WO2012084810A1 - Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-thioether based ruthenium complexes - Google Patents
Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-thioether based ruthenium complexes Download PDFInfo
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- WO2012084810A1 WO2012084810A1 PCT/EP2011/073223 EP2011073223W WO2012084810A1 WO 2012084810 A1 WO2012084810 A1 WO 2012084810A1 EP 2011073223 W EP2011073223 W EP 2011073223W WO 2012084810 A1 WO2012084810 A1 WO 2012084810A1
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- WIPO (PCT)
- Prior art keywords
- group
- optionally substituted
- alkyl
- groups
- formula
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title claims description 10
- 150000003303 ruthenium Chemical class 0.000 title abstract description 6
- 150000002148 esters Chemical class 0.000 title description 4
- 239000003446 ligand Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000002576 ketones Chemical class 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012041 precatalyst Substances 0.000 claims abstract description 11
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract description 5
- 125000000879 imine group Chemical group 0.000 claims abstract 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 74
- 125000000217 alkyl group Chemical group 0.000 claims description 66
- 125000003118 aryl group Chemical group 0.000 claims description 50
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- -1 benzene- 1,2-diyl Chemical group 0.000 claims description 37
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 34
- 125000003342 alkenyl group Chemical group 0.000 claims description 31
- 125000004429 atom Chemical group 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 125000003545 alkoxy group Chemical group 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 19
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 10
- 229910052705 radium Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 5
- 239000012327 Ruthenium complex Substances 0.000 claims description 5
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 5
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 150000003568 thioethers Chemical group 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000004407 fluoroaryl group Chemical group 0.000 claims description 3
- 241000295146 Gallionellaceae Species 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910010276 inorganic hydride Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 15
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 6
- 125000000101 thioether group Chemical group 0.000 abstract description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 98
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 60
- 238000005481 NMR spectroscopy Methods 0.000 description 60
- 239000002585 base Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 23
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 17
- 150000002430 hydrocarbons Chemical group 0.000 description 16
- 150000001993 dienes Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000004820 halides Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000005671 trienes Chemical class 0.000 description 4
- 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
- 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
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 230000015572 biosynthetic process Effects 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
- 125000005394 methallyl group Chemical group 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
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 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 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
- 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
- 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical class O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 150000002466 imines Chemical group 0.000 description 2
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical class C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- HQGYGGZHZWXFSI-UHFFFAOYSA-N 1,4-cycloheptadiene Chemical compound C1CC=CCC=C1 HQGYGGZHZWXFSI-UHFFFAOYSA-N 0.000 description 1
- CVZCGTSPOXVTIG-WOJBJXKFSA-N 1-(2-methylsulfanylphenyl)-N-[(1R,2R)-2-[(2-methylsulfanylphenyl)methylideneamino]cyclohexyl]methanimine Chemical compound CSC1=CC=CC=C1C=N[C@H]1[C@H](N=CC=2C(=CC=CC=2)SC)CCCC1 CVZCGTSPOXVTIG-WOJBJXKFSA-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
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical class C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MYUHMLQNUDWBFR-UHFFFAOYSA-N 2-(1-adamantylsulfanyl)benzaldehyde Chemical compound O=CC1=CC=CC=C1SC1(C2)CC(C3)CC2CC3C1 MYUHMLQNUDWBFR-UHFFFAOYSA-N 0.000 description 1
- BIHUZDQZJYDCKQ-UHFFFAOYSA-N 2-(4-fluorophenyl)sulfanylbenzaldehyde Chemical compound C1=CC(F)=CC=C1SC1=CC=CC=C1C=O BIHUZDQZJYDCKQ-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- HGWOSUKIFQMEIF-ZETCQYMHSA-N 3-bromo-L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(Br)=C1 HGWOSUKIFQMEIF-ZETCQYMHSA-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical class O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth 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
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride 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
- 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
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical class O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 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
- 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
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 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
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 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
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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
- 238000006467 substitution reaction Methods 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
- 150000003573 thiols Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
- C07D317/64—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/32—All rings being cycloaliphatic the ring system containing at least eleven carbon atoms
Definitions
- the present invention relates to the field of catalytic hydrogenation and, more particularly, to the use of specific ruthenium catalysts, or pre-catalysts, in hydrogenation processes for the reduction of ketones or aldehydes into the corresponding alcohols.
