JP6070079B2 - Method for producing hindered phenol - Google Patents
Method for producing hindered phenol Download PDFInfo
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- JP6070079B2 JP6070079B2 JP2012242718A JP2012242718A JP6070079B2 JP 6070079 B2 JP6070079 B2 JP 6070079B2 JP 2012242718 A JP2012242718 A JP 2012242718A JP 2012242718 A JP2012242718 A JP 2012242718A JP 6070079 B2 JP6070079 B2 JP 6070079B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 54
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 107
- 125000004432 carbon atom Chemical group C* 0.000 claims description 71
- 239000002253 acid Substances 0.000 claims description 58
- -1 naphthalene-2,6-diyl group Chemical group 0.000 claims description 53
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 32
- 125000001153 fluoro group Chemical group F* 0.000 claims description 30
- 125000002947 alkylene group Chemical group 0.000 claims description 29
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 11
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 5
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 239000002815 homogeneous catalyst Substances 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 43
- 229910052741 iridium Inorganic materials 0.000 description 35
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 239000004973 liquid crystal related substance Substances 0.000 description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000003638 chemical reducing agent Substances 0.000 description 16
- 239000012535 impurity Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 235000011054 acetic acid Nutrition 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 13
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 12
- 239000011591 potassium Substances 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 10
- 235000019253 formic acid Nutrition 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000012267 brine Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 239000010948 rhodium Substances 0.000 description 8
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 6
- YLSZOZPQTCFBIR-UHFFFAOYSA-J tetrabromopalladium Chemical compound Br[Pd](Br)(Br)Br YLSZOZPQTCFBIR-UHFFFAOYSA-J 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 4
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 4
- 229940106681 chloroacetic acid Drugs 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 229960005215 dichloroacetic acid Drugs 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229910003445 palladium oxide Inorganic materials 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 4
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- 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 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 4
- 229960004319 trichloroacetic acid Drugs 0.000 description 4
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 4
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- 239000012046 mixed solvent Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
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- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- PENAXHPKEVTBLF-UHFFFAOYSA-L palladium(2+);prop-1-ene;dichloride Chemical compound [Pd+]Cl.[Pd+]Cl.[CH2-]C=C.[CH2-]C=C PENAXHPKEVTBLF-UHFFFAOYSA-L 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- TWIRRPLUAGEFNJ-UHFFFAOYSA-L palladium(2+);sulfate;dihydrate Chemical compound O.O.[Pd+2].[O-]S([O-])(=O)=O TWIRRPLUAGEFNJ-UHFFFAOYSA-L 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- XAFJSPPHVXDRIE-UHFFFAOYSA-L platinum(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Pt+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XAFJSPPHVXDRIE-UHFFFAOYSA-L 0.000 description 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- ZKDAHTCWUNDJGF-UHFFFAOYSA-N potassium iridium(3+) Chemical compound [K+].[Ir+3] ZKDAHTCWUNDJGF-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- BTZFRWBQBSCKGO-UHFFFAOYSA-L rhodium(2+);dibenzoate Chemical compound [Rh+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 BTZFRWBQBSCKGO-UHFFFAOYSA-L 0.000 description 1
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- CDPPVBDJYWOMMV-UHFFFAOYSA-K rhodium(3+);phosphate Chemical compound [Rh+3].[O-]P([O-])([O-])=O CDPPVBDJYWOMMV-UHFFFAOYSA-K 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- FQSDTIQFGVAWNS-UHFFFAOYSA-N rhodium;(triphenyl-$l^{5}-phosphanylidene)methanone Chemical compound [Rh].C=1C=CC=CC=1P(C=1C=CC=CC=1)(=C=O)C1=CC=CC=C1 FQSDTIQFGVAWNS-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- RXFATFKBDIQXLS-UHFFFAOYSA-N ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RXFATFKBDIQXLS-UHFFFAOYSA-N 0.000 description 1
- OIWNHEPSSHYXTG-UHFFFAOYSA-L ruthenium(2+);triphenylphosphane;dichloride Chemical compound Cl[Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OIWNHEPSSHYXTG-UHFFFAOYSA-L 0.000 description 1
- PMMMCGISKBNZES-UHFFFAOYSA-K ruthenium(3+);tribromide;hydrate Chemical compound O.Br[Ru](Br)Br PMMMCGISKBNZES-UHFFFAOYSA-K 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- UIEKGNOQMSLELJ-UHFFFAOYSA-N sodium ruthenium(6+) Chemical compound [Ru+6].[Na+] UIEKGNOQMSLELJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MIIRGGNUGGPNST-UHFFFAOYSA-N sodium;gold(1+) Chemical compound [Na+].[Au+] MIIRGGNUGGPNST-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- CXYONDPKSOUOGE-UHFFFAOYSA-N sulfuric acid;trifluoromethanesulfonic acid Chemical compound OS(O)(=O)=O.OS(=O)(=O)C(F)(F)F CXYONDPKSOUOGE-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KBXXFKPVKJZGJG-UHFFFAOYSA-K tribromoiridium;hydrate Chemical compound O.Br[Ir](Br)Br KBXXFKPVKJZGJG-UHFFFAOYSA-K 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はヒンダードフェノール骨格を有する化合物の製造法、当該製造法により得られた化合物から製造される化合物、当該製造法により得られた化合物を含有する組成物及び当該組成物を用いた樹脂、オイル、オイルフィルター、油脂、インキ、医薬品、化粧品、洗剤、液晶材料、農薬、ポリマー、樹脂、顔料、染料、粘着剤接着剤、印刷物、食品、光学異方体、表示素子又は電子デバイスに関する。 The present invention relates to a method for producing a compound having a hindered phenol skeleton, a compound produced from the compound obtained by the production method, a composition containing the compound obtained by the production method, and a resin using the composition, The present invention relates to oils, oil filters, oils and fats, inks, pharmaceuticals, cosmetics, detergents, liquid crystal materials, agricultural chemicals, polymers, resins, pigments, dyes, adhesive adhesives, printed materials, foods, optical anisotropic bodies, display elements, and electronic devices.
TFT液晶材料に使用される液晶化合物及び添加剤は、ディスプレイに焼き付きを引き起こす不純物を含有しないことは元より、なるべく高純度であることが好ましいとされている。 The liquid crystal compounds and additives used in the TFT liquid crystal material are preferably as pure as possible from the viewpoint of not containing impurities that cause image sticking to the display.
TFT液晶表示素子の種類の一つであるPSA(Polymer Sustained Alignment)型液晶表示素子は、セル内にプレチルト角を制御するためのポリマー構造を有しており、高コントラスト表示及び高速応答が可能である。この素子は、重合性化合物を添加した液晶組成物をセル内に注入し、電圧を印加した状態でUV照射を行い、重合性化合物を重合させることによって作製される。従って、この素子に使用される液晶化合物及び添加剤には、特にUV照射によってパネルに焼き付き等の悪影響を及ぼす不純物を含有しないことが求められる。 A PSA (Polymer Sustained Alignment) type liquid crystal display element, which is one of the types of TFT liquid crystal display elements, has a polymer structure for controlling the pretilt angle in the cell, enabling high-contrast display and high-speed response. is there. This device is produced by injecting a liquid crystal composition to which a polymerizable compound is added into a cell, and performing UV irradiation in a state where a voltage is applied to polymerize the polymerizable compound. Therefore, it is required that the liquid crystal compound and the additive used in this element do not contain impurities that adversely affect the panel, particularly by UV irradiation.
通常、TFT液晶材料の劣化を防止する目的で、酸化防止剤が液晶材料に添加されている。当該酸化防止剤として、製造が容易で、液晶組成物への相溶性が高く、液晶の配向性に悪影響を及ぼさないといった理由から、アルキレン基を有するフェノール誘導体がしばしば利用される(特許文献1〜2)。 Usually, for the purpose of preventing the deterioration of the TFT liquid crystal material, an antioxidant is added to the liquid crystal material. As the antioxidant, phenol derivatives having an alkylene group are often used because they are easy to produce, have high compatibility with liquid crystal compositions, and do not adversely affect the alignment of liquid crystals (Patent Documents 1 to 3). 2).
このアルキレン基を有するフェノール誘導体の製造方法としては、対応するカルボニルアルキレン基を有するフェノール誘導体中に存在するカルボニル基を、接触水素化により還元する方法が知られている(非特許文献1)。しかしながらこの方法を用いると、カルボニル基の還元と同時に芳香環の核還元が進行し種々の核還元体を生じてしまうため、高品質の目的物を収率良く得ることは困難であった。この問題を解決するために、カルボニルアルキレン基を有するフェノール誘導体中に存在するカルボニル基をヒドロキシル基へと予め還元した後、接触水素化により還元する段階的合成法が報告されている(特許文献3)。この方法によると、種々の核還元体のうちシクロヘキサノール体の副生成を大幅に抑制することが可能である。しかしながら、カルボニル基をヒドロキシル基へと予め還元した後に、後処理・精製工程が必要となることから、工程数が多くなり、好ましくなかった。また、フェノール芳香環上に嵩高い基を有するヒンダードフェノールに適用した場合、副生成する種々の核還元体のうちシクロヘキサノール構造を有する核還元体の生成を抑制することは可能であるものの、シクロヘキサノン構造を有する核還元体の生成を抑制することは困難であった。 As a method for producing a phenol derivative having an alkylene group, a method is known in which a carbonyl group present in a corresponding phenol derivative having a carbonylalkylene group is reduced by catalytic hydrogenation (Non-patent Document 1). However, when this method is used, since the nuclear reduction of the aromatic ring proceeds simultaneously with the reduction of the carbonyl group to produce various nuclear reductants, it has been difficult to obtain a high-quality target product in good yield. In order to solve this problem, a stepwise synthesis method in which a carbonyl group present in a phenol derivative having a carbonylalkylene group is previously reduced to a hydroxyl group and then reduced by catalytic hydrogenation has been reported (Patent Document 3). ). According to this method, it is possible to significantly suppress the by-production of cyclohexanol form among various nuclear reductants. However, since a post-treatment / purification step is required after the carbonyl group is reduced to a hydroxyl group in advance, the number of steps increases, which is not preferable. In addition, when applied to hindered phenol having a bulky group on the phenol aromatic ring, although it is possible to suppress the production of a nuclear reductant having a cyclohexanol structure among various by-product nuclear reductants, It was difficult to suppress the production of a nuclear reductant having a cyclohexanone structure.
