JP6732744B2 - ルテニウム触媒作用によるアゾベンゾール類からのビフェニルアミン類の製造方法 - Google Patents
ルテニウム触媒作用によるアゾベンゾール類からのビフェニルアミン類の製造方法 Download PDFInfo
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- JP6732744B2 JP6732744B2 JP2017523880A JP2017523880A JP6732744B2 JP 6732744 B2 JP6732744 B2 JP 6732744B2 JP 2017523880 A JP2017523880 A JP 2017523880A JP 2017523880 A JP2017523880 A JP 2017523880A JP 6732744 B2 JP6732744 B2 JP 6732744B2
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- acid
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- methyl
- carbonate
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 10
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical class NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006555 catalytic reaction Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims description 50
- 239000000460 chlorine Substances 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 28
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 claims description 22
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 125000001589 carboacyl group Chemical group 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims description 10
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 235000011181 potassium carbonates Nutrition 0.000 claims description 7
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- JRUKSSBDIZXQDX-UHFFFAOYSA-N 2,3,6-trimethylbenzoic acid Chemical compound CC1=CC=C(C)C(C(O)=O)=C1C JRUKSSBDIZXQDX-UHFFFAOYSA-N 0.000 claims description 4
- XZRHNAFEYMSXRG-UHFFFAOYSA-N 2,5-dimethylbenzoic acid Chemical compound CC1=CC=C(C)C(C(O)=O)=C1 XZRHNAFEYMSXRG-UHFFFAOYSA-N 0.000 claims description 4
- OPVAJFQBSDUNQA-UHFFFAOYSA-N 3,4-dimethylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C OPVAJFQBSDUNQA-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 2
- WJPISYUIIFJNPA-UHFFFAOYSA-N 2,3,5-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C)C(C(O)=O)=C1 WJPISYUIIFJNPA-UHFFFAOYSA-N 0.000 claims description 2
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 claims description 2
- HCBHQDKBSKYGCK-UHFFFAOYSA-N 2,6-dimethylbenzoic acid Chemical compound CC1=CC=CC(C)=C1C(O)=O HCBHQDKBSKYGCK-UHFFFAOYSA-N 0.000 claims description 2
- HQRZURAZLLFYBT-UHFFFAOYSA-N 2-(2,3,4,6-tetramethylphenyl)acetic acid Chemical compound CC1=CC(C)=C(CC(O)=O)C(C)=C1C HQRZURAZLLFYBT-UHFFFAOYSA-N 0.000 claims description 2
- CJALGXCLNXAAAC-UHFFFAOYSA-N 2-(2,3,5,6-tetramethylphenyl)acetic acid Chemical compound CC1=CC(C)=C(C)C(CC(O)=O)=C1C CJALGXCLNXAAAC-UHFFFAOYSA-N 0.000 claims description 2
- WQNDCWLYPYMUMV-UHFFFAOYSA-N 2-(2,3,6-trimethylphenyl)acetic acid Chemical compound CC1=CC=C(C)C(CC(O)=O)=C1C WQNDCWLYPYMUMV-UHFFFAOYSA-N 0.000 claims description 2
- GXMWLJKTGBZMBH-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=C(Cl)C=C1Cl GXMWLJKTGBZMBH-UHFFFAOYSA-N 0.000 claims description 2
- RUSCTNYOPQOXDJ-UHFFFAOYSA-N 2-(2,5-dimethylphenyl)acetic acid Chemical compound CC1=CC=C(C)C(CC(O)=O)=C1 RUSCTNYOPQOXDJ-UHFFFAOYSA-N 0.000 claims description 2
- IUJAAIZKRJJZGQ-UHFFFAOYSA-N 2-(2-chlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1Cl IUJAAIZKRJJZGQ-UHFFFAOYSA-N 0.000 claims description 2
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 claims description 2