- hydride processes in which a silyl or metal hydride salt, such as L1AIH 4 , or PMHS (polymethylhydrosiloxane) is used;
- a silyl or metal hydride salt such as L1AIH 4 , or PMHS (polymethylhydrosiloxane) is used;
- One of the mandatory and characterizing elements of direct hydrogenation processes is the catalyst or the catalytic system that is used to activate the molecular hydrogen to promote of the reduction.
- the development of useful catalysts or catalytic systems for the hydrogenation of a ketone, aldehyde or ester functional group represents an important, difficult, and unpredictable task in chemistry.
- ruthenium catalysts or catalytic systems known to perform direct hydrogenations are based on complexes containing ligands possessing at least one coordinating phosphorus atom, the best systems having a P2N2 coordination sphere.
- Typical examples are the (PP)(NN) type (see EP 0901997 and EP 1813621 for ketones and aldehydes, or more recently WO08/065588 for esters), or (PN)(PN)/(P 2 N 2 ) type (see WO02/022526 or WO02/40155).
- Ru complexes having the metal centre coordinated by two nitrogen atoms and two sulfur atoms can be used as catalyst or pre-catalyst in the direct hydrogenation of ketone or aldehyde groups.
- These ligands are cheap, much less sensitive toward oxidation than phosphines and allow a great structural diversity.
- the present invention relates to processes for the reduction by hydrogenation, using molecular 3 ⁇ 4, of a C 3 -C70 substrate containing one, two or three ketones and/or aldehydes functional groups into the corresponding alcohol, characterized in that said process is carried out in the presence of at least a base and at least one catalyst or pre-catalyst in the form of a C8-C56 ruthenium complex comprising in the coordination sphere a tetradentate ligand (L4) coordinating the ruthenium with:
- the substrate can be a C 3 -30 compound, in particular of formula of formula (I) wherein R a represents a hydrogen atom or a R b group; and
- R b represents a C1-C29 hydrocarbon group optionally substituted and optionally comprising one or two carbonyl groups, a Ci-C 6 hydrocarbon group substituted by a C 3 -8 heterocycle (aromatic or not) comprising one or two atoms selected amongst sulfur, nitrogen or oxygen, or a C 3 -8 heterocycle (aromatic or not) comprising one or two atoms selected amongst sulfur, nitrogen or oxygen optionally substituted by one or two Ci-C 6 hydrocarbon group;
- R a and R b are bonded together and form a C 3 -C20, preferably C4-C20 , saturated or unsaturated hydrocarbon group, optionally substituted and optionally comprising one or two carbonyl groups.
- the substrate can be a C 3 -30 compound, in particular of formula of formula (I) wherein R a represents a hydrogen atom or a C1-C2 8 hydrocarbon group, optionally substituted; and
- R b represents a C1-C29 hydrocarbon group, optionally substituted and optionally comprising one or two carbonyl groups; or represents a C 3 -8 heterocycle (aromatic or not) comprising one or two atoms selected amongst sulfur, nitrogen or oxygen;
- R a and R b are bonded together and form a C 3 -C20, preferably C4-C20 , saturated or unsaturated hydrocarbon group, optionally substituted and optionally comprising one or two carbonyl groups.
- said R b group comprises zero or one carbonyl group.
- said compounds (Il-a) can be in a racemic or optically active form, depending on the nature of the substrate and on the catalyst/pre-catalyst used.
- R a or R b can be in the form of a linear, branched or cyclic aromatic, alkyl, alkenyl, or alkynyl group, e.g., a linear alkyl group, or can also be in the form of a mixture of said type of groups, e.g. a specific R a may comprise a linear alkyl, a branched alkenyl (e.g. having one or more carbon-carbon double bonds), a (poly)cyclic alkyl and an aryl moiety, unless a specific limitation to only one type is mentioned.
- a group when a group is mentioned as being in the form of more than one type of topology (e.g. linear, cyclic or branched) and/or unsaturation (e.g. saturated, unsaturated or aromatic, or more particularly alkyl, aromatic or alkenyl), it is meant also a group which may comprise moieties having any one of said topologies or unsaturations, as explained above.
- topology e.g. linear, cyclic or branched
- unsaturation e.g. saturated, unsaturated or aromatic, or more particularly alkyl, aromatic or alkenyl
- the substrate is a ketone or aldehyde that will provide an alcohol that is useful in the pharmaceutical, agrochemical or perfumery industry as final product or as an intermediate.
- Particularly preferred substrate is a ketone or aldehyde that will provide an alcohol useful, as final product or as an intermediate, in the perfumery industry.
