMLGNVGPLPOCC-LOYHVIPDSA-N 0.000 description 3
- QAMZLMNXCZGTJW-DNQXCXABSA-N 1-[2-tert-butylsulfanyl-4-(trifluoromethyl)phenyl]-N-[(1R,2R)-2-[[2-tert-butylsulfanyl-4-(trifluoromethyl)phenyl]methylideneamino]cyclohexyl]methanimine Chemical compound CC(C)(C)SC1=CC(C(F)(F)F)=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC(=CC=2)C(F)(F)F)SC(C)(C)C)CCCC1 QAMZLMNXCZGTJW-DNQXCXABSA-N 0.000 description 3
- JXQCYDWJBFEAMT-VSGBNLITSA-N 4-tert-butylsulfanyl-3-[[(1R,2R)-2-[[2-tert-butylsulfanyl-5-(dimethylamino)phenyl]methylideneamino]cyclohexyl]iminomethyl]-N,N-dimethylaniline Chemical compound CN(C)C1=CC=C(SC(C)(C)C)C(C=N[C@H]2[C@@H](CCCC2)N=CC=2C(=CC=C(C=2)N(C)C)SC(C)(C)C)=C1 JXQCYDWJBFEAMT-VSGBNLITSA-N 0.000 description 3
- 229910017008 AsF 6 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910020366 ClO 4 Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 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 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 150000005671 trienes Chemical class 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- WSOLOQWEWUEUQF-LOYHVIPDSA-N (1R,2R)-1-N,2-N-bis[(2-cyclohexylsulfanylphenyl)methyl]cyclohexane-1,2-diamine Chemical compound N([C@@H]1CCCC[C@H]1NCC=1C(=CC=CC=1)SC1CCCCC1)CC1=CC=CC=C1SC1CCCCC1 WSOLOQWEWUEUQF-LOYHVIPDSA-N 0.000 description 2
- RQWGRKWGZKVPSR-XRSDMRJBSA-N (1R,2R)-1-N,2-N-bis[(2-naphthalen-1-ylphenyl)methyl]cyclohexane-1,2-diamine Chemical compound C1=CC=C2C(C3=CC=CC=C3CN[C@H]3[C@@H](CCCC3)NCC=3C(=CC=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 RQWGRKWGZKVPSR-XRSDMRJBSA-N 0.000 description 2
- JUCUKMPBKCUGEE-KKLWWLSJSA-N (1R,2R)-N,N'-bis[(2-tert-butylsulfanylphenyl)methyl]-1,2-diphenylethane-1,2-diamine Chemical compound CC(C)(C)SC1=CC=CC=C1CN[C@H](C=1C=CC=CC=1)[C@@H](C=1C=CC=CC=1)NCC1=CC=CC=C1SC(C)(C)C JUCUKMPBKCUGEE-KKLWWLSJSA-N 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- POMQDHIBLRSVGQ-ROJLCIKYSA-N 1-(1-tert-butylsulfanylnaphthalen-2-yl)-N-[(1R,2R)-2-[(1-tert-butylsulfanylnaphthalen-2-yl)methylideneamino]cyclohexyl]methanimine Chemical compound C1=CC2=CC=CC=C2C(SC(C)(C)C)=C1C=N[C@H]1[C@H](N=CC=2C(=C3C=CC=CC3=CC=2)SC(C)(C)C)CCCC1 POMQDHIBLRSVGQ-ROJLCIKYSA-N 0.000 description 2