そのため、TFT液晶材料等の特に高純度の化合物が要求される分野においては、ヒンダードフェノールに連結したカルボニル基の還元工程において、接触水素化反応が用いられることは無く、クレメンゼン還元又はヒドリド還元が用いられてきた(非特許文献1〜3)。この方法をヒンダードフェノールの製造に採用すると、従来型のTFT液晶材料用途での酸化防止剤としては十分に高品質の酸化防止効果が得られた。一方、前述の通り、接触水素化還元を用いると、ヒンダードフェノール部位の芳香環が核還元された除去困難な副生成物が生じてしまい最終的に得られる化合物の純度が低下してしまうため、当該用途に使用することはできなかった。 Therefore, in a field where a particularly high purity compound such as a TFT liquid crystal material is required, the catalytic hydrogenation reaction is not used in the reduction process of the carbonyl group linked to the hindered phenol, and the Clementen reduction or hydride reduction is not performed. Have been used (Non-Patent Documents 1 to 3). When this method was employed for the production of hindered phenol, a sufficiently high quality antioxidant effect was obtained as an antioxidant for conventional TFT liquid crystal material applications. On the other hand, as described above, when catalytic hydrogenation reduction is used, the aromatic ring at the hindered phenol moiety is reduced by a nucleus, resulting in a by-product that is difficult to remove and the purity of the compound finally obtained is lowered. , Could not be used for this purpose.
しかしながら、PSA型表示素子用液晶材料に対し、クレメンゼン還元又はヒドリド還元によって製造したヒンダードフェノールを添加すると、製造後のパネルが焼き付きを起こしやすいといった問題があった。これは、この還元方法によって製造したヒンダードフェノールに含まれていた極微量の不純物が、パネル製造の際のUV照射工程において、焼き付きに悪影響を及ぼす物質に変質したためであると推定された。 However, when a hindered phenol produced by Clementen reduction or hydride reduction is added to a liquid crystal material for a PSA type display device, there is a problem that the panel after production tends to be burned. This was presumed to be because an extremely small amount of impurities contained in the hindered phenol produced by this reduction method was transformed into a substance that adversely affects image sticking in the UV irradiation process during panel production.
以上の反応経路の他に、アルキレン基を有するヒンダードフェノールの公知の製造方法として、アルキレン基を有するフェノールに、硫酸又はルイス酸存在下、tert−ブチルアルコール、tert−ブチルクロリド又はイソブテンを反応させる方法(特許文献1、非特許文献5)が知られていた。しかしながら、これらの反応経路では反応時間が長時間掛かってしまったり、ガスを反応液中に吹き込むため特殊な設備が必要であったりする問題があった。また、ベンゾキノンを原料とする方法(特許文献4)が知られていたが、原料の合成が煩雑であったりする問題があった。 In addition to the above reaction route, as a known production method of hindered phenol having an alkylene group, tert-butyl alcohol, tert-butyl chloride or isobutene is reacted with phenol having an alkylene group in the presence of sulfuric acid or Lewis acid. Methods (Patent Document 1, Non-Patent Document 5) have been known. However, these reaction paths have a problem that it takes a long time to react and a special facility is required for blowing gas into the reaction solution. Moreover, although the method (patent document 4) which uses benzoquinone as a raw material was known, there existed a problem that the synthesis | combination of a raw material was complicated.
以上のことから、焼き付きに悪影響を及ぼすような不純物を含有しないアルキレン基を有するヒンダードフェノールの製造方法の開発が求められていた。 From the above, development of a method for producing a hindered phenol having an alkylene group not containing impurities that adversely affect image sticking has been demanded.
本願発明が解決しようとする課題は、高品質なヒンダードフェノールの製造方法及び、当該製造方法により得られる化合物を提供することである。 The problem to be solved by the present invention is to provide a method for producing a high-quality hindered phenol and a compound obtained by the production method.
少なくとも一つのカルボニル基及び少なくとも一つのヒンダードフェノール基を有する化合物(A)の一つ又は複数のカルボニル基を、接触水素化還元によってメチレン基へと変換することによる、少なくとも一つのメチレン基及び少なくとも一つのヒンダードフェノール基を有する化合物(B)の製造方法及び、当該製造方法により得られる化合物を提供し、更に当該化合物を中間体とする化合物並びに、当該化合物を使用した組成物を提供する。 At least one methylene group and at least one by converting one or more carbonyl groups of compound (A) having at least one carbonyl group and at least one hindered phenol group to a methylene group by catalytic hydrogenation reduction. Provided are a method for producing a compound (B) having one hindered phenol group, a compound obtained by the production method, a compound having the compound as an intermediate, and a composition using the compound.
本願発明の製造方法により製造されるヒンダードフェノール骨格を有する化合物は、液晶材料等の組成物に添加した場合に、組成物の変質防止効果が高いことから、種々の組成物の構成部材として有用である。また、本願発明の製造方法により製造される化合物を含有する組成物は樹脂、オイル、オイルフィルター、油脂、インキ、医薬品、化粧品、洗剤、液晶材料、農薬、ポリマー、樹脂、顔料、染料、粘着剤接着剤、印刷物、食品、光学異方体、表示素子又は電子デバイスの用途に有用である。 A compound having a hindered phenol skeleton produced by the production method of the present invention is useful as a constituent member of various compositions because it has a high effect of preventing deterioration of the composition when added to a composition such as a liquid crystal material. It is. The composition containing the compound produced by the production method of the present invention is a resin, oil, oil filter, oil, fat, ink, pharmaceutical, cosmetics, detergent, liquid crystal material, agricultural chemical, polymer, resin, pigment, dye, adhesive. It is useful for applications such as adhesives, printed materials, foods, optical anisotropic bodies, display elements or electronic devices.
少なくとも一つのカルボニル基及び少なくとも一つのヒンダードフェノール骨格を有する化合物(A)の一つ又は複数のカルボニル基を、接触水素化還元によってメチレン基へと変換する化合物(B)の製造方法を提供する。但し、ヒンダードフェノールとは、フェノール芳香環上の水素原子が嵩高い置換基により置換された化合物のことを表す。また、そのような構造をヒンダードフェノール骨格と表す。 Provided is a method for producing a compound (B) in which one or more carbonyl groups of the compound (A) having at least one carbonyl group and at least one hindered phenol skeleton are converted into methylene groups by catalytic hydrogenation reduction. . However, the hindered phenol represents a compound in which a hydrogen atom on the phenol aromatic ring is substituted with a bulky substituent. Such a structure is represented as a hindered phenol skeleton.
これらの実施形態において、化合物(A)が、ヒンダードフェノール骨格に直接結合した少なくとも一つのカルボニル基を有することが好ましく、触媒として均一系触媒又は不均一系触媒を用いることが好ましく、水素圧が10MPa以下であることが好ましく、反応温度が−100℃から200℃であることが好ましい。 In these embodiments, the compound (A) preferably has at least one carbonyl group directly bonded to the hindered phenol skeleton, preferably a homogeneous catalyst or a heterogeneous catalyst is used as the catalyst, and the hydrogen pressure is The pressure is preferably 10 MPa or less, and the reaction temperature is preferably −100 ° C. to 200 ° C.
さらに、化合物(A)は、下記一般式(I)で表される化合物であることが好ましい。 Furthermore, the compound (A) is preferably a compound represented by the following general formula (I).
(式中、Gは4価の有機基を表し、Rは下記一般式(II) (In the formula, G represents a tetravalent organic group, and R represents the following general formula (II).