- the substrate is a C3-C20, or a C5-C15, compound of formula (I), and in particular one may cite those wherein R a represent a hydrogen atom or a R b group, R b representing a linear, branched or cyclic C2-C19 hydrocarbon group optionally substituted; or R a and R b are bonded together and form a C5-C19 saturated or unsaturated hydrocarbon group, optionally substituted.
- R a and R b are one, two, or three halogen, OR c , NR°2, SR C , groups, in which R c is a hydrogen atom, a halogenated Ci-C 2 group or a Ci to Ci 0 cyclic, linear or branched alkyl or alkenyl group, preferably a Ci to C 4 linear or branched alkyl or alkenyl group.
- said substituents are one or two OR c groups, in which R c is a hydrogen atom or a Ci to C 6 cyclic, linear or branched alkyl or alkenyl group.
- Non- limiting examples of substrates are the following:
- a di-(Ci-i5 alkyl)ketone a C 8 -C15 (un)substituted-benzyl alkyl ketone, a C 8 -C15 (un)substituted-styryl alkyl ketone, a C12-C15 ketone comprising a 2,6,6-trimethyl cyclohexenyl/cyclohexyl group, a C1 3 -C15 ketone comprising a 2,2,3-trimethyl- cyclopentenyl or 2,2,3-trimethyl-cyclopentyl group, a C4-C12 (un)substituted cyclic ketone, a Cio-i 8 (un)substituted cyclopentenone or (un)substituted cyclopentanone alpha substituted by a C5-12 hydrocarbon group, a Cn-is (un) substituted cyclohexenone or cyclohexanone alpha substituted by
- aryl it is meant a phenyl or naphthyl group.
- Ru complex As mentioned above, the present invention requires the use of a particular Ru catalyst or pre-catalyst (Ru complex). Many Ru complexes can be used, but all have the same common point: i.e. a coordination sphere comprising a tetradentate ligand (L4) coordinating the ruthenium with two amino/imino groups and two thioether groups (i.e. ligand providing a coordination sphere of the type N2S2).
- L4 tetradentate ligand
- ligand providing a coordination sphere of the type N2S2
- the ruthenium catalyst or pre-catalyst (also referred to from herein as complex) can be of the general formula
- r 0, 1 or 2;
- L4 represents one C 10-40 tetradentate ligand coordinating the Ru metal with:
- each L represents, simultaneously or independently, a neutral C1-C26 neutral monodentate ligand
- each Y represents, simultaneously or independently, a halogen atom, a hydrogen atom, a BH4 group, a hydroxyl group, a C1-C10 alkoxyl group or an C 3 -C15 allyl group;
- each Z represents, simultaneously or independently, CIO4 " , BF 4 -, PF 6 -, SbCl 6 -, AsCl 6 -, SbF g -, AsF g -, a R d S0 3 ⁇ wherein R d is a chlorine of fluoride atom or an Ci-C 8 alkyl, aryl, fluoroalkyl or fluoroaryl group, or a BRV wherein R e is a phenyl group optionally substituted by one to five groups such as halide atoms and/or methyl and/or CF 3 groups.
- each Y represents, simultaneously or independently, a hydrogen atom, a hydroxyl, a Ci to Cio alkoxyl group, such as a methoxyl, ethoxyl or isopropoxyl group, or a C 3 -C6 allyl group group, such as allyl (i.e. propenyl), 2-methyl-allyl (i.e. 2-methyl-propenyl).
- each Z represents, simultaneously or independently, CIO4 “ , BF 4 , PF 6 “, SbCL/, AsCL/, SbF 6 “, AsF 6 ", a R d S0 3 ⁇ wherein R d is a chlorine of fluoride atom or a CF 3 group, or a BRV wherein R e is a phenyl group optionally substituted by one, two or three groups such as halide atoms and/or methyl and/or CF 3 groups.
- the monodentate ligand L can be a C 3 _2 4 mono-phosphine, like PPh 3 , CO (carbon monoxide) or even, and preferably, a solvent.
- solvent it has to be understood the usual meaning in the art and in particular compounds used as diluents in the preparation of the complex or during the invention's process.
- Non limiting examples of such solvent are acetonitrile, an alcohol (e.g. an C1-C4 alcohol), water, an ether (e.g. THF or diethylether), pyridine, a C 3 -C8 ester, or the substrate of the invention's process.
- the complexes of the invention can be added into the reaction medium of the invention's process in a large range of concentrations.
- concentration values those ranging from 10 ppm to 50000 ppm, relative to the amount of substrate.