- VJQJHYRSDVAWAT-LQFQNGICSA-N 1-(2-naphthalen-1-ylsulfanylphenyl)-N-[(1R,2R)-2-[(2-naphthalen-1-ylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound C1=CC=C2C(SC3=CC=CC=C3C=N[C@H]3[C@H](N=CC=4C(=CC=CC=4)SC=4C5=CC=CC=C5C=CC=4)CCCC3)=CC=CC2=C1 VJQJHYRSDVAWAT-LQFQNGICSA-N 0.000 description 2
- VIZCHOAOWALKNQ-ROJLCIKYSA-N 1-[2-(2,6-dimethylphenyl)sulfanylphenyl]-N-[(1R,2R)-2-[[2-(2,6-dimethylphenyl)sulfanylphenyl]methylideneamino]cyclohexyl]methanimine Chemical compound CC1=CC=CC(C)=C1SC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)SC=2C(=CC=CC=2C)C)CCCC1 VIZCHOAOWALKNQ-ROJLCIKYSA-N 0.000 description 2
- OGYVQWITWQPCMU-LQFQNGICSA-N 1-[2-(4-tert-butylphenyl)sulfanylphenyl]-N-[(1R,2R)-2-[[2-(4-tert-butylphenyl)sulfanylphenyl]methylideneamino]cyclohexyl]methanimine Chemical compound C1=CC(C(C)(C)C)=CC=C1SC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)SC=2C=CC(=CC=2)C(C)(C)C)CCCC1 OGYVQWITWQPCMU-LQFQNGICSA-N 0.000 description 2
- WKNQCKPTPVZUQD-UHFFFAOYSA-N 2,6-bis(tert-butylsulfanyl)benzaldehyde Chemical compound CC(C)(C)SC1=CC=CC(SC(C)(C)C)=C1C=O WKNQCKPTPVZUQD-UHFFFAOYSA-N 0.000 description 2
- QYKFMBKSADHQSF-UHFFFAOYSA-N 2-(2,6-dimethylphenyl)sulfanylbenzaldehyde Chemical compound CC1=CC=CC(C)=C1SC1=CC=CC=C1C=O QYKFMBKSADHQSF-UHFFFAOYSA-N 0.000 description 2
- ZCQFZJLUZCLFQW-UHFFFAOYSA-N 2-cyclohexylsulfanylbenzaldehyde Chemical compound O=CC1=CC=CC=C1SC1CCCCC1 ZCQFZJLUZCLFQW-UHFFFAOYSA-N 0.000 description 2
- GYDSXMPGWUNZJC-UHFFFAOYSA-N 2-phenylsulfanylbenzaldehyde Chemical compound O=CC1=CC=CC=C1SC1=CC=CC=C1 GYDSXMPGWUNZJC-UHFFFAOYSA-N 0.000 description 2
- UGPQFYISFDNTAZ-UHFFFAOYSA-N 2-propan-2-ylsulfanylbenzaldehyde Chemical compound CC(C)SC1=CC=CC=C1C=O UGPQFYISFDNTAZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- 238000004440 column chromatography Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
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- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
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- BSMVFEPXWGOCMW-UHFFFAOYSA-N 1-(2-methylsulfanylphenyl)-n-[2-[(2-methylsulfanylphenyl)methylideneamino]ethyl]methanimine Chemical compound CSC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1SC BSMVFEPXWGOCMW-UHFFFAOYSA-N 0.000 description 1