(式中、Y1及びY2は各々独立して、水素原子、炭素原子数1から18のアルキル基、炭素原子数1から18のアルコキシ基又は炭素原子数1から18のアルカノイル基を表し、Spは1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−S−、−CO−、−COO−、−OCO−、−CO−S−、−S−CO−、−O−CO−O−、−CO−NH−、−NH−CO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)又は−C≡C−で置換されても良い炭素原子数1から20のアルキレン基又は単結合を表し、Xは各々独立して−O−、−S−、−OCH2−、−CH2O−、−CO−、−COO−、−OCO−、−CO−S−、−S−CO−、−O−CO−O−、−CO−NH−、−NH−CO−、−SCH2−、−CH2S−、−CF2O−、−OCF2−、−CF2S−、−SCF2−、−CH2CF2−、−CF2CH2−、−CF2CF2−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−COO−CH2−、−OCO−CH2−、−CH2−COO−、−CH2−OCO−、−CY11=CY11−(式中、Y11は各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)、−C≡C−又は単結合を表し、Aは各々独立して1,4−フェニレン基、ナフタレン−2,6−ジイル基、1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基、1,4−ビシクロ[2.2.2]オクチレン基、デカヒドロナフタレン−2,6−ジイル基、1,2,3,4−テトラヒドロナフタレン−2,6−ジイル基、ピリジン−2,6−ジイル基、ピリミジン−2,5−ジイル基、1,3−ジオキサン−2,5−ジイル基を表すが、これらの基は無置換であるか又は、各々独立してハロゲン、シアノ基、ニトロ基、ペンタフルオロスルフラニル基又は炭素原子数1から10のアルキル基によって置換されていても良いが、このアルキル基は各々独立して1個以上の水素原子がフッ素原子又は塩素原子により置き換えられても良く、このアルキル基上の1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−S−、−CO−、−COO−、−OCO−、−CO−S−、−S−CO−、−O−CO−O−、−CO−NH−、−NH−CO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)又は−C≡C−に置換されても良く、Zは各々独立して−O−、−S−、−OCH2−、−CH2O−、−CO−、−COO−、−OCO−、−CO−S−、−S−CO−、−O−CO−O−、−CO−NH−、−NH−CO−、−SCH2−、−CH2S−、−CF2O−、−OCF2−、−CF2S−、−SCF2−、−CH2CF2−、−CF2CH2−、−CF2CF2−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−COO−CH2−、−OCO−CH2−、−CH2−COO−、−CH2−OCO−、−CY12=CY12−(式中、Y12は各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)、−C≡C−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−S−、−CO−、−COO−、−OCO−、−CO−S−、−S−CO−、−O−CO−O−、−CO−NH−、−NH−CO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−CY13=CY13−(式中、Y13は各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)又は−C≡C−で置換されても良い炭素原子数1から20のアルキレン基又は単結合を表し、nは0から5の整数を表すが、Aが複数存在する場合にはそれらは同一であっても異なっていてもよく、Zが複数存在する場合にはそれらは同一であっても異なっていてもよい。)を表し、mは1から4の整数を表し、Rが複数存在する場合にはそれらは同一であっても異なっていてもよい。)で表される。 Wherein Y 1 and Y 2 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkanoyl group having 1 to 18 carbon atoms, Sp represents one —CH 2 — or two or more non-adjacent —CH 2 — each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—. S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CY = CY- (wherein Y independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group). ) Or an alkylene group having 1 to 20 carbon atoms which may be substituted with —C≡C— or a single bond , - - -O and, X is each independently S -, - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO- , —O—CO—O—, —CO—NH—, —NH—CO—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, — SCF 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, -OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CY 11 = CY 11 - ( wherein, Y 1 are each independently hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group), -. C≡C- or a single bond, A is each independently 1 , 4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, decahydronaphthalene -2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5-diyl group, 1,3-dioxane- 2,5-diyl group, these groups are unsubstituted or each independently by a halogen, a cyano group, a nitro group, a pentafluorosulfuranyl group or an alkyl group having 1 to 10 carbon atoms Even if it is replaced The alkyl groups may each independently have one or more hydrogen atoms replaced by fluorine or chlorine atoms, one —CH 2 — or two or more non-adjacent ones on the alkyl group. Each of —CH 2 — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CY = CY- ( In the formula, each Y independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group. ) Or —C≡C—, and each Z is independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—. , -CO-S -, - S -CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O-, -OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CY 12 = CY 12 - (wherein, Y 12 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group.), - C≡C-, 1 piece —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, — S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, — OCO—CH═CH—, —CY 13 = CY 13 — (wherein Y 13 independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, or a cyano group). Or an alkylene group having 1 to 20 carbon atoms which may be substituted with -C≡C- or a single bond; Represents an integer of 0 to 5, but when a plurality of A are present, they may be the same or different, and when a plurality of Z are present, they may be the same or different. Good. M represents an integer of 1 to 4, and when a plurality of Rs are present, they may be the same or different. ).
さらに、化合物(B)は、下記一般式(III)で表される化合物であることが好ましい。 Furthermore, the compound (B) is preferably a compound represented by the following general formula (III).
(式中、G及びmは一般式(I)と同様の意味を表し、R’は下記一般式(IV) Wherein G and m represent the same meaning as in general formula (I), and R ′ represents the following general formula (IV)
(式中、Y1、Y2、Sp、X、A、Z及びnは一般式(II)と同一の意味を表すが、これらの基が一般式(II)において−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−CY=CY−、−CY11=CY11−、−CY12=CY12−、−CY13=CY13−(式中、Y、Y11、Y12、Y13は各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)又は−C≡C−を表す場合、一般式(IV)において各々−CH2−CH2−COO−、−CH2−CH2−OCO−、−COO−CH2−CH2−、−OCO−CH2−CH2−、−CHY−CHY−、−CHY11−CHY11−、−CHY12−CHY12−、−CHY13−CHY13−又は−CH2−CH2−を表す。)を表す。)
さらに一般式(I)及び一般式(II)で表される化合物は液晶組成物とした際に、他の成分との相溶性の観点から、Y1及びY2は各々独立して、水素原子、炭素原子数1から18のアルキル基又は炭素原子数1から18のアルコキシ基である場合が好ましく、各々独立して、水素原子、炭素原子数1から8のアルキル基又は炭素原子数1から8のアルコキシ基である場合がより好ましく、Y1及びY2のうち一方が水素原子を表し、他方が水素原子、炭素原子数1から8のアルキル基又は炭素原子数1から8のアルコキシ基である場合がさらに好ましく、Y1及びY2がtert−ブチル基である場合が特に好ましく、Spは1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合が好ましく、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がより好ましく、炭素原子数1から20のアルキレン基又は単結合である場合がさらに好ましく、炭素原子数1から10のアルキレン基又は単結合である場合がさらにより好ましく、炭素原子数1から5のアルキレン基又は単結合である場合がさらにより好ましく、炭素原子数1から5のアルキレン基である場合が特に好ましく、Xは各々独立して−O−、−OCH2−、−CH2O−、−COO−、−OCO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)、−C≡C−又は単結合である場合が好ましく、各々独立して−O−、−COO−、−OCO−又は単結合である場合がより好ましく、各々独立して−O−又は単結合である場合がさらにより好ましく、各々独立して単結合である場合が特に好ましく、Aは各々独立して無置換若しくは、各々独立してハロゲン又は各々独立して1個以上の水素原子がフッ素原子又は塩素原子により置き換えられても良く、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−に置換されても良い炭素原子数1から10のアルキル基によって置換されても良い1,4−フェニレン基、ナフタレン−2,6−ジイル基、1,4−シクロヘキシレン基、1,3−ジオキサン−2,5−ジイル基である場合が好ましく、各々独立して無置換若しくは、各々独立してフッ素原子又は塩素原子若しくは、各々独立して1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−に置換されても良い炭素原子数1から10のアルキル基によって置換されても良い1,4−フェニレン基、ナフタレン−2,6−ジイル基、1,4−シクロヘキシレン基、1,3−ジオキサン−2,5−ジイル基である場合がより好ましく、各々独立して無置換若しくは、各々独立してフッ素原子若しくは、各々独立して1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−に置換されても良い炭素原子数1から5のアルキル基によって置換されても良い1,4−フェニレン基又は1,4−シクロヘキシレン基である場合がさらに好ましく、各々独立して無置換若しくは、各々独立してフッ素原子、メチル基、エチル基又はメトキシ基によって置換されても良い1,4−フェニレン基又は1,4−シクロヘキシレン基である場合がさらにより好ましく、各々独立して無置換若しくは、各々独立してフッ素原子、メチル基又はメトキシ基によって置換されても良い1,4−フェニレン基又は無置換の1,4−シクロヘキシレン基である場合が特に好ましく、Zは各々独立して−O−、−OCH2−、−CH2O−、−COO−、−OCO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)、−C≡C−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−S−、−CO−、−COO−、−OCO−、−CO−S−、−S−CO−、−O−CO−O−、−CO−NH−、−NH−CO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)又は−C≡C−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合が好ましく、各々独立して−OCH2−、−CH2O−、−COO−、−OCO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から4のアルキル基又はフッ素原子を表す。)、−C≡C−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がより好ましく、各々独立して−OCH2−、−CH2O−、−COO−、−OCO−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がさらに好ましく、各々独立して−COO−、−OCO−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がさらにより好ましく、各々独立して−COO−、−OCO−又は単結合である場合が特に好ましく、nは0から3の整数である場合が好ましく、0から2の整数である場合がより好ましく、0又は1である場合がさらに好ましく、0である場合が特に好ましく、mは1から4の整数である場合が好ましく、1、2又は4である場合がより好ましく、1又は2である場合が特に好ましい。
(Wherein Y 1 , Y 2 , Sp, X, A, Z and n represent the same meaning as in general formula (II), but these groups are —CH═CH—COO— in general formula (II)). , -CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - CY = CY -, - CY 11 = CY 11 -, - CY 12 = CY 12 -, - CY 13 = CY 13 - (. wherein, Y, Y 11, Y 12 , Y 13 each independently represent a hydrogen atom, an alkyl group having from 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group), or - when referring to C≡C-, each in the general formula (IV) -CH 2 -CH 2 -COO -, - CH 2 -CH 2 -OCO -, - COO-CH 2 -CH 2 -, - OCO-CH 2 -CH 2 -, - CHY-CHY -, - CHY 11 -CHY 11 , -CHY 12 -CHY 12 -, - CHY 13 -CHY 13 - or -CH 2 -CH 2 -. Representing a) represents a. )
Furthermore, when the compound represented by the general formula (I) and the general formula (II) is a liquid crystal composition, Y 1 and Y 2 are each independently a hydrogen atom from the viewpoint of compatibility with other components. And preferably an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. More preferably, one of Y 1 and Y 2 represents a hydrogen atom, and the other is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. More preferably, Y 1 and Y 2 are particularly preferably a tert-butyl group, and Sp represents one —CH 2 — or two or more non-adjacent —CH 2 — independently. O-, -COO- or -O Preferred is an alkylene group having 1 to 20 carbon atoms which may be substituted with CO-, or a single bond, and one —CH 2 — or two or more non-adjacent —CH 2 — are each independently More preferably an alkylene group having 1 to 20 carbon atoms which may be substituted with —O— or a single bond, more preferably an alkylene group having 1 to 20 carbon atoms or a single bond, More preferably, it is an alkylene group having 1 to 10 carbon atoms or a single bond, more preferably an alkylene group having 1 to 5 carbon atoms or a single bond, and an alkylene group having 1 to 5 carbon atoms. Are particularly preferred, and each X independently represents —O—, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CH═CH—COO—, —CH═CH—OCO—, — C O-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- , -CY = CY- (wherein Y independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group), -C≡C- or a single bond Are preferably each independently -O-, -COO-, -OCO- or a single bond, more preferably each independently -O- or a single bond, Particularly preferably, they are independently a single bond, and each A is independently unsubstituted, or each independently halogen, or each independently one or more hydrogen atoms may be replaced by a fluorine atom or a chlorine atom. One —CH 2 — or Two or more non-adjacent —CH 2 — may be each independently substituted with an alkyl group having 1 to 10 carbon atoms which may be substituted with —O—, —COO— or —OCO—. , 4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, preferably each independently unsubstituted or Independently a fluorine atom or a chlorine atom, or each independently one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —COO— or —OCO—. 