- the complex concentration will be comprised between 100 and 10000, or even 1000, ppm. It goes without saying that the optimum concentration of complex will depend, as the person skilled in the art knows, on the nature of the latter, on the nature of the substrate and on the pressure of 3 ⁇ 4 used during the process, as well as the desired time and temperature of reaction.
- the hydrogenation process of the invention is carried out in the presence of a base.
- Said base can be the substrate itself, if the latter is basic, a corresponding alkoxide or any organic or inorganic base having preferentially a pK a above 10.
- the base may also be provided by the complex itself (e.g. Y is hydrogen or a OH or alkoxyl group or a methylallyl). In such case, the base is considered as being present in the process in up to two molar equivalents compared to the Ru complex.
- said base may have a pK a above 14. It is also understood that preferably said base does not reduce by itself a substrate of formula (I).
- a substrate of formula (I) As non- limiting examples one may cite the following types of base: an aluminum or boron hydride, an alkaline or alkaline-earth metal hydroxide, or an alkoxide of formula (R 31 0) 2 M or R 31 OM', wherein M is an alkaline-earth metal, M' is an alkaline metal or an ammonium NR 32 4 + , R 31 stands for hydro gen or a Ci to Cs hydrocarbon group and R 32 stands for a Ci to Ci 0 linear or branched alkyl group, such as sodium or potassium alkoxides.
- R 31 stands for hydro gen or a Ci to Cs hydrocarbon group
- R 32 stands for a Ci to Ci 0 linear or branched alkyl group, such as sodium or potassium alkoxides.
- other suitable bases can be used
- said base is a Ci -8 alkoxide, alkaline or alkaline-earth hydroxides, such as sodium, potassium or calcium hydroxide, or inorganic hydrides such as NaBH 4 , NaH or KH.
- Useful quantities of base, added to the reaction mixture, may be comprised in a relatively large range. From the definition of formula (1) and of the base, it is evident that said base can be also comprised or incorporated in the catalyst itself. However, it is always beneficial to add an additional amount of base especially if working with a low catalyst load.
- One can cite, as non-limiting examples, ranges between 1 to 50000 molar equivalents, relative to the complex (e.g. base/com up to 50000), preferably 1 to 2000, and even more preferably between 1 and 100 molar equivalents.
- the hydrogenation reaction can be carried out in the presence or absence of a solvent.
- the process is carried out in the presence of a solvent (in general for practical reasons), and any solvent current in hydrogenation reactions can be used for the purposes of the invention.
- a solvent in general for practical reasons
- Non-limiting examples include C2-5 nitril alkyl such as acetonitril, C 3 -8 ⁇ , ⁇ -dialkyl amide such as dimethyl formamide, C 3 -9 ethers such as tetrahydrofuran or MTBE, polar solvents such as dimethyl sulfoxide or Ci -5 primary or secondary alcohols such as isopropanol or ethanol, or mixtures thereof.
- said solvent can be selected amongst Ci -5 primary or secondary alcohols such as methanol, isopropanol or ethanol, or mixtures thereof or mixtures of said alcohols with the other herein above mentioned solvents.
- the reaction can be carried out at a 3 ⁇ 4 pressure comprised between 10 5 Pa and 80xl0 5 Pa (1 to 80 bars) or even more if desired.
- a person skilled in the art is well able to adjust the pressure as a function of the catalyst load and of the dilution of the substrate in the solvent.
- the temperature at which the hydrogenation can be carried out is comprised between 0°C and 120°C, preferably in the range of between 20°C and 100°C.
- a person skilled in the art is also able to select the preferred temperature as a function of the melting and boiling point of the starting and final products as well as the desired time of reaction or conversion.
- L4 can be a compound of formula
- each z and z' is 1, in which case the all dotted and hatched lines represent a single bond (amino group); or z' is 1 and z is 0, in which case the all hatched lines represent a single bond and all dotted lines represent a double bond (imino group); or z' is 0 and z is 1, in which case the all dotted lines represent a single bond and all hatched lines represent a double bond (imino group); and each R 1 represents a linear, branched or cyclic Ci to Ci 2 alkyl or alkenyl group optionally substituted or an C 6- io aromatic group optionally substituted; and
- each R 2 represents a hydrogen atom, a Ci-io alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted; two adjacent R 2 , taken together, may form a saturated or unsaturated cycle containing 5 to 12 atoms and including the atoms to which said R 2 are bonded, and being optionally substituted;
- each R 3 represents a hydrogen atom or a Ci-io alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted;
- each R 4 represents a hydrogen atom, a Ci-io alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted;
- each Q' represents a Cio-Ci 6 metallocenediyl, a diphen-2,2' -yl, a l, l ' -binaphthalene-2,2'- diyl, a benzene- 1 ,2-diyl, a naphthalenediyl group optionally substituted;
- Q represents a Q' group
- each R 5 and R 6 represent, simultaneously or independently, a hydrogen atom, a Ci-io alkyl or alkenyl group optionally substituted, a C 6- io aromatic group optionally substituted; two distinct R 6 and/or R 5 groups, taken together, may form a C3-8, or even up to Ci 0 , saturated, unsaturated or aromatic ring optionally substituted, including the atoms to which said R 6 and/or R 5 groups are bonded.