- BBUASFZYHPAPPR-LOYHVIPDSA-N 1-(2-phenylsulfanylphenyl)-N-[(1R,2R)-2-[(2-phenylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound N([C@@H]1CCCC[C@H]1N=CC=1C(=CC=CC=1)SC=1C=CC=CC=1)=CC1=CC=CC=C1SC1=CC=CC=C1 BBUASFZYHPAPPR-LOYHVIPDSA-N 0.000 description 1
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 description 1
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- YDCGXIYNHVEWHN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)sulfanylbenzaldehyde Chemical compound C1=CC(C(C)(C)C)=CC=C1SC1=CC=CC=C1C=O YDCGXIYNHVEWHN-UHFFFAOYSA-N 0.000 description 1
- RXIJKMDUYCCMKW-UHFFFAOYSA-N 2-naphthalen-1-ylsulfanylbenzaldehyde Chemical compound O=CC1=CC=CC=C1SC1=CC=CC2=CC=CC=C12 RXIJKMDUYCCMKW-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- NETIVEXOFHNWKP-UHFFFAOYSA-N 2-tert-butylsulfanyl-4,5-dimethoxybenzaldehyde Chemical compound COC1=CC(SC(C)(C)C)=C(C=O)C=C1OC NETIVEXOFHNWKP-UHFFFAOYSA-N 0.000 description 1
- HIAOWJWYTCTQJF-UHFFFAOYSA-N 2-tert-butylsulfanyl-4-(trifluoromethyl)benzaldehyde Chemical compound CC(C)(C)SC1=CC(C(F)(F)F)=CC=C1C=O HIAOWJWYTCTQJF-UHFFFAOYSA-N 0.000 description 1
- WPUSIMVJCOABPC-UHFFFAOYSA-N 2-tert-butylsulfanyl-4-phenylbenzaldehyde Chemical compound C1=C(C=O)C(SC(C)(C)C)=CC(C=2C=CC=CC=2)=C1 WPUSIMVJCOABPC-UHFFFAOYSA-N 0.000 description 1
- PIUHDRBSAMHVOI-UHFFFAOYSA-N 2-tert-butylsulfanyl-5-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(SC(C)(C)C)C(C=O)=C1 PIUHDRBSAMHVOI-UHFFFAOYSA-N 0.000 description 1
- OSAHAKZGIIQAFL-UHFFFAOYSA-N 2-tert-butylsulfanyl-5-nitrobenzaldehyde Chemical compound CC(C)(C)SC1=CC=C([N+]([O-])=O)C=C1C=O OSAHAKZGIIQAFL-UHFFFAOYSA-N 0.000 description 1
- KCKZIWSINLBROE-UHFFFAOYSA-N 3,4-dihydro-1h-naphthalen-2-one Chemical class C1=CC=C2CC(=O)CCC2=C1 KCKZIWSINLBROE-UHFFFAOYSA-N 0.000 description 1
- OXZJXGPDIMNUQD-UHFFFAOYSA-N 4,5-dimethoxy-2-phenylsulfanylbenzaldehyde Chemical compound C1=C(OC)C(OC)=CC(SC=2C=CC=CC=2)=C1C=O OXZJXGPDIMNUQD-UHFFFAOYSA-N 0.000 description 1
- BAHKCZAAQJLGAK-UHFFFAOYSA-N 4-bromo-2-tert-butylsulfanylbenzaldehyde Chemical compound CC(C)(C)SC1=CC(Br)=CC=C1C=O BAHKCZAAQJLGAK-UHFFFAOYSA-N 0.000 description 1
- OBGYJKBJUOGMSK-UHFFFAOYSA-N 4-tert-butyl-2-tert-butylsulfanylbenzaldehyde Chemical compound CC(C)(C)SC1=CC(C(C)(C)C)=CC=C1C=O OBGYJKBJUOGMSK-UHFFFAOYSA-N 0.000 description 1