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,3-dioxane which may be substituted with an alkyl group having 1 to 10 carbon atoms which may be substituted with -2,5-jii More preferably is a group, each independently unsubstituted or fluorine atom or each independently, each independently one -CH 2 - or nonadjacent two or more -CH 2 - are each More preferably, it is a 1,4-phenylene group or a 1,4-cyclohexylene group which may be independently substituted with an alkyl group having 1 to 5 carbon atoms which may be independently substituted with —O—, and each independently More preferably, it is unsubstituted or is a 1,4-phenylene group or a 1,4-cyclohexylene group, each of which may be independently substituted by a fluorine atom, a methyl group, an ethyl group or a methoxy group, Independently unsubstituted, each independently 1,4-phenylene group which may be substituted with a fluorine atom, methyl group or methoxy group or unsubstituted 1,4-cyclohexyl Particularly preferred is when it is alkylene group, Z is each independently -O -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CH = CH-COO -, - CH = CH -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 —OCO—, —CY═CY— (wherein Y independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group). ), —C≡C—, one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, — OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO- , -COO-CH = CH-, -OCO-CH = CH-, -CY = CY- (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) Or a cyano group) or an alkylene group having 1 to 20 carbon atoms which may be substituted with —C≡C— or a single bond is preferable, and each independently represents —OCH 2 — or —CH 2 O. -, -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = C -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CY = CY -(Wherein each Y independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine atom), -C≡C-, one -CH 2 -or not adjacent 2 It is more preferable that two or more —CH 2 — are each independently an alkylene group having 1 to 20 carbon atoms which may be substituted with —O—, —COO— or —OCO—, or a single bond. -OCH 2 and -, - CH 2 O -, - COO -, - OCO-, 1 single -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O-, Alkyl having 1 to 20 carbon atoms which may be substituted with -COO- or -OCO- More preferably represents emission group or a single bond, each independently -COO -, - OCO-, 1 single -CH 2 - or nonadjacent two or more -CH 2 - are each independently - Even more preferable is an alkylene group having 1 to 20 carbon atoms which may be substituted with O- or a single bond, particularly preferably each independently -COO-, -OCO- or a single bond, n Is preferably an integer from 0 to 3, more preferably an integer from 0 to 2, more preferably 0 or 1, particularly preferably 0, and m is an integer from 1 to 4. Some cases are preferred, one, two or four are more preferred, and one or two are particularly preferred.
さらに一般式(III)及び一般式(IV)で表される化合物は液晶組成物とした際に、他の成分との相溶性の観点から、Y1及びY2は各々独立して、水素原子、炭素原子数1から18のアルキル基又は炭素原子数1から18のアルコキシ基である場合が好ましく、各々独立して、水素原子、炭素原子数1から8のアルキル基又は炭素原子数1から8のアルコキシ基である場合がより好ましく、Y1及びY2のうち一方が水素原子を表し、他方が水素原子、炭素原子数1から8のアルキル基又は炭素原子数1から8のアルコキシ基である場合がさらに好ましく、Y1及びY2がtert−ブチル基である場合が特に好ましく、Spは1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合が好ましく、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がより好ましく、炭素原子数1から20のアルキレン基又は単結合である場合がさらに好ましく、炭素原子数1から10のアルキレン基又は単結合である場合がさらにより好ましく、炭素原子数1から5のアルキレン基又は単結合である場合がさらにより好ましく、炭素原子数1から5のアルキレン基である場合が特に好ましく、Xは各々独立して−O−、−OCH2−、−CH2O−、−COO−、−OCO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)、−C≡C−又は単結合である場合が好ましく、各々独立して−O−、−COO−、−OCO−又は単結合である場合がより好ましく、各々独立して−O−又は単結合である場合がさらにより好ましく、各々独立して単結合である場合が特に好ましく、Aは各々独立して無置換若しくは、各々独立してハロゲン又は各々独立して1個以上の水素原子がフッ素原子又は塩素原子により置き換えられても良く、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−に置換されても良い炭素原子数1から10のアルキル基によって置換されても良い1,4−フェニレン基、ナフタレン−2,6−ジイル基、1,4−シクロヘキシレン基、1,3−ジオキサン−2,5−ジイル基である場合が好ましく、各々独立して無置換若しくは、各々独立してフッ素原子又は塩素原子若しくは、各々独立して1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−に置換されても良い炭素原子数1から10のアルキル基によって置換されても良い1,4−フェニレン基、ナフタレン−2,6−ジイル基、1,4−シクロヘキシレン基、1,3−ジオキサン−2,5−ジイル基である場合がより好ましく、各々独立して無置換若しくは、各々独立してフッ素原子若しくは、各々独立して1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−に置換されても良い炭素原子数1から5のアルキル基によって置換されても良い1,4−フェニレン基又は1,4−シクロヘキシレン基である場合がさらに好ましく、各々独立して無置換若しくは、各々独立してフッ素原子、メチル基、エチル基又はメトキシ基によって置換されても良い1,4−フェニレン基又は1,4−シクロヘキシレン基である場合がさらにより好ましく、各々独立して無置換若しくは、各々独立してフッ素原子、メチル基又はメトキシ基によって置換されても良い1,4−フェニレン基又は無置換の1,4−シクロヘキシレン基である場合が特に好ましく、Zは各々独立して−O−、−OCH2−、−CH2O−、−COO−、−OCO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)、−C≡C−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−S−、−CO−、−COO−、−OCO−、−CO−S−、−S−CO−、−O−CO−O−、−CO−NH−、−NH−CO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から12のアルキル基、フッ素原子、塩素原子又はシアノ基を表す。)又は−C≡C−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合が好ましく、各々独立して−OCH2−、−CH2O−、−COO−、−OCO−、−CH=CH−COO−、−CH=CH−OCO−、−COO−CH=CH−、−OCO−CH=CH−、−COO−CH2CH2−、−OCO−CH2CH2−、−CH2CH2−COO−、−CH2CH2−OCO−、−CY=CY−(式中、Yは各々独立して水素原子、炭素原子数1から4のアルキル基又はフッ素原子を表す。)、−C≡C−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がより好ましく、各々独立して−OCH2−、−CH2O−、−COO−、−OCO−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−、−COO−又は−OCO−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がさらに好ましく、各々独立して−COO−、−OCO−、1個の−CH2−又は隣接していない2個以上の−CH2−が各々独立して−O−で置換されても良い炭素原子数1から20のアルキレン基又は単結合である場合がさらにより好ましく、各々独立して−COO−、−OCO−又は単結合である場合が特に好ましく、nは0から3の整数である場合が好ましく、0から2の整数である場合がより好ましく、0又は1である場合がさらに好ましく、0である場合が特に好ましく、mは1から4の整数である場合が好ましく、1、2又は4である場合がより好ましく、1又は2である場合が特に好ましい。 Furthermore, when the compound represented by the general formula (III) and the general formula (IV) is a liquid crystal composition, Y 1 and Y 2 are each independently a hydrogen atom from the viewpoint of compatibility with other components. And preferably an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. More preferably, one of Y 1 and Y 2 represents a hydrogen atom, and the other is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. More preferably, Y 1 and Y 2 are particularly preferably a tert-butyl group, and Sp represents one —CH 2 — or two or more non-adjacent —CH 2 — independently. O-, -COO- or Preferred is an alkylene group having 1 to 20 carbon atoms which may be substituted with —OCO— or a single bond, and one —CH 2 — or two or more non-adjacent —CH 2 — are each independently More preferably an alkylene group having 1 to 20 carbon atoms which may be substituted with -O- or a single bond, more preferably an alkylene group having 1 to 20 carbon atoms or a single bond. More preferably, it is an alkylene group having 1 to 10 atoms or a single bond, more preferably an alkylene group having 1 to 5 carbon atoms or a single bond, and an alkylene group having 1 to 5 carbon atoms. If particularly preferably, X is each independently -O -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CH = CH-COO -, - CH = CH-OCO-, COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- , -CY = CY- (wherein Y independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group), -C≡C- or a single bond Are preferably each independently -O-, -COO-, -OCO- or a single bond, more preferably each independently -O- or a single bond, Particularly preferably, they are independently a single bond, and each A is independently unsubstituted, or each independently halogen, or each independently one or more hydrogen atoms may be replaced by a fluorine atom or a chlorine atom. 1 —CH 2 — Alternatively, two or more non-adjacent —CH 2 — may be each independently substituted with an alkyl group having 1 to 10 carbon atoms which may be substituted with —O—, —COO— or —OCO—. Preferred are 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, each independently being unsubstituted or Each independently a fluorine atom or chlorine atom, or each independently one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —COO— or —OCO. 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,3-cyclohexyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms which may be substituted with- Dioxane-2,5- More preferably represents yl group, each independently unsubstituted or fluorine atom or each independently, each independently one -CH 2 - or nonadjacent two or more -CH 2 - is More preferably, each is independently a 1,4-phenylene group or a 1,4-cyclohexylene group which may be substituted with an alkyl group having 1 to 5 carbon atoms which may be substituted with -O-, Even more preferably, it is independently unsubstituted or a 1,4-phenylene group or a 1,4-cyclohexylene group which may be independently substituted with a fluorine atom, a methyl group, an ethyl group or a methoxy group, Each independently unsubstituted, or each independently 1,4-phenylene group which may be substituted by fluorine atom, methyl group or methoxy group or unsubstituted 1,4-cyclo Particularly preferred are cases xylene group, Z is each independently -O -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - CH = CH-COO -, - CH = CH -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 —OCO—, —CY═CY— (wherein Y independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom or a cyano group). ), —C≡C—, one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —CO—, —COO—, — OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO- , -COO-CH = CH-, -OCO-CH = CH-, -CY = CY- (wherein Y is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom) Or a cyano group) or an alkylene group having 1 to 20 carbon atoms which may be substituted with —C≡C— or a single bond is preferable, and each independently represents —OCH 2 — or —CH 2 O. -, -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = C -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CY = CY -(Wherein each Y independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine atom), -C≡C-, one -CH 2 -or not adjacent 2 It is more preferable that two or more —CH 2 — are each independently an alkylene group having 1 to 20 carbon atoms which may be substituted with —O—, —COO— or —OCO—, or a single bond. -OCH 2 and -, - CH 2 O -, - COO -, - OCO-, 1 single -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O-, Alkyl having 1 to 20 carbon atoms which may be substituted with -COO- or -OCO- More preferably represents emission group or a single bond, each independently -COO -, - OCO-, 1 single -CH 2 - or nonadjacent two or more -CH 2 - are each independently - Even more preferable is an alkylene group having 1 to 20 carbon atoms which may be substituted with O- or a single bond, particularly preferably each independently -COO-, -OCO- or a single bond, n Is preferably an integer from 0 to 3, more preferably an integer from 0 to 2, more preferably 0 or 1, particularly preferably 0, and m is an integer from 1 to 4. Some cases are preferred, one, two or four are more preferred, and one or two are particularly preferred.