- WFPMUFXQDKMVCO-UHFFFAOYSA-N 2-(3-chlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Cl)=C1 WFPMUFXQDKMVCO-UHFFFAOYSA-N 0.000 claims description 2
- GXXXUZIRGXYDFP-UHFFFAOYSA-N 2-(4-methylphenyl)acetic acid Chemical compound CC1=CC=C(CC(O)=O)C=C1 GXXXUZIRGXYDFP-UHFFFAOYSA-N 0.000 claims description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 2
- OWBVULKHVZHYPN-UHFFFAOYSA-N 3,4,5-trimethylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC(C)=C1C OWBVULKHVZHYPN-UHFFFAOYSA-N 0.000 claims description 2
- UMVOQQDNEYOJOK-UHFFFAOYSA-N 3,5-dimethylbenzoic acid Chemical compound CC1=CC(C)=CC(C(O)=O)=C1 UMVOQQDNEYOJOK-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- CDPKJZJVTHSESZ-UHFFFAOYSA-N 4-chlorophenylacetic acid Chemical compound OC(=O)CC1=CC=C(Cl)C=C1 CDPKJZJVTHSESZ-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- CLOXAWYNXXEWBT-UHFFFAOYSA-N tert-butyl n-(3-oxocyclopentyl)carbamate Chemical compound CC(C)(C)OC(=O)NC1CCC(=O)C1 CLOXAWYNXXEWBT-UHFFFAOYSA-N 0.000 claims description 2
- HDIJZFORGDBEKL-UHFFFAOYSA-N 2,3,4-trimethylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(C)=C1C HDIJZFORGDBEKL-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229960003975 potassium Drugs 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- QENJZWZWAWWESF-UHFFFAOYSA-N tri-methylbenzoic acid Natural products CC1=CC(C)=C(C(O)=O)C=C1C QENJZWZWAWWESF-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 51
- 239000000741 silica gel Substances 0.000 description 34
- 229910002027 silica gel Inorganic materials 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 239000012043 crude product Substances 0.000 description 17
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 17
- 238000004896 high resolution mass spectrometry Methods 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- 150000000094 1,4-dioxanes Chemical class 0.000 description 16
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 14
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- -1 Biaryl compounds Chemical class 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- PFFWZSLJTAMXNU-WCWDXBQESA-N COC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)C)\N=N\C1=CC(=CC=C1)C Chemical compound COC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)C)\N=N\C1=CC(=CC=C1)C PFFWZSLJTAMXNU-WCWDXBQESA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- CZNGTXVOZOWWKM-UHFFFAOYSA-N methyl 4-bromobenzoate Chemical compound COC(=O)C1=CC=C(Br)C=C1 CZNGTXVOZOWWKM-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- HPSZIXYLILUGIP-FOCLMDBBSA-N CC=1C=C(C=CC=1)/N=N/C1=CC(=CC=C1)C Chemical compound CC=1C=C(C=CC=1)/N=N/C1=CC(=CC=C1)C HPSZIXYLILUGIP-FOCLMDBBSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 3
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 0 C*CC(C1)C1(C)NC Chemical compound C*CC(C1)C1(C)NC 0.000 description 3
- IAZJBPYVKVBVSI-FMQUCBEESA-N C1(=C(C=CC=C1)\N=N\C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=C(C=CC=C1)\N=N\C1=CC=CC=C1)C1=CC=CC=C1 IAZJBPYVKVBVSI-FMQUCBEESA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HPSZIXYLILUGIP-UHFFFAOYSA-N bis(3-methylphenyl)diazene Chemical compound CC1=CC=CC(N=NC=2C=C(C)C=CC=2)=C1 HPSZIXYLILUGIP-UHFFFAOYSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