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- JXDSWNYTPPIEJB-HLVKTBDNSA-N CC(C)(C)Sc1cccc2c1/C=N/C(CCCC1)C1/N=C/c(c(SC(C)(C)C)ccc1)c1SC(C)(C)CC(C)(C)S2 Chemical compound CC(C)(C)Sc1cccc2c1/C=N/C(CCCC1)C1/N=C/c(c(SC(C)(C)C)ccc1)c1SC(C)(C)CC(C)(C)S2 JXDSWNYTPPIEJB-HLVKTBDNSA-N 0.000 description 1
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- BIRBVFLWFKSURX-JZFGTTBJSA-N CC(C1)(c2cccc(cc3)c22)Sc2c3/C=N/C(CCCC2)C2/N=C/c2ccc3c4c2SC1(C)c4ccc3 Chemical compound CC(C1)(c2cccc(cc3)c22)Sc2c3/C=N/C(CCCC2)C2/N=C/c2ccc3c4c2SC1(C)c4ccc3 BIRBVFLWFKSURX-JZFGTTBJSA-N 0.000 description 1
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- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- DMCUBCDYHQYAKH-UHFFFAOYSA-M [F-].[Cl+] Chemical group [F-].[Cl+] DMCUBCDYHQYAKH-UHFFFAOYSA-M 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclo-pentanone Natural products O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical class O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-PTQBSOBMSA-N cyclohexanone Chemical class O=[13C]1CCCCC1 JHIVVAPYMSGYDF-PTQBSOBMSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- ICPMUWPXCAVOOQ-UHFFFAOYSA-N cycloocta-1,3,5-triene Chemical compound C1CC=CC=CC=C1 ICPMUWPXCAVOOQ-UHFFFAOYSA-N 0.000 description 1
- BGTOWKSIORTVQH-HOSYLAQJSA-N cyclopentanone Chemical class O=[13C]1CCCC1 BGTOWKSIORTVQH-HOSYLAQJSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- HYPQBCJISMRWNA-UHFFFAOYSA-N n,n'-bis[(2-hexylsulfanylphenyl)methyl]ethane-1,2-diamine Chemical compound CCCCCCSC1=CC=CC=C1CNCCNCC1=CC=CC=C1SCCCCCC HYPQBCJISMRWNA-UHFFFAOYSA-N 0.000 description 1
- ACIIFBBQQVBFTN-UHFFFAOYSA-N n-[(2-benzylsulfanylphenyl)methyl]-n'-[(2-tert-butylsulfanylphenyl)methyl]ethane-1,2-diamine Chemical compound CC(C)(C)SC1=CC=CC=C1CNCCNCC1=CC=CC=C1SCC1=CC=CC=C1 ACIIFBBQQVBFTN-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 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
- 239000002304 perfume Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/32—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to an acyclic carbon atom of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/45—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms doubly-bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