以下にさらに具体的な実施形態を記載する。 More specific embodiments will be described below.
接触水素還元に使用する触媒としては、均一系触媒又は不均一系触媒が好ましいが、合成の容易さ及び精製のしやすさの観点から不均一系触媒がより好ましい。好ましい金属種としては、パラジウム、白金、イリジウム、ルテニウム、ロジウム、金、銀、ニッケルが挙げられるが、これら単体であっても、酸化物、水酸化物、塩、合金、担持金属であっても良い。具体例としては、Pdカーボン、Pdアルミナ、Pd硫酸バリウム、Pdブラック、Pd炭酸カルシウム、酸化パラジウム、水酸化パラジウム、Ptカーボン、Ptサルファイテッドカーボン、Ptアルミナ、Ptブラック、酸化白金、ニッケル、ラネーニッケル、Ruカーボン、Ruアルミナ、Ruブラック、酸化ルテニウム、Ruチタニア、Rhカーボン、Rhアルミナ、Rhブラック、酸化ロジウム、塩化パラジウム(II)、硝酸パラジウム(II)、硫酸パラジウム(II)、酢酸パラジウム(II)、プロピオン酸パラジウム(II)、ジニトロジアンミンパラジウム(II)、臭化パラジウム(II)、ヨウ化パラジウム(II)、ジクロロビス(アセトニトリル)パラジウム(II)、ジクロロビス(ベンゾニトリル)パラジウム(II)、ジクロロ(η−1,5−シクロオクタジエン)パラジウム(II)、ジクロロ(η−2,5−ノルボルナジエン)パラジウム(II)、ジ−μ−クロロビス[(η−アリル)パラジウム(II)]、ビス(アセチルアセトナト)パラジウム(II)、ジクロロビス(トリフェニルホスフィン)パラジウム(II)、テトラアンミンパラジウム(II)塩化物水和物、テトラクロロパラジウム(II)酸、テトラクロロパラジウム(II)酸ナトリウム、テトラクロロパラジウム(II)酸カリウム、テトラクロロパラジウム(II)酸アンモニウム、ヘキサクロロパラジウム(IV)酸カリウム、ヘキサクロロパラジウム(IV)酸アンモニウム、テトラブロモパラジウム(II)酸、テトラブロモパラジウム(II)酸リチウム、テトラブロモパラジウム(II)酸ナトリウム、テトラブロモパラジウム(II)酸カリウム、テトラブロモパラジウム(II)酸アンモニウム、テトラブロモパラジウム(II)酸セチルトリメチルアンモニウム、硫酸パラジウム(II)水和物、シアン化パラジウム(II)、テトラシアノパラジウム(II)酸カリウム水和物、テトラニトロパラジウム(II)酸カリウム水和物、テトラアンミンパラジウム(II)塩化物、テトラアンミンパラジウム(II)酢酸塩、テトラアンミンパラジウム(II)硝酸塩、テトラアンミンパラジウム(II)硫酸塩水和物、テトラアンミンパラジウム(II)スルファミン酸塩、テトラアンミンパラジウム(II)メタンスルホン酸塩、トランス−ジクロロジアンミンパラジウム(II)、トランス−ジブロモジアンミンパラジウム(II)、ビス(エチレンジアミン)パラジウム(II)塩化物、ジクロロ(エチレンジアミン)パラジウム(II)、テトラキス(トリフェニルホスフィン)パラジウム(0)、ビス(ジベンジリデンアセトン)パラジウム(0)、ビス(ジメチルグリオキシマト)パラジウム(II)、テトラアンミンパラジウム(II)炭酸塩、テトラアンミンパラジウム(II)酢酸塩、ジクロロビス(N,N’−ジメチルホルムアミド)パラジウム(II)、テトラヒドロキソパラジウム(II)酸ナトリウム、トリス(ジベンジリデンアセトン)二パラジウム(0)、[1,1’−ビス(ジフェニルホスフィノ)フェロセン]パラジウム(II)クロライド、[1,1’−ビス(ジフェニルホスフィノ)フェロセン]パラジウム(II)クロライドジクロロメタン付加物、ヘキサクロロ白金(IV)酸水和物、ヘキサクロロ白金(IV)酸カリウム、ヘキサクロロ白金(IV)酸アンモニウム、シス−ジクロロジアンミン白金(II)、シス−ジニトロジアンミン白金(II)、シス−ジクロロビス(トリフェニルホスフィン)白金(II)、テトラキス(トリフェニルホスフィン)白金(0)、テトラアンミン白金(II)塩化物水和物、塩化白金(II)、ヨウ化白金(II)、ヘキサクロロ白金(IV)酸ナトリウム、ヘキサクロロ白金(IV)酸水和物、ヘキサクロロ白金(IV)酸カリウム、ヘキサクロロ白金(IV)酸アンモニウム、テトラクロロ白金(II)酸、テトラクロロ白金(II)酸カリウム、テトラクロロ白金(II)酸アンモニウム、テトラブロモ白金(II)酸カリウム、テトラニトロ白金(II)酸カリウム、テトラシアノ白金(II)酸カリウム水和物、テトラキス(チオシアナト)白金(II)酸カリウム、ヘキサヒドロソ白金(IV)酸、ヘキサヒドロソ白金(IV)酸カリウム水和物、テトラアンミン白金(II)酢酸塩、テトラアンミン白金(II)酢酸塩水和物、テトラアンミン白金(II)硝酸塩、テトラアンミン白金(II)硫酸塩、クロロペンタアンミン白金(IV)塩化物水和物、ヒドロキソペンタアンミン白金(IV)塩化物水和物、テトラクロロ白金(II)酸テトラアンミン白金(II)、トランス−ジクロロジアンミン白金(II)、シス−ビス(チオシアナト)ジアンミン白金(II)、シス−ジヨードジアンミン白金(II)、シス−ジクロロビス(イソプロピルアミン)白金(II)、トランス−ジクロロビス(イソプロピルアミン)白金(II)、ビス(アセチルアセトナト)白金(II)、ビス(ジベンジリデンアセトン)白金(0)、ジクロロ(η−1,5−シクロオクタジエン)白金(II)、ヘキサクロロ白金(IV)酸リチウム、テトラシアノ白金(II)酸バリウム水和物、テトラアンミン白金(II)スルファミン酸塩、テトラアンミン白金(II)炭酸塩、ヘキサヒドロキソ白金(IV)酸ナトリウム、クロロビス(アセチルアセトナト)白金(II)酸カリウム水和物、テトラアンミン白金(II)炭酸水素、Pt−VTS−IPA、Pt−VTS−キシレン、Pt−VTS−トルエン、Pt−CTS−IPA、Pt−CTS−キシレン、Pt−CTS−トルエン、塩化ルテニウム水和物、トリス(アセチルアセトナト)ルテニウム(III)、ドデカカルボニル三ルテニウム(0)、クロロペンタアンミンルテニウム(III)塩化物、ヘキサアンミンルテニウム(III)塩化物、ジクロロベンゼンルテニウム(II)ダイマー、ジクロロ(tert−ブチルビニリデン)ビストリシクロヘキシルホスフィンルテニウム(II)、ジクロロ(p−シメン)ルテニウム(II)ダイマー、ジヨード(p−シメン)ルテニウム(II)ダイマー、臭化ルテニウム水和物、ヨウ化ルテニウム(III)、ペンタクロロアクアルテニウム(III)酸アンモニウム、ペンタクロロアクアルテニウム(III)酸カリウム,ヘキサクロロルテニウム(IV)酸アンモニウム、ヘキサクロロルテニウム(IV)酸カリウム、ペンタクロロニトロシルルテニウム酸(II)カリウム、硝酸Ruニトロシル水溶液(トリニトラトニトロシルジアクアルテニウム溶液)、ルテニウム(VI)酸ナトリウム、ヘキサアンミンルテニウム(II)塩化物、ヘキサアンミンルテニウム(II)臭化物、ヘキサアンミンルテニウム(III)臭化物、ヘキサアンミンルテニウム(III)ヨウ化物、ヘキサアンミンルテニウム(III)硫酸塩水和物、ヘキサアンミンルテニウム(III)硝酸塩、ジ−μ−オキソテトラデカアンミン三ルテニウム(III−IV)塩化物水和物、ブロモペンタアンミンルテニウム(III)臭化物、ニトロシルペンタアンミンルテニウム(III)塩化物、ヒドロキソニトロシルテトラアンミンルテニウム(II)硝酸塩、ホルマトジカルボニルルテニウム(I)、μ3−オキソ−ヘキサ−μアセタトトリアクア三ルテニウム(I)酢酸塩水和物、ジクロロ(η−1,5−シクロオクタジエン)ルテニウム(II)、ジクロロテトラキス(トリフェニルホスフィン)ルテニウム(II)、ジクロロトリス(トリフェニルホスフィン)ルテニウム(II)、クロロヒドリドトリス(トリフェニルホスフィン)ルテニウム(II)トルエン付加物、ジヒドリドテトラキス(トリフェニルホスフィン)ルテニウム(II)、ヘキサシアノルテニウム(II)酸カリウム水和物、ヒドロキソニトロシルテトラアンミンルテニウム(II)硝酸塩、テトラニトロヒドロキソニトロシルルテニウム(II)酸カリウム、クロロヒドリドカルボニルトリス(トリフェニルホスフィン)ルテニウム(II)、ジヒドリドカルボニルトリス(トリフェニルホスフィン)ルテニウム(II)、デカクロロ−μ−オキソ二ルテニウム(IV)酸カリウム水和物、塩化ロジウム(III)水和物、ヨウ化ロジウム(III)、硝酸ロジウム(III)、硫酸ロジウム(III)、酢酸ロジウム(II)、クロロトリス(トリフェニルホスフィン)ロジウム(I)、クロロカルボニルビス(トリフェニルホスフィン)ロジウム(I)、トランス−ヒドリドカルボニルトリス(トリフェニルホスフィン)ロジウム(I)、ジ−μ−クロロテトラカルボニル二ロジウム(I)、ドデカカルボニル四ロジウム(0)、ヘキサデカカルボニル六ロジウム(0)、(アセチルアセトナト)ジカルボニルロジウム(I)、トリス(アセチルアセトナト)ロジウム(III)、ジ−μ−クロロビス[(η−1,5−シクロオクタジエン)ロジウム(I)]、ジアセタトビス(シクロオクタジエン)二ロジウム(I)、臭化ロジウム(III)水和物、ヘキサクロロロジウム(III)酸、ヘキサブロモロジウム(III)酸、水酸化ロジウム(III)水和物、リン酸ロジウム(III)、ヘキサニトロロジウム(III)酸カリウム、クロロペンタアンミンロジウム(III)塩化物、ペンタアンミンアクアロジウム(III)硝酸塩水和物、ヘキサアンミンロジウム(III)塩化物、ヘキサアンミンロジウム(III)酸性硝酸塩、(アセチルアセトナト)カルボニル(トリフェニルホスフィン)ロジウム(I)、ジ−μ−クロロジカルボニルビス(トリフェニルホスフィン)二ロジウム(I)、安息香酸ロジウム(II)、オクタン酸ロジウム(II)、酢酸ロジウム(II)水和物、ヘキサクロロロジウム(III)酸アンモニウム水和物、ペンタクロロアクアロジウム(III)酸アンモニウム、ペンタアンミンアクアロジウム(III)塩化物、ペンタアンミンアクアロジウム(III)硝酸塩溶液、ヘキサニトロロジウム(III)酸ナトリウム、ヘキサシアノロジウム(III)酸カリウム、アセチルアセトナト[(η−1,5−シクロオクタジエン)ロジウム(I)]、ジクロロビス[(ノルボルナジエン)ロジウム(I)]、シアン化金(I)、ジシアノ金(I)酸カリウム、テトラクロロ金(III)酸水和物、テトラシアノ金(III)酸カリウム、ジスルフィド金(I)酸ナトリウム、ジスルフィド金(I)アンモニウム、テトラクロロ金(III)酸ナトリウム、テトラクロロ金(III)酸カリウム水和物、クロロ(トリエチルホスフィン)金(I)、クロロ(トリフェニルホスフィン)金(I)、ジシアノ金(I)酸アンモニウム、ジシアノ金(I)酸バリウム水和物、塩化イリジウム水和物、ヘキサクロロイリジウム(IV)酸、ヘキサクロロイリジウム(IV)酸アンモニウム、ヘキサクロロイリジウム(IV)酸カリウム、ヘキサクロロイリジウム(IV)酸ナトリウム水和物、ヘキサクロロイリジウム(III)酸ナトリウム水和物、ヘキサクロロイリジウム(III)酸カリウム水和物、臭化イリジウム(III)水和物、ヘキサブロモイリジウム(III)酸、酸化イリジウム(IV)、トリス(オキサラト)イリジウム(III)酸カリウム水和物、クロロペンタアンミンイリジウム(III)塩化物水和物、クロロカルボニルビス(トリフェニルホスフィン)イリジウム(I)、ジ−μ−クロロビス(η−1,5−シクロオクタジエン)二イリジウム(I)、ヘキサニトロイリジウム(III)ナトリウム、ヘキサブロモイリジウム(IV)酸カリウム、ペンタクロロアクアイリジウム(III)酸カリウム、シアン化金(I)、ジシアノ金(I)酸カリウム、テトラクロロ金(III)酸水和物、テトラシアノ金(III)酸カリウム、ジスルフィド金(I)酸ナトリウム、ジスルフィド金(I)酸アンモニウム、テトラクロロ金(I
II)酸ナトリウム、テトラクロロ金(III)酸カリウム水和物、クロロ(トリエチルホスフィン)金(I)、クロロ(トリフェニルホスフィン)金(I)、ジシアノ金(I)酸アンモニウム、ジシアノ金(I)酸バリウム水和物、塩化イリジウム水和物、ヘキサクロロイリジウム(IV)酸、ヘキサクロロイリジウム(IV)酸アンモニウム、ヘキサクロロイリジウム(IV)酸カリウム、ヘキサクロロイリジウム(IV)酸ナトリウム水和物、ヘキサクロロイリジウム(III)酸ナトリウム水和物、ヘキサクロロイリジウム(III)酸カリウム水和物、臭化イリジウム(III)水和物、ヘキサブロモイリジウム(III)酸、酸化イリジウム(IV)、トリス(オキサラト)イリジウム(III)酸カリウム水和物、クロロペンタアンミンイリジウム(III)塩化物水和物、クロロカルボニルビス(トリフェニルホスフィン)イリジウム(I)、ジ−μ−クロロビス(η−1,5−シクロオクタジエン)二イリジウム(I)、ヘキサニトロイリジウム(III)ナトリウム、ヘキサブロモイリジウム(IV)酸カリウム、ペンタクロロアクアイリジウム(III)酸カリウムが挙げられるが、不均一系触媒として、Pdカーボン、Pdアルミナ、Pd硫酸バリウム、Pdブラック、Pd炭酸カルシウム、酸化パラジウム、水酸化パラジウム、Ptカーボン、Ptサルファイテッドカーボン、Ptアルミナ、Ptブラック、酸化白金、ニッケル、ラネーニッケル、Ruカーボン、Ruアルミナ、Ruブラック、酸化ルテニウム、Ruチタニア、Rhカーボン、Rhアルミナ、Rhブラック、酸化ロジウムがより好ましく、コスト及び入手の容易さの観点から、Pdカーボン、Pdアルミナ、Pd硫酸バリウム、Pdブラック、Pd炭酸カルシウム、酸化パラジウム、水酸化パラジウム、Ptカーボン、Ptサルファイテッドカーボン、Ptアルミナ、Ptブラック、酸化白金、ニッケル、ラネーニッケルがさらに好ましく、Pdカーボン、Pdアルミナ、Pd硫酸バリウム、Pdブラック、Pd炭酸カルシウム、酸化パラジウム、水酸化パラジウム、ニッケル、ラネーニッケルがさらにより好ましく、Pdカーボン、ラネーニッケルがさらにより好ましく、Pdカーボンが特に好ましい。また触媒は含水品であっても乾燥品であっても構わない。