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- ADVYOHUHSZKDLC-UHFFFAOYSA-N methyl 4-(2-amino-4-methylphenyl)benzoate Chemical compound COC(=O)C1=CC=C(C=C1)C1=C(C=C(C=C1)C)N ADVYOHUHSZKDLC-UHFFFAOYSA-N 0.000 description 2
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- 235000011056 potassium acetate Nutrition 0.000 description 2
- WFMNHCSATCWAAQ-UHFFFAOYSA-M potassium;2,2-dimethylpropanoate Chemical compound [K+].CC(C)(C)C([O-])=O WFMNHCSATCWAAQ-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- SJRDNQOIQZOVQD-UHFFFAOYSA-M sodium;2,2-dimethylpropanoate Chemical compound [Na+].CC(C)(C)C([O-])=O SJRDNQOIQZOVQD-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GVCIEWAYDUQTTQ-UHFFFAOYSA-J 1,2,3,4,5,6-hexamethylbenzene;ruthenium(2+);tetrachloride Chemical compound Cl[Ru]Cl.Cl[Ru]Cl.CC1=C(C)C(C)=C(C)C(C)=C1C.CC1=C(C)C(C)=C(C)C(C)=C1C GVCIEWAYDUQTTQ-UHFFFAOYSA-J 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- BKYWPNROPGQIFZ-UHFFFAOYSA-N 2,4-dimethylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(C)=C1 BKYWPNROPGQIFZ-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 1
- KNCHDRLWPAKSII-UHFFFAOYSA-N 5-ethyl-2-methylpyridine Natural products CCC1=CC=NC(C)=C1 KNCHDRLWPAKSII-UHFFFAOYSA-N 0.000 description 1
- KPZJCKOWXYFUTQ-FMQUCBEESA-N C(C)(C)C=1C=C(C=CC=1)\N=N\C1=CC(=CC=C1)C(C)C Chemical compound C(C)(C)C=1C=C(C=CC=1)\N=N\C1=CC(=CC=C1)C(C)C KPZJCKOWXYFUTQ-FMQUCBEESA-N 0.000 description 1
- ROSQHUWYUXRAHZ-ISLYRVAYSA-N C(C)C=1C=C(C=CC=1)\N=N\C1=CC(=CC=C1)CC Chemical compound C(C)C=1C=C(C=CC=1)\N=N\C1=CC(=CC=C1)CC ROSQHUWYUXRAHZ-ISLYRVAYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- YGXMUPKIEHNBNQ-UHFFFAOYSA-J benzene;ruthenium(2+);tetrachloride Chemical compound Cl[Ru]Cl.Cl[Ru]Cl.C1=CC=CC=C1.C1=CC=CC=C1 YGXMUPKIEHNBNQ-UHFFFAOYSA-J 0.000 description 1
- WNVWWDKUMKBZQV-UHFFFAOYSA-N bis(4-methylphenyl)diazene Chemical compound C1=CC(C)=CC=C1N=NC1=CC=C(C)C=C1 WNVWWDKUMKBZQV-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- XZIAFENWXIQIKR-UHFFFAOYSA-N ethyl 4-bromobenzoate Chemical compound CCOC(=O)C1=CC=C(Br)C=C1 XZIAFENWXIQIKR-UHFFFAOYSA-N 0.000 description 1
- 125000004672 ethylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- MMBKOHVRHFSAJP-UHFFFAOYSA-M lithium;2,2-dimethylpropanoate Chemical compound [Li+].CC(C)(C)C([O-])=O MMBKOHVRHFSAJP-UHFFFAOYSA-M 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/42—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitrogen-to-nitrogen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
-
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- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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Description
R1は、水素、ヒドロキシル、フッ素、塩素、C1−C4−アルキル、C1−C4−アルコキシ、C1−C4−アルキルチオまたはC1−C4−ハロアルキルであり、
X1は、水素、アルコキシ、アルカノイル、アルキルカルボキシレート、フッ素または塩素であり、
X2は、水素、アルコキシ、アルカノイル、アルキルカルボキシレート、フッ素または塩素であり、
X3は、水素、アルコキシ、アルカノイル、アルキルカルボキシレート、フッ素または塩素である。]の製造方法であって、
(1)第1段階で、
下記式(II)のアゾベンゼン類:
X1、X2およびX3は上記で定義の通りであり、
Halはヨウ素、臭素または塩素である。)と、ルテニウム触媒、活性化剤および塩基からなる触媒系の存在下に反応させ、
(2)第2段階で、そうして得られた式(IV)のアゾベンゼン類:
番号1から6および1′から6′は、表1に記載の化合物における、そして本明細書での式(IV)における位置に関連しての残基R1の位置を定義するものである。)を水素化して、式(I)のビフェニルアミン類を得ることを特徴とする方法を提供する。
R1は好ましくはトリフルオロメチルであり、トリフルオロメチルは好ましくは、個々の化合物の4′または5′位にあり、さらに好ましくは5′位にある。
R1は、好ましくはメトキシまたはメチルチオであり、好ましくは個々の化合物の4′、5′または6′位にあり、さらに好ましくは5′位にある。
ケトン、例えばアセトン、ジエチルケトン、メチルエチルケトンおよびメチルイソブチルケトン;
ニトリル類、例えばアセトニトリルおよびブチロニトリル;