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Description
本発明は、接触水素化の分野に関し、更に詳細には、特定のルテニウム触媒又はプレ触媒を、ケトン又はアルデヒドの対応するアルコールへの還元のための水素化法に用いる使用に関する。
ケトン又はアルデヒド官能基中のC=O結合の対応するアルコールへの還元は、有機化学の基本的な反応の1つであり、多くの化学プロセスで用いられている。一般的に、かかる転換を達成するために以下の3つの方法が公知である:
a)シリル又は金属水素化物塩、例えば、LiAlH4、又はPMHS(ポリメチルヒドロシロキサン)が使用される、水素化物法;
b)二水素供与体(例えば、HCOOH又はiPrOH)が使用される、水素移動法;
c)分子状の水素が使用される、直接水素化法。
前述の問題を解決するために、本発明は、1個、2個又は3個のケトン及び/又はアルデヒド官能基を有するC3〜C70基質を、分子状H2を用いて、水素化によって対応するアルコールに還元する方法であって、前記方法を、少なくとも1種の塩基及びC8〜C56ルテニウム錯体の形の少なくとも1種の触媒又はプレ触媒の存在下で実施し、該ルテニウム錯体は、以下の原子:
− それぞれが第1級又は第2級アミン(即ち、NH2基又はNH基)又はN−アルキルイミン官能基(即ち、C=N基)の形である、2つの窒素原子、及び
− それぞれがチオエーテル官能基の形である、2つの硫黄原子
によってルテニウムに配位している四座配位子(L4)を配位圏に含むことを特徴とする、前記方法に関するものである。
Rbは、任意に置換され且つ任意に1個又は2個のカルボニル基を含むC1〜C29炭化水素基、硫黄、窒素若しくは酸素の中から選択される1個又は2個の原子を含むC3〜8ヘテロ環(芳香族又はそれ以外)によって置換されるC1〜C6炭化水素基、又は硫黄、窒素若しくは酸素の中から選択される1個又は2個の原子を含み、任意に1個又は2個のC1〜C6炭化水素基によって置換されるC3〜8ヘテロ環(芳香族又はそれ以外)を表し;
Ra及びRbは一緒に結合して、任意に置換され且つ任意に1個又は2個のカルボニル基を含む、C3〜C20、好ましくはC4〜C20飽和又は不飽和炭化水素基を形成する)
の化合物であってよい。
Rbは、任意に置換され且つ任意に1個又は2個のカルボニル基を含むC1〜C29炭化水素基を表すか;又は硫黄、窒素若しくは酸素の中から選択される1個又は2個の原子を含むC3〜8ヘテロ環(芳香族又はそれ以外)を表し;
Ra及びRbは一緒に結合して、任意に置換され且つ任意に1個又は2個のカルボニル基を含む、C3〜C20、好ましくはC4〜C20飽和又は不飽和炭化水素基を形成する)
の化合物であってよい。
アルデヒド:
C3〜15アルカナール、C4〜153−メチル−2−アルケナール、C10〜183−(非)置換アリール−3−(C1〜6アルキル)−2−プロペナール、C10〜183−(非)置換アリール−2−(C1〜6アルキル)−2−プロペナール、C10〜183−(非)置換アリール−3−(C1〜6アルキル)−2−メチル−2−プロペナール、C4〜15共役又は非共役アルケナール又はアルクジエナール、(非)置換アリール基を含むC7〜15アルデヒド、酸素原子又は硫黄原子を含む芳香族又は非芳香族複素環を含むC5〜10(非)置換アルデヒド;及び
ケトン:
ジ−(C1〜15アルキル)ケトン、C8〜C15(非)置換ベンジルアルキルケトン、C8〜C15(非)置換スチリルアルキルケトン、2,6,6−トリメチルシクロヘキシル/シクロヘキシル基を含むC12〜C15ケトン、2,2,3−トリメチルシクロペンテニル又は2,2,3−トリメチル−シクロペンチル基を含むC13〜C15ケトン、C4〜C12(非)置換環状ケトン、C10〜18(非)置換シクロペンテノン又はC5〜12炭化水素基でアルファ置換された(非)置換シクロペンタノン、C11〜18(非)置換シクロヘキセノン又はC6〜12炭化水素基でアルファ置換されたシクロヘキサノン、C8〜16(非)置換アリールアルキルケトン、C4〜151−アルケンアルキルケトン、C4〜15−1−アルキンアルキルケトン、C9〜18(非)置換1−インダノン、C10〜20(非)置換1−テトラロン、C10〜20(非)置換2−テトラロン;
その際、「(非)置換」とは、前記ケトン又はアルデヒドがRa又はRbについて上で規定された1つ以上の基によって置換され得ることを意味し;
「アリール」とは、フェニル基又はナフチル基を意味する。
[Ru(L4)(L)2−rYr](Z)2−r (1)
(式中、rは0、1又は2を表し;
L4は、以下の原子:
− それぞれが第1級又は第2級アミン(即ち、NH2又はNH基)又はN−アルキルイミン官能基(即ち、C=N基)の形である、2つの窒素原子、及び
− それぞれがチオエーテル官能基の形である、2つの硫黄原子
によってRu金属に配位している1つのC10〜40四座配位子を表し;且つ
それぞれのLは、同時に又は独立して、中性のC1〜C26中性単座配位子を表し;
それぞれのYは、同時に又は独立して、ハロゲン原子、水素原子、BH4基、ヒドロキシル基、C1〜C10アルコキシル基又はC3〜C15アリル基を表し;