The catalyst used for the catalytic hydrogen reduction is preferably a homogeneous catalyst or a heterogeneous catalyst, but a heterogeneous catalyst is more preferred from the viewpoint of ease of synthesis and ease of purification. Preferable metal species include palladium, platinum, iridium, ruthenium, rhodium, gold, silver, and nickel. Even if they are simple substances, they may be oxides, hydroxides, salts, alloys, and supported metals. good. Specific examples include Pd carbon, Pd alumina, Pd barium sulfate, Pd black, Pd calcium carbonate, palladium oxide, palladium hydroxide, Pt carbon, Pt sulfitized carbon, Pt alumina, Pt black, platinum oxide, nickel, Raney nickel, Ru carbon, Ru alumina, Ru black, ruthenium oxide, Ru titania, Rh carbon, Rh alumina, Rh black, rhodium oxide, palladium chloride (II), palladium nitrate (II), palladium sulfate (II), palladium acetate (II) , Palladium (II) propionate, dinitrodiammine palladium (II), palladium (II) bromide, palladium (II) iodide, dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) para Um (II), dichloro (η-1,5-cyclooctadiene) palladium (II), dichloro (η-2,5-norbornadiene) palladium (II), di-μ-chlorobis [(η-allyl) palladium ( II)], bis (acetylacetonato) palladium (II), dichlorobis (triphenylphosphine) palladium (II), tetraamminepalladium (II) chloride hydrate, tetrachloropalladium (II) acid, tetrachloropalladium (II ) Sodium salt, potassium tetrachloropalladium (II), ammonium tetrachloropalladium (II), potassium hexachloropalladium (IV), ammonium hexachloropalladium (IV), tetrabromopalladium (II), tetrabromopalladium ( II) Acid Lithium Sodium tetrabromopalladium (II), potassium tetrabromopalladium (II), ammonium tetrabromopalladium (II), cetyltrimethylammonium tetrabromopalladium (II), palladium (II) sulfate hydrate, cyanide Palladium (II) iodide, tetracyanopalladium (II) potassium hydrate, tetranitropalladium (II) potassium hydrate, tetraammine palladium (II) chloride, tetraammine palladium (II) acetate, tetraammine palladium (II ) Nitrate, tetraamminepalladium (II) sulfate hydrate, tetraamminepalladium (II) sulfamate, tetraamminepalladium (II) methanesulfonate, trans-dichlorodiamminepalladium (II) Trans-dibromodiamminepalladium (II), bis (ethylenediamine) palladium (II) chloride, dichloro (ethylenediamine) palladium (II), tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0) Bis (dimethylglyoximato) palladium (II), tetraamminepalladium (II) carbonate, tetraamminepalladium (II) acetate, dichlorobis (N, N'-dimethylformamide) palladium (II), tetrahydroxopalladium (II) Acid sodium, tris (dibenzylideneacetone) dipalladium (0), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) chloride, [1,1′-bis (diphenylphosphino) f Locene] palladium (II) chloride dichloromethane adduct, hexachloroplatinum (IV) acid hydrate, potassium hexachloroplatinum (IV), ammonium hexachloroplatinum (IV), cis-dichlorodiammine platinum (II), cis-dinitrodiammine Platinum (II), cis-dichlorobis (triphenylphosphine) platinum (II), tetrakis (triphenylphosphine) platinum (0), tetraammineplatinum (II) chloride hydrate, platinum (II) chloride, platinum iodide ( II), sodium hexachloroplatinum (IV), hexachloroplatinum (IV) acid hydrate, potassium hexachloroplatinum (IV), ammonium hexachloroplatinum (IV), tetrachloroplatinum (II), tetrachloroplatinum (II) ) Potassium acid, tetrachloroplatinum (II) acid Ammonium, potassium tetrabromoplatinate (II), potassium tetranitroplatinum (II), potassium tetracyanoplatinum (II) hydrate, potassium tetrakis (thiocyanato) platinum (II), hexahydrosoplatinum (IV), hexahydrosoplatinum ( IV) Potassium acid hydrate, tetraammineplatinum (II) acetate, tetraammineplatinum (II) acetate hydrate, tetraammineplatinum (II) nitrate, tetraammineplatinum (II) sulfate, chloropentammineplatinum (IV) chloride Hydrate, hydroxopentaammineplatinum (IV) chloride hydrate, tetrachloroplatinum (II) tetraammineplatinum (II), trans-dichlorodiammineplatinum (II), cis-bis (thiocyanato) diammineplatinum (II) Cis-diiododiammine platinum ( I), cis-dichlorobis (isopropylamine) platinum (II), trans-dichlorobis (isopropylamine) platinum (II), bis (acetylacetonato) platinum (II), bis (dibenzylideneacetone) platinum (0), dichloro (Η-1,5-cyclooctadiene) platinum (II), lithium hexachloroplatinate (IV), barium tetracyanoplatinate (II), tetraammineplatinum (II) sulfamate, tetraammineplatinum (II) carbonate Salt, sodium hexahydroxoplatinate (IV), potassium chlorobis (acetylacetonato) platinum (II), tetraammineplatinum (II) bicarbonate, Pt-VTS-IPA, Pt-VTS-xylene, Pt-VTS -Toluene, Pt-CTS-IPA, Pt-CTS-Xylene , Pt-CTS-toluene, ruthenium chloride hydrate, tris (acetylacetonato) ruthenium (III), dodecacarbonyltriruthenium (0), chloropentaammineruthenium (III) chloride, hexaammineruthenium (III) chloride , Dichlorobenzene ruthenium (II) dimer, dichloro (tert-butylvinylidene) bistricyclohexylphosphine ruthenium (II), dichloro (p-cymene) ruthenium (II) dimer, diiodo (p-cymene) ruthenium (II) dimer, bromide Ruthenium hydrate, ruthenium (III) iodide, ammonium pentachloroaquarthenium (III), potassium pentachloroaquarthenium (III), ammonium hexachlororuthenium (IV), hexac Potassium ruthenium (IV), potassium pentachloronitrosyl ruthenate (II), Ru nitrosyl