- Non-limiting examples of possible substituents of said R 1 , R 2 , R 3 , R 4 , R 5 , R 6 or Q' are one, two, three or four groups selected amongst i) halogen atom (in particular when said substituents are on aromatic moieties), ii) C 5- i 2 cycloalkyl or cycloalkenyl, iii) Ci-io alkoxy, alkyl, alkenyl, polyalkyleneglycols or halo- or perhalo-hydrocarbon, iv) a benzyl group or a fused or non-fused phenyl or indanyl group, said group being optionally substituted by one, two or three halogen, Ci -8 alkyl, alkoxy, or halo- or perhalo- hydrocarbon groups.
- the Q' group may also be substituted by one or two amino, nitro or sulfonate groups or by one or two groups of formula 0-(CR 8 2) n -0 or 0-(CR 8 2) n -NR 7 wherein n is 1 or 2 and R 8 being a hydrogen atom or a C1-4 alkyl group.
- halo- or perhalo-hydrocarbon has here the usual meaning in the art, e.g. groups such as CF 3 or CCIH2 for instance.
- the atoms which may coordinate the Ru atom are the N atom and the S atom.
- any one of the embodiments of the present invention whenever two groups of formula (A) are taken together to form a cycle or ring said cycle or ring can be a mono or bi-cyclic group.
- the ligand of formula (A) can be in a racemic or optically active form.
- said ligand is one wherein a is 0 and b is 0 or 1.
- each R 1 represents, a linear, branched or cyclic Ci to Ci 0 alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted.
- each R 2 represents a hydrogen atom, a Ci -6 alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted; two adjacent R 2 , taken together, may form a saturated or unsaturated cycle containing 5 to 8 atoms and including the atoms to which said R 2 are bonded, and being optionally substituted.
- each R 3 represents a hydrogen atom or a Ci -6 alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted.
- each R 4 represents a hydrogen atom, a Ci -6 alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted.
- Q represents a Q' group
- R 5 and R 6 represent, simultaneously or independently, a hydrogen atom, a Ci_ 6 alkyl or alkenyl group optionally substituted, or a phenyl group optionally substituted; two distinct R 6 and/or R 5 groups, taken together, may form a C3-6 saturated or unsaturated ring optionally substituted, including the atoms to which said R 6 and/or R 5 groups are bonded.
- the possible substituents of said R 1 , R 2 , R 3 , R 4 , R 5 , R 6 or Q' are one, two or three groups selected amongst i) halogen atom (in particular when said substituents are on aromatic moieties), ii) C5-6 cycloalkyl or cycloalkenyl, iii) Ci -6 alkoxy, alkyl or halo- or perhalo-hydrocarbon, iv) a benzyl group or a fused or non-fused phenyl or indanyl group, said group being optionally substituted by one, two or three halogen, Ci_ 4 alkyl or alkoxy groups.
- said ligand can be a compound of formula
- b is 0 or 1 ;
- each z is 1, in which case the all dotted lines represent a single bond (amino group); or z is 0, in which case the all dotted lines represent a double bond (imino group); and each R 1 represents, a linear, branched or cyclic Ci to Ci 0 alkyl group optionally substituted or a C 6- io aromatic group optionally substituted; and
- each R 2 or R 2 represents a hydrogen atom, a Ci -6 alkyl or alkenyl group optionally substituted or a C 6- io aromatic group optionally substituted; two adjacent R 2 , or R 2 and R 2 , taken together, may form a saturated or unsaturated cycle containing 5 to 6 atoms and including the atoms to which said R 2 or R 2 are bonded, and being optionally substituted; each R 3 represents a hydrogen atom or a Ci -6 alkyl group optionally substituted;
- each Q' represents a 2,2'-diphenyl, a l,l'-binaphthalene-2,2'-diyl, a benzene- 1,2-diyl, a naphthalene- 1,2-diyl or a naphthalene-2,3-diyl group optionally substituted;
- Q represents a Q' group
- R 5 and R 6 represent, simultaneously or independently, a hydrogen atom, a Ci -6 alkyl or alkenyl group optionally substituted, or a phenyl group optionally substituted; two distinct R 6 and/or R 5 groups, taken together, may form a C3-6 saturated or unsaturated ring optionally substituted, including the atoms to which said R 6 and/or R 5 groups are bonded.