エーテル類、例えばジメトキシエタン(DME)、テトラヒドロフラン(THF)、2−メチル−THFおよび1,4−ジオキサン;アルコール類、例えばn−プロパノール、イソプロパノール、tert−ブタノール、イソアミルアルコールまたはtert−アミルアルコール;
炭化水素およびハロゲン化炭化水素、例えばヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン、トルエン、オルト−キシレン、メタ−キシレン、パラ−キシレン、メシチレン、クロロベンゼン、オルト−ジクロロベンゼンまたはニトロベンゼン
などがある。
トルエンを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。収率は理論値の83%であった。
オルト−キシレンを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。収率は理論値の84%であった。
tert−アミルアルコールを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。収率は理論値の75%であった。
炭酸ナトリウムを炭酸カリウムに代えて塩基として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。収率は理論値の75%であった。
酢酸カリウムをMesCO2Hに代えて添加剤として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。収率は理論値の79%であった。
ピバリン酸をMesCO2Hに代えて添加剤として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。収率は理論値の76%であった。
N,N−ジメチルホルムアミドを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
N,N−ジメチルアセトアミドを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
メタノールを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
N−メチルピロリジノンを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
γ−バレロラクトンを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
ジメチルスルホキシドを1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
水を1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
酢酸を1,4−ジオキサンに代えて溶媒として用いたという点で異なる以外、実施例1について記載の方法に従って実験を行った。標的生成物は全く得られなかった。
Claims (14)
- 下記一般式(I)のビフェニルアミン類:
[式中、
R1は、水素、ヒドロキシル、フッ素、塩素、C1−C4−アルキル、C1−C4−アルコキシ、C1−C4−アルキルチオまたはC1−C4−ハロアルキルであり、
X1は、水素、アルコキシ、アルカノイル、アルキルカルボキシレート、フッ素または塩素であり、
X2は、水素、アルコキシ、アルカノイル、アルキルカルボキシレート、フッ素または塩素であり、
X3は、水素、アルコキシ、アルカノイル、アルキルカルボキシレート、フッ素または塩素である。]の製造方法であって、
第1段階で、
下記式(II)のアゾベンゼン類:
(R1は上記で定義の通りである。)を、下記式(III)の芳香族化合物:
(式中、
X1、X2およびX3はそれぞれ上記で定義の通りであり、
Halはヨウ素、臭素または塩素である。)と、ルテニウム触媒、カルボン酸である活性化剤および塩基からなる触媒系の存在下、およびケトン類、ニトリル類、エーテル類、炭化水素類およびハロゲン化炭化水素類および分岐アルコール類ならびにこれら溶媒の混合物を含む群から選択される溶媒の存在下に反応させ、
第2段階で、そうして得られた式(IV)のアゾベンゼン類:
(R1、X1、X2およびX3は上記で定義の通りである。)を水素化して、式(I)のビフェニルアミン類を得ることを特徴とする方法。 - 前記溶媒が、エーテル類、芳香族炭化水素類、塩素化芳香族炭化水素類および分岐アルコール類、またはこれら溶媒の混合物を含む群から選択される請求項1に記載の方法。
- 前記溶媒が、1,4−ジオキサン、トルエン、オルト−キシレン、メタ−キシレン、パラ−キシレンおよびこれら溶媒の混合物を含む群から選択される請求項1または2に記載の方法。
- 前記触媒が[{RuCl2(p−シメン)}2]である請求項1から3のいずれか1項に記載の方法。
- 前記活性化剤が、ギ酸、酢酸、プロピオン酸、ピバリン酸、安息香酸、2−メチル安息香酸、3−メチル安息香酸、4−メチル安息香酸、2,3−ジメチル安息香酸、2,4−ジメチル安息香酸、2,5−ジメチル安息香酸、2,6−ジメチル安息香酸、3,4−ジメチル安息香酸、3,5−ジメチル安息香酸、2,4,6−トリメチル安息香酸、2,3,4−トリメチル安息香酸、3,4,5−トリメチル安息香酸、2,3,5−トリメチル安息香酸、2,3,6−トリメチル安息香酸、フェニル酢酸、2−メチルフェニル酢酸、3−メチルフェニル酢酸、4−メチルフェニル酢酸、2,5−ジメチルフェニル酢酸、2,3,6−トリメチルフェニル酢酸、2,3,5,6−テトラメチルフェニル酢酸、2,3,4,6−テトラメチルフェニル酢酸、2−クロロフェニル酢酸、3−クロロフェニル酢酸、4−クロロフェニル酢酸および2,4−ジクロロフェニル酢酸からなる群から選択されるカルボン酸である請求項1から4のいずれか1項に記載の方法。
- 前記活性化剤が2,4,6−トリメチル安息香酸である請求項1から5のいずれか1項に記載の方法。
- 前記塩基が無機塩基である請求項1から6のいずれか1項に記載の方法。
- 前記塩基が、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸カルシウムおよび炭酸マグネシウムからなる群から選択される請求項1から7のいずれか1項に記載の方法。
- 前記塩基が炭酸カリウムである請求項1から8のいずれか1項に記載の方法。
- 前記活性化剤を、式(III)の芳香族化合物に対して0.1から100モルパーセントの量で使用する請求項1から9のいずれか1項に記載の方法。
- 前記ルテニウム触媒を、式(III)の芳香族化合物に対して1から20モルパーセントの量で使用する請求項1から10のいずれか1項に記載の方法。
- 式(II)のアゾベンゼンの式(III)のハロ芳香族化合物に対するモル比が1:0.4から1である請求項1から11のいずれか1項に記載の方法。
- 式(II)のアゾベンゼンの式(III)のハロ芳香族化合物に対するモル比が1:0.45から0.9である請求項1から12のいずれか1項に記載の方法。
- 前記溶媒が1,4−ジオキサンであり、前記活性化剤が2,4,6−トリメチル安息香酸であり、前記式(III)の芳香族化合物が臭素化芳香族化合物であり、前記塩基が炭酸カリウムであり、前記触媒が[{RuCl2(p−シメン)}2]である請求項1から13のいずれか1項に記載の方法。
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