nitrate aqueous solution (trinitratonitrosyldiaquaterthenium solution), ruthenium (VI) sodium, hexaammineruthenium (II) chloride, hexaammine Ruthenium (II) bromide, hexaammineruthenium (III) bromide, hexaammineruthenium (III) iodide, hexaammineruthenium (III) sulfate hydrate, hexaammineruthenium (III) nitrate, di-μ-oxotetradecaammine Triruthenium (III-IV) chloride hydrate, bromopentaammineruthenium (III) bromide, nitrosylpentaammineruthenium (III) chloride, hydroxonitrosyltetraammineruthenium ( II) Nitrate, formatodicarbonylruthenium (I), μ3-oxo-hexa-μ acetatotriaqua triruthenium (I) acetate hydrate, dichloro (η-1,5-cyclooctadiene) ruthenium (II), Dichlorotetrakis (triphenylphosphine) ruthenium (II), dichlorotris (triphenylphosphine) ruthenium (II), chlorohydridotris (triphenylphosphine) ruthenium (II) toluene adduct, dihydridotetrakis (triphenylphosphine) ruthenium (II) II), potassium hexacyanoruthenium (II) hydrate, hydroxonitrosyltetraammineruthenium (II) nitrate, potassium tetranitrohydroxonitrosylruthenium (II), chlorohydridocarbonyltris (trifer Ruphosphine) ruthenium (II), dihydridocarbonyltris (triphenylphosphine) ruthenium (II), decachloro-μ-oxodiruthenium (IV) potassium hydrate, rhodium (III) chloride hydrate, rhodium iodide (III), rhodium nitrate (III), rhodium sulfate (III), rhodium acetate (II), chlorotris (triphenylphosphine) rhodium (I), chlorocarbonylbis (triphenylphosphine) rhodium (I), trans-hydridocarbonyl Tris (triphenylphosphine) rhodium (I), di-μ-chlorotetracarbonyl dirhodium (I), dodecacarbonyl tetrarhodium (0), hexadecacarbonyl hexarhodium (0), (acetylacetonato) dicarbonyl rhodium ( I), Tris (Ace Ruacetonato) rhodium (III), di-μ-chlorobis [(η-1,5-cyclooctadiene) rhodium (I)], diacetatobis (cyclooctadiene) dirhodium (I), rhodium bromide (III) hydrated , Hexachlororhodium (III) acid, hexabromorhodium (III) acid, rhodium hydroxide (III) hydrate, rhodium (III) phosphate, potassium hexanitrorhodium (III), chloropentamminerhodium (III) Chloride, pentaammine aqua rhodium (III) nitrate hydrate, hexaammine rhodium (III) chloride, hexaammine rhodium (III) acidic nitrate, (acetylacetonato) carbonyl (triphenylphosphine) rhodium (I), di -Μ-chlorodicarbonylbis (triphenylphosphite ) Rhodium (I), rhodium (II) benzoate, rhodium (II) octoate, rhodium acetate (II) hydrate, ammonium hexachlororhodium (III) ammonium hydrate, ammonium pentachloroaquarodium (III) , Pentaammine aquadium (III) chloride, pentaammine aquadium (III) nitrate solution, sodium hexanitrorhodium (III), potassium hexacyanorhodium (III), acetylacetonate [(η-1,5-cyclo Octadiene) rhodium (I)], dichlorobis [(norbornadiene) rhodium (I)], gold cyanide (I), potassium dicyanogold (I), tetrachlorogold (III) hydrate, tetracyanogold (III ) Potassium acid, disulfide gold (I) sodium acid, dis Fido gold (I) ammonium, sodium tetrachloro gold (III), potassium tetrachloro gold (III) hydrate, chloro (triethylphosphine) gold (I), chloro (triphenylphosphine) gold (I), dicyano Gold (I) acid ammonium, dicyano gold (I) acid barium hydrate, iridium chloride hydrate, hexachloroiridium (IV) acid, hexachloroiridium (IV) ammonium, hexachloroiridium (IV) potassium, hexachloroiridium ( IV) Sodium acid hydrate, sodium hexachloroiridium (III) hydrate, potassium hexachloroiridium (III) potassium hydrate, iridium bromide (III) hydrate, hexabromoiridium (III) acid, iridium oxide (IV), Tris (oxalato) Lithium (III) potassium hydrate, chloropentaammine iridium (III) chloride hydrate, chlorocarbonylbis (triphenylphosphine) iridium (I), di-μ-chlorobis (η-1,5-cycloocta Diene) diiridium (I), sodium hexanitroiridium (III), potassium hexabromoiridium (IV), potassium pentachloroaquadium (III), gold (I) cyanide, potassium dicyanogold (I), Tetrachlorogold (III) acid hydrate, potassium tetracyanogold (III), sodium disulfide gold (I), ammonium disulfide gold (I), tetrachlorogold (I
II) Sodium acid, potassium tetrachloroaurate (III) hydrate, chloro (triethylphosphine) gold (I), chloro (triphenylphosphine) gold (I), ammonium dicyanogold (I), dicyanogold (I ) Barium acid hydrate, iridium chloride hydrate, hexachloroiridium (IV) acid, ammonium hexachloroiridium (IV) acid, potassium hexachloroiridium (IV) acid, sodium hexachloroiridium (IV) acid hydrate, hexachloroiridium ( III) Sodium hydrate, potassium hexachloroiridium (III) potassium hydrate, iridium (III) bromide hydrate, hexabromoiridium (III) acid, iridium (IV) oxide, tris (oxalato) iridium (III ) Potassium acid hydrate, chloropen Ammine iridium (III) chloride hydrate, chlorocarbonylbis (triphenylphosphine) iridium (I), di-μ-chlorobis (η-1,5-cyclooctadiene) diiridium (I), hexanitroiridium ( III) Sodium, potassium hexabromoiridium (IV), potassium pentachloroaquairidium (III), and heterogeneous catalysts include Pd carbon, Pd alumina, Pd barium sulfate, Pd black, Pd calcium carbonate, Palladium oxide, palladium hydroxide, Pt carbon, Pt sulfated carbon, Pt alumina, Pt black, platinum oxide, nickel, Raney nickel, Ru carbon, Ru alumina, Ru black, ruthenium oxide, Ru titania, Rh carbon, Rh aluminum Rh black and rhodium oxide are more preferable, and from the viewpoint of cost and availability, Pd carbon, Pd alumina, Pd barium sulfate, Pd black, Pd calcium carbonate, palladium oxide, palladium hydroxide, Pt carbon, Pt sulfitized Carbon, Pt alumina, Pt black, platinum oxide, nickel, Raney nickel are more preferred, Pd carbon, Pd alumina, Pd barium sulfate, Pd black, Pd calcium carbonate, palladium oxide, palladium hydroxide, nickel, Raney nickel are even more preferred, Pd carbon and Raney nickel are even more preferable, and Pd carbon is particularly preferable. The catalyst may be a water-containing product or a dry product.