- Possible substituents of said R 1 , R 2 , R 2 , R 3 , R 5 , R 6 or Q' , in formula (B), are one, two or three groups selected amongst i) halogen atom (in particular when said substituents are on aromatic moieties), ii) C5-6 cycloalkyl or cycloalkenyl, iii) Ci -6 alkoxy, alkyl or perhalo-hydrocarbon, iv) a benzyl group or a fused or non-fused phenyl or indanyl group, said group being optionally substituted by one, two or three halogen, C1-4 alkyl or alkoxy, groups.
- R 1 , R 2 , R 2 , R 3 , R 5 , R 6 Q or Q' are one, two or three groups selected amongst i) halogen atom (in particular when said substituents are on aromatic moieties), ii) C5-6 cycloalkyl or cycloalkenyl, iii) C1-4 or Ci -6 alkoxy, alkyl or perhalo-hydrocarbon, iv) a fused or non-fused phenyl group being optionally substituted by one, two or three halogen, C1-4 alkyl or alkoxy, groups.
- halogen atom in particular when said substituents are on aromatic moieties
- C5-6 cycloalkyl or cycloalkenyl iii) C1-4 or Ci -6 alkoxy, alkyl or perhalo-hydrocarbon
- iv) a fused or non-fused phenyl group being optionally substituted by one, two or three halogen,
- said ligand is one wherein b is 0.
- said ligand can be a compound of formula
- each z is 1, in which case the all dotted lines represent a single bond (amino group); or z is 0, in which case the all dotted lines represent a double bond (imino group);
- each R 1 represents, a linear, branched or cyclic Ci to Ci 0 alkyl group optionally substituted or a C 6- io aromatic group optionally substituted;
- each R 2 or R 2 represents a hydrogen atom, a Ci -6 alkyl or alkenyl group optionally substituted or a C 6- io phenyl group optionally substituted; two adjacent R 2 , or R 2 and R 2 , taken together, may form a saturated or unsaturated cycle containing 5 to 6 atoms and including the atoms to which said R 2 or R 2 are bonded, and being optionally substituted; each R 3 represents a hydrogen atom or a Ci -6 alkyl group optionally substituted; and each R 9 represents a hydrogen atom, a halogen atom, such as CI or F, a Ci_ 6 alkoxy, alkyl or perhalo-hydrocarbon, or a benzyl or phenyl group optionally substituted; or two adjacent R 9 bonded to the same benzene ring, taken together, represents a fused phenyl or indanyl group, said group being optionally substituted by one, two or three halogen, Ci_ 4
- Possible substituents of said R 1 , R 2 , R 2 , R 3 or R 9 , in formula (C), are one or two groups selected amongst i) halogen atom (in particular when said substituents are on aromatic moieties), ii) Ci -6 alkoxy, alkyl or perhalo-hydrocarbon.
- each R 9 represents a hydrogen atom, a halogen atom, such as CI or F, a Q_ 4 alkoxy, alkyl or perhalo- hydrocarbon, or a phenyl group optionally substituted; or two adjacent R 9 bonded to the same benzene ring, taken together, represents a fused phenyl group, said group being optionally substituted by one, two or three halogen, Q_ 4 alkyl or alkoxy groups.
- each R 3 represents a hydrogen atom.
- each R 2 represents a hydrogen atom, a Ci -4 alkyl group or phenyl group optionally substituted as above mentioned.
- each R 2 represents a hydrogen atom, a Ci_ 4 alkyl group or phenyl group optionally substituted as above mentioned; or two adjacent R 2 , taken together, may form a saturated cycle containing 5 to 6 atoms and including the atoms to which said R 2 or R 2 are bonded, and being optionally substituted as above mentioned.
- each R 2 may represent a hydrogen atom, a Ci_4 alkyl group or phenyl group optionally substituted as above mentioned; or two adjacent R 2 , taken together, may form a cyclohexyl group including the atoms to which said R 2 or R 2 are bonded.
- said R 1 , R 2 , R 2 , R 3 or R 4 are unsubstituted groups as defined above (i.e. the optionally substitution is not applicable).