それぞれのZは、同時に又は独立して、ClO4 −、BF4 −、PF6 −、SbCl6 −、AsCl6 −、SbF6 −、AsF6 −、RdSO3 −を表し、ここでRdは塩素又はフッ素原子又はC1〜C8アルキル基、アリール基、フルオロアルキル基又はフルオロアリール基、又はBRe 4 −であり、ここでReはハライド原子及び/又はメチル基及び/又はCF3基などの1〜5個の基によって任意に置換されるフェニル基である)
の化合物であってよい。
[Ru(L4)Y2] (1’)
(式中、L4及びYは上に示した意味を有する)
の化合物が使用されてよい。
それぞれのz及びz’が1である場合、全ての点線及び斜線は単結合(アミノ基)を表すか;又はz’が1であり且つzが0である場合、全ての斜線は単結合を表し且つ全ての点線は二重結合(イミノ基)を表すか;又はz’が0であり且つzが1である場合、全ての点線は単結合を表し且つ全ての斜線は二重結合(イミノ基)を表し;且つ
それぞれのR1は、任意に置換される直鎖状、分枝鎖状又は環状のC1〜C12アルキル又はアルケニル基又は任意に置換されるC6〜10芳香族基を表し;且つ
それぞれのR2は、水素原子、任意に置換されるC1〜10アルキル基若しくはアルケニル基又は任意に置換されるC6〜10芳香族基を表し;2つの隣接R2は、一緒になって、飽和又は不飽和環を形成してよく、該環は5〜12個の原子を有し且つ前記R2が結合される原子を含み、且つ任意に置換され;
それぞれのR3は、水素原子、又は任意に置換されるC1〜10アルキル基若しくはアルケニル基又は任意に置換されるC6〜10芳香族基を表し;
それぞれのR4は、水素原子、任意に置換されるC1〜10アルキル基若しくはアルケニル基又は任意に置換されるC6〜10芳香族基を表し;
それぞれのQ’は、任意に置換されるC10〜C16メタロセンジイル、ジフェン−2,2’−イル、1,1’−ビナフタレン−2,2’−ジイル、ベンゼン−1,2−ジイル、ナフタレンジイル基を表し;且つ
QはQ’基を表すか又は
以下の式
それぞれのR5及びR6は、同時に又は独立して、水素原子、任意に置換されるC1〜10アルキル基又はアルケニル基、任意に置換されるC6〜10芳香族基を表し;2つの別個のR6基及び/又はR5基は、一緒になって、前記R6及び/又はR5基が結合される原子を含む、任意に置換されるC3〜8の又は更にC10までの飽和、不飽和又は芳香環を形成してよい)
の基を表す)
の化合物であってよい。
以下の式
R5及びR6は、同時に又は独立して、水素原子、任意に置換されるC1〜6アルキル基若しくはアルケニル基、又は任意に置換されるフェニル基を表し;2つの別個のR6及び/又はR5基は一緒になって、任意に置換され、前記R6及び/又はR5基が結合される原子を含む、C3〜6飽和又は不飽和環を形成してよい)
の基を表す。
それぞれのzが1である場合、全ての点線は単結合(アミノ基)を表すか;又はzが0である場合、全ての点線は二重結合(イミノ基)を表し;且つ
それぞれのR1は、任意に置換される直鎖状、分枝鎖状又は環状のC1〜C10アルキル基又は任意に置換されるC6〜10芳香族基を表し;且つ
それぞれのR2又はR2’は、水素原子、任意に置換されるC1〜6アルキル基若しくはアルケニル基又は任意に置換されるC6〜10芳香族基を表し;2つの隣接R2、又はR2及びR2’は一緒になって飽和又は不飽和環を形成してよく、該環は5〜6個の原子を有し且つ前記R2又はR2’が結合される原子を含み、且つ任意に置換され;
それぞれのR3は、水素原子、又は任意に置換されるC1〜6アルキル基を表し;
それぞれのQ’は、任意に置換される2,2’−ジフェニル、1,1’−ビナフタレン−2,2’−ジイル、ベンゼン−1,2−ジイル、ナフタレン−1,2−ジイル又はナフタレン−2,3−ジイル基を表し;且つ
QはQ’基を表すか又は
以下の式
の基を表す)
の化合物であってよい。
それぞれのR1は、任意に置換される直鎖状、分枝鎖状又は環状のC1〜C12アルキル基又は任意に置換されるC6〜10芳香族基を表し;且つ
それぞれのR2又はR2’は、水素原子、任意に置換されるC1〜6アルキル基若しくはアルケニル基又は任意に置換されるC6〜10フェニル基を表し;2つの隣接R2、又はR2及びR2’は一緒になって飽和又は不飽和環を形成してよく、該環は5〜6個の原子を有し且つ前記R2又はR2’が結合される原子を含み、且つ任意に置換され;
それぞれのR3は、水素原子、又は任意に置換されるC1〜6アルキル基を表し;且つ
それぞれのR9が、水素原子、ハロゲン原子、例えば、Cl又はF、C1〜6アルコキシ基、アルキル基又は過ハロゲン化炭化水素基、又は任意に置換されるベンジル基又はフェニル基を表すか;又は同じベンゼン環に結合される2つの隣接するR9が、一緒になって、縮合フェニル基又はインダニル基を表し、前記基は任意に1個、2個又は3個のハロゲン、C1〜4アルキル又はアルコキシ基によって置換される)
の化合物であってよい。
1)以下の式
[Ru(「ジエン」)(L’)vE2−v] (2)
(式中、vは0、1又は2を表し;
Eはモノアニオンを表し;
「ジエン」は、任意に置換される、2つの炭素−炭素二重結合を含む直鎖状又は分枝鎖状のC4〜C15炭化水素基、又は任意に置換される、2つの炭素−炭素二重結合を含む環状C7〜C20炭化水素基を表し;且つ