- non-limiting examples of such alkyl group may be a Me, 'Pr, 'Bu, 3 ⁇ 4u, s Bu, "Pentyl cyclopently, cylohexyl or adamantly group.
- non-limiting examples of aromatic group optionally substituted are indanyl, C 6 H5 (phenyl), C10H7 (naphthyl), (X) r C 6 H 5 - r or (X) r Ci 0 H 7 _ r , r being 1 or 2 and X being F, CI, CF 3 , (X) r C 6 H 5 - r or a Ci_ 4 alkoxy, sulfide or alkyl group (such as 'Bu or OMe or Me).
- R 1 is a group as exemplified herein above for alkyl or aromatic groups.
- non-limiting examples of Q' are C 6 H 4 (benzene- 1,2-diyl), CioH 6 (naphthalene- 1,2-diyl or a naphthalene-2,3-diyl), (X) r C 6 H 4 _ r or (X) r Ci 0 H 6 _ r , r being 1 or 2 and X being F, CI, CF 3 , (X) v C 6 H 5 -v or a d_ 4 alkoxy or alkyl group (such as 'Bu or OMe or Me).
- Q is a group of formula (i) and non-limiting examples of said Q are CH2, CMe2 or CH2CH2.
- aromatic group or ring it is meant a phenyl or naphthyl group, and in particular a phenyl group.
- said ligand is one wherein all the dotted lines represent a double bond (imino group) and at least one R 1 group is an alkyl group.
- said ligand is one wherein the all dotted lines represent a single bond (amino group).
- said R 3 is a hydrogen atom.
- lines represent a single/double bond", or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. that the whole bonding (solid and dotted/hatched line) between the atoms connected by said lines is a single or double bond.
- L4 ligands As non limiting examples of L4 ligands one can cite the following ones:
- the invention's ligands can be obtained by applying standard general methods which are well known in the state of the art and by the person skilled in the art. In particular said ligands can be prepared as described in the Examples.
- the complexes of formula (1) or ( ), as above described, are also another object of the invention since are new compounds, at the exception of complex RuCl 2 (IV) (N,N- bis(2-(1 ⁇ 2 ⁇ butylthio-KS)benzylidene)-l,2-ethanediamino-KA/,KN)dichlororuthenium(II)), RuCl 2 (VIII) ((N,N-bis(2-(im-butylthio-KS)benzylidene)- 1 ,2-cyclohexyldiamino- RuCl 2 (XXXII) (N,N-bis(2-( ri-butylthio- S)benzylidene)- 1 ,3-propanediamino- N, N , )dichlororuthenium(II)) and RuCl 2 (XXXVI) N,N-bis(2-( ⁇ 'r butylthio- S)benzylidene) ,2-prop
- the complex (1) of the invention can be used in the form of a preformed complex or can be generated in situ, in the reaction medium of the hydrogenation.
- the catalyst or pre-catalyst is obtained or obtainable by a process comprising reacting together:
- E represents a mono anion
- iene represents a linear or branched C4-C15 hydrocarbon group comprising two carbon-carbon double bonds, optionally substituted, or a cyclic C 7 -C 2 o hydrocarbon group comprising two carbon-carbon double bonds, optionally substituted; and L' represents a C 3 -C15 allyl, a C 6 -Ci2 aromatic ring optionally substituted or a C7-C15 triene;
- Optional substituent of the "diene" or of L' are one or two C1-C10 alkyl or aryl groups, Ci-C 6 alkoxy groups or -C(0)0-(Ci-C 6 alkyl) groups.
- triene possesses the usual meaning in the art, i.e. a group comprising three non aromatic carbon- carbon double bonds.
- E represents a mono anion selected amongst the group consisting of halides (e.g. CI, Br, I,), BF 4 , CIO4 " , PF 6 -, SbCl 6 -, AsCl g -, SbF g -, AsF g -, hydroxylate, C1-C10 carboxylates (e.g.
- Suitable ruthenium precursors one can cite the compound (2) wherein "diene” stands for a C7-C10, hydrocarbon group comprising two carbon-carbon double bonds, such as for example COD (cycloocta-l,5-diene) or NBD (norbornadiene) , or yet cyclohepta- 1 ,4-diene.
- diiene stands for a C7-C10, hydrocarbon group comprising two carbon-carbon double bonds, such as for example COD (cycloocta-l,5-diene) or NBD (norbornadiene) , or yet cyclohepta- 1 ,4-diene.