L’はC3〜C15アリル、任意に置換されるC6〜C12芳香環又はC7〜C15トリエンを表す)
のルテニウム前駆体と;
2)上で規定される、配位子L4と;
3)任意に約0.5〜5モル当量の間の塩基と
を一緒に反応させることを含む方法によって得られる又は得ることが可能である。
[Ru(「ジエン」)(「アリル」)2]、例えば、[Ru(COD)(2−メタリル)2]、[Ru(COD)(アリル)2]、[Ru(NBD)(2−メタリル)2]又は[Ru(NBD)(アリル)2];
[Ru(「ジエン」)E2]、例えば、[Ru(COD)(Cl)2]又は[Ru(NBD)(Cl)2];
[Ru(「ジエン」)(「トリエン」)]、例えば、[Ru(COD)(COT)];又は
[Ru(「ジエン」)(「アレーン」)]、例えば、[Ru(COD)(C6H6)]、[Ru(C6H6)(シクロヘキサジエン)]、[Ru(COD)(C8H8)]、[Ru(COD)(1,4−C6H4Me2)]又は[Ru(COD)(1,3,5−C6H3Me3)]。
本発明は、ここで以下の実施例によって更に詳細に記載されており、その際、温度は摂氏度で示され、省略形は当該技術分野における通常の意味を有する。
種々の本発明のルテニウム錯体を用いるケトンAの接触水素化
水素化の基質A(20ミリモル)、触媒前駆体RuCl2(L4)(0.01ミリモル)、塩基、及びイソプロパノール(10ml)を、圧力反応器内に置き、表1に示した温度及び時間で水素下(50バール)で撹拌した。
種々の本発明のルテニウム錯体を用いるケトン又はアルデヒドの接触水素化
水素化の基質(20ミリモル)、塩基(表2に示す通り)、イソプロパノール(10ml)、及び触媒前駆体RuCl2(L4)(0.01ミリモル)を圧力反応器内に置き、表2に示すように所定時間、所定温度でH2(50バール)の下で撹拌した。
外部塩基を用いずにインサイチュで生成した種々の本発明のルテニウム錯体を用いるケトンの接触水素化
ルテニウム前駆体[Ru(COD)(2−メチルアリル)2](0.02ミリモル)、配位子L4(0.02ミリモル)、及びイソプロパノール(1ml)をバイアル内に置き、60℃で1時間にわたりアルゴン下で撹拌した。この溶液を、圧力反応器内で基質(20ミリモル)及びイソプロパノール(9ml)の溶液に添加し、この混合物を、表3に示す時間にわたり水素(50バール)下にて60℃で撹拌した。
インサイチュで生成した種々の本発明のルテニウム錯体及び外部塩基を用いるケトン又はアルデヒドの接触水素化
ルテニウム前駆体[Ru(COD)Cl2](0.01ミリモル)、配位子L4(0.01ミリモル)、塩基及びケトン又はアルデヒドを、圧力反応器内でイソプロパノール(10ml)中に溶解させ、表4に示す時間にわたり水素(50バール)下にて60℃で撹拌した。
2−チオエーテルベンズアルデヒドの一般手順
2−ニトロベンズアルデヒド(33ミリモル)及びK2CO3(37ミリモル)を、窒素雰囲気下で乾燥DMF(50ml)中に溶解した。次に、チオール(35ミリモル)を、発熱反応を制御するのに適した速度で撹拌しながら、室温で添加し、混合物を80℃で16時間撹拌した。混合物を室温で冷却し、H2O(200ml)を添加し、この混合物をMTBE/ペンタン(1:1)で抽出した。有機層を水性の飽和NH4Cl溶液及び塩水で洗い、MgSO4で乾燥させて、この溶媒を減圧下で蒸留した。粗生成物を、バルブ−バルブ蒸留又はカラムクロマトグラフィー(シリカゲル、ペンタン/Et2O)によって精製した。
2−チオエーテルベンズアルデヒド(2当量)及び適切なジアミン(1当量)を、EtOH(1M)中に溶解し、80℃で一晩撹拌した。溶媒を減圧によって除去し、残留物をEtOH中に再溶解した。現時点で、生成物を自然に沈殿させるか又は溶媒を蒸発させて、残留物を高真空下で乾燥させると定量的な収率で粘性油が残り、これは十分に純粋であり、更なる精製を行わずに使用されるべきである。
適切なシッフ塩基配位子を、室温でNaBH4(2.2当量)のEtOH(1M)懸濁液に添加した。混合物を4時間撹拌しながら還流させて、次いで室温まで冷却した。NaOH溶液(H2O中で5w/w%)を添加し、撹拌を30分間継続した。混合物をMTBEで希釈し且つ抽出した。有機層を飽和K2CO3水溶液で洗い、MgSO4で乾燥させた。溶媒を蒸発させて、残留物をカラムクロマトグラフィー(シリカゲル、2%のEt3Nで5:1のヘプタン/EtOAc)で精製した。
RuCl2(PPh3)3と適切な四座配位子との当モルの混合物を、窒素下でトルエン(0.5〜1M)中に溶解し、80℃で一晩撹拌した。室温で冷却した後、混合物を濃縮し、Et2O又はヘキサンを添加して錯体を沈殿させた。あるいは、粗ルテニウム錯体を、酸化アルミニウムで濾過して精製し、最初にトルエン、次いでCH2Cl2ですすいで錯体を溶出させた。
Claims (3)
- 前記塩基がC1〜C8アルコキシド、アルカリ又はアルカリ土類水酸化物、又は無機水素化物であることを特徴とする、請求項1に記載の方法。
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