- Suitable ruthenium precursors one can cite the compound (2) wherein "aromatic ring” stands for a C 6 -Ci2 group comprising a benzene ring, such as an indane or a p-cymene such as for example benzene, para-cymene (6-isopropyl-toluene) or hexamethyl benzene.
- aromatic ring stands for a C 6 -Ci2 group comprising a benzene ring, such as an indane or a p-cymene such as for example benzene, para-cymene (6-isopropyl-toluene) or hexamethyl benzene.
- triene stands for a C7-C10 hydrocarbon group comprising three non aromatic carbon-carbon double bonds, such as for example COT (cyclooctatriene).
- the preparation of the catalyst may benefit from the presence of a base, in particular when in compound (2) E represents a halogen or a carboxylate group.
- Said base can be defined as for the base of the hydrogenation process described herein above.
- ruthenium precursor (2) As specific, but non limiting, examples of said ruthenium precursor (2), one may cite the following:
- [Ru("diene")("allyl") 2 such as [Ru(COD)(2-methallyl) 2 ], [Ru(COD)(allyl) 2 ], [Ru(NBD)(2-methallyl) 2 ] or [Ru(NBD)(allyl) 2 ];
- [Ru("diene”)E 2 ] such as [Ru(COD)(Cl) 2 ] or [Ru(NBD)(Cl) 2 ];
- the preparation of the catalyst/pre-catalyst can be carried out in a suitable solvent.
- Said solvent could be the substrate of the hydrogenation processes itself or another one. Typically there is used the same solvent as for the subsequent hydrogenation as described herein above. Typical non-limiting examples are given herein below, when describing the hydrogenation process.
- ketones and aldehydes from A to Y are the substrates used examples 1 to 57:
- the hydrogenation substrate (20 mmol), the base (as in Table 2), ⁇ -propanol (10 ml), and the catalyst precursor RuCl 2 (L4) (0.01 mmol) were placed into a pressure reactor and stirred under 3 ⁇ 4 (50 bar) at the given temperature for the given amount of time as indicated in Table 2.
- the ruthenium precursor [Ru(COD)(2-Methylallyl) 2 ] (0.02 mmol), the ligand L4 (0.02 mmol), and isopropanol (1 ml) were placed in a vial and stirred under argon at 60°C for lh. This solution was added to a solution of substrate (20 mmol) and isopropanol (9 ml) in a pressure reactor and the mixture was stirred at 60°C under hydrogen (50 bar) for the period of time as indicated in Table 3.
- the base is the anion of the catalyst.
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EP11811015.4A EP2655303B1 (en) | 2010-12-21 | 2011-12-19 | Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-thioether based ruthenium complexes |
JP2013545259A JP6080774B2 (en) | 2010-12-21 | 2011-12-19 | Hydrogenation of ester or carbonyl groups with tetradentate amino / imino-thioether based ruthenium complexes |
MX2013005703A MX2013005703A (en) | 2010-12-21 | 2011-12-19 | Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-thioether based ruthenium complexes. |
BR112013012050A BR112013012050A2 (en) | 2010-12-21 | 2011-12-19 | hydrogenation of esters or carbonyl groups with ruthenium complexes based on tetradented amine / imine |
US13/996,847 US8614345B2 (en) | 2010-12-21 | 2011-12-19 | Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-thioether based ruthenium complexes |
ES11811015.4T ES2624265T3 (en) | 2010-12-21 | 2011-12-19 | Hydrogenation of ester or carbonyl groups with tetradentate amino / imino-thioether based ruthenium complexes |
CN201180060602.0A CN103261133B (en) | 2010-12-21 | 2011-12-19 | Hydrogenation of esters or carbonyl groups with tetradentate amino/imino-hioether based ruthenium complexes |
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US10370314B2 (en) * | 2016-05-13 | 2019-08-06 | Dms Ip Assets B.V. | Selective reduction of esters to alcohols |
US11498901B2 (en) * | 2018-03-02 | 2022-11-15 | Firmenich Sa | Hydrogenation of imines with Ru complexes |
CN112239384B (en) * | 2020-08-07 | 2023-05-12 | 浙江理工大学 | Preparation method of thioester compound |
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MX2013005703A (en) | 2013-07-05 |
CN103261133A (en) | 2013-08-21 |
BR112013012050A2 (en) | 2016-08-16 |
US8614345B2 (en) | 2013-12-24 |
JP6080774B2 (en) | 2017-02-15 |
CN103261133B (en) | 2015-04-15 |
ES2624265T3 (en) | 2017-07-13 |
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