接触水素還元の反応時の圧力は、大気圧を0MPaとして、水素圧が0MPaから10MPaであることが好ましいが、設備の観点及び安全性の観点から大気圧を0MPaとして、水素圧が0MPaから1MPaであることがより好ましく、大気圧を0MPaとして、水素圧が0MPaより大きく、0.5MPaまでであることが特に好ましい。 The pressure during the catalytic hydrogen reduction reaction is preferably 0 MPa to 10 MPa with an atmospheric pressure of 0 MPa, but from the viewpoint of equipment and safety, the atmospheric pressure is 0 MPa and the hydrogen pressure is 0 to 1 MPa. It is more preferable that the atmospheric pressure is 0 MPa, and the hydrogen pressure is more than 0 MPa and particularly preferably up to 0.5 MPa.
接触水素還元の反応温度は、−100℃から200℃であることが好ましく、設備の観点及び収率の観点から、−20℃から100℃であることがより好ましく、0℃から60℃であることがさらに好ましく、0℃から40℃であることがより好ましく、0℃から室温以下であることが特に好ましい。 The reaction temperature for catalytic hydrogen reduction is preferably from −100 ° C. to 200 ° C., more preferably from −20 ° C. to 100 ° C., and from 0 ° C. to 60 ° C. from the viewpoints of equipment and yield. More preferably, it is more preferably 0 ° C. to 40 ° C., and particularly preferably 0 ° C. to room temperature or lower.
接触水素還元に使用する反応溶媒としては例えば、tert−ブチルアルコール、イソブチルアルコール、イソプロピルアルコール、イソペンチルアルコール、シクロヘキサノール、1−ブタノール、2−ブタノール、1−オクタノール、2−メトキシエタノール、エチレングリコール、ジエチレングリコール、メタノール、メチルシクロヘキサノール、エタノール、プロパノール、クロロホルム、四塩化炭素、ジクロロメタン、1,2−ジクロロエタン、1,2−ジクロロエチレン、1,1,2,2−テトラクロロエタン、トリクロロエチレン、1−クロロブタン、二硫化炭素、アセトン、アセトニトリル、ベンゾニトリル、N,N−ジメチルアセトアミド、ジメチルスルホキシド、ジエチルエーテル、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールジエチルエーテル、o−ジクロロベンゼン、キシレン、o−キシレン、p−キシレン、m−キシレン、クロロベンゼン、酢酸イソブチル、酢酸イソプロピル、酢酸イソアミル、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸ペンチル、酢酸メチル、酢酸2−メトキシエチル、ヘキサメチルリン酸トリアミド、トリス(ジメチルアミノ)ホスフィン、シクロヘキサノン、1,4−ジオキサン、スチレン、テトラクロロエチレン、テトラヒドロフラン、ピリジン、1−メチル−2−ピロリジノン、1,1,1−トリクロロエタン、トルエン、ヘキサン、ペンタン、シクロヘキサン、シクロペンタン、ヘプタン、ベンゼン、メチルイソブチルケトン、tert−ブチルメチルエーテル、メチルエチルケトン、メチルシクロヘキサノン、メチルブチルケトン、ジエチルケトン、ガソリン、コールタールナフサ、石油エーテル、石油ナフサ、石油ベンジン、テレビン油、ミネラルスピリット、水が挙げられるが、収率、後処理及び入手の容易さの観点から、tert−ブチルアルコール、イソブチルアルコール、イソプロピルアルコール、イソペンチルアルコール、シクロヘキサノール、1−ブタノール、2−ブタノール、1−オクタノール、2−メトキシエタノール、エチレングリコール、ジエチレングリコール、メタノール、メチルシクロヘキサノール、エタノール、プロパノール、ジエチルエーテル、ジエチレングリコールジエチルエーテル、o−ジクロロベンゼン、キシレン、o−キシレン、p−キシレン、m−キシレン、1,4−ジオキサン、テトラヒドロフラン、1−メチル−2−ピロリジノン、トルエン、ヘキサン、ペンタン、シクロヘキサン、シクロペンタン、ヘプタン、ベンゼン、メチルイソブチルケトン、tert−ブチルメチルエーテル、メチルエチルケトン、石油エーテル、水が好ましく、イソプロピルアルコール、メタノール、エタノール、プロパノール、ジエチルエーテル、キシレン、o−キシレン、p−キシレン、m−キシレン、1,4−ジオキサン、テトラヒドロフラン、トルエン、ヘキサン、ペンタン、シクロヘキサン、シクロペンタン、ヘプタン、ベンゼン、tert−ブチルメチルエーテル、石油エーテル、水がより好ましく、イソプロピルアルコール、メタノール、エタノール、プロパノール、1,4−ジオキサン、テトラヒドロフラン、トルエン、ヘキサン、ペンタン、シクロヘキサン、シクロペンタン、ヘプタン、tert−ブチルメチルエーテル、水がさらに好ましく、イソプロピルアルコール、メタノール、エタノール、プロパノール、1,4−ジオキサン、テトラヒドロフラン、tert−ブチルメチルエーテル、水がさらにより好ましい。また、反応溶媒は単一の溶媒であっても前記溶媒を2種類以上混合して用いても構わない。 Examples of the reaction solvent used for catalytic hydrogen reduction include tert-butyl alcohol, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, cyclohexanol, 1-butanol, 2-butanol, 1-octanol, 2-methoxyethanol, ethylene glycol, Diethylene glycol, methanol, methylcyclohexanol, ethanol, propanol, chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethylene, 1-chlorobutane, two Carbon sulfide, acetone, acetonitrile, benzonitrile, N, N-dimethylacetamide, dimethyl sulfoxide, diethyl ether, ethylene glycol monoethyl ether Acetate, diethylene glycol diethyl ether, o-dichlorobenzene, xylene, o-xylene, p-xylene, m-xylene, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, acetic acid Methyl, 2-methoxyethyl acetate, hexamethylphosphate triamide, tris (dimethylamino) phosphine, cyclohexanone, 1,4-dioxane, styrene, tetrachloroethylene, tetrahydrofuran, pyridine, 1-methyl-2-pyrrolidinone, 1,1,1 -Trichloroethane, toluene, hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, methyl isobutyl ketone, tert-butyl methyl ether, methyl ethyl ketone, Examples include tilcyclohexanone, methyl butyl ketone, diethyl ketone, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit, and water, from the viewpoint of yield, post-treatment and availability. tert-butyl alcohol, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, cyclohexanol, 1-butanol, 2-butanol, 1-octanol, 2-methoxyethanol, ethylene glycol, diethylene glycol, methanol, methylcyclohexanol, ethanol, propanol, Diethyl ether, diethylene glycol diethyl ether, o-dichlorobenzene, xylene, o-xylene, p-xylene, m-xylene, 1,4-dioxane, Tetrahydrofuran, 1-methyl-2-pyrrolidinone, toluene, hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, methyl isobutyl ketone, tert-butyl methyl ether, methyl ethyl ketone, petroleum ether, water are preferred, isopropyl alcohol, methanol, ethanol , Propanol, diethyl ether, xylene, o-xylene, p-xylene, m-xylene, 1,4-dioxane, tetrahydrofuran, toluene, hexane, pentane, cyclohexane, cyclopentane, heptane, benzene, tert-butyl methyl ether, petroleum Ether and water are more preferable, isopropyl alcohol, methanol, ethanol, propanol, 1,4-dioxane, tetrahydrofuran, toluene, Xylene, pentane, cyclohexane, cyclopentane, heptane, tert-butyl methyl ether, and water are more preferable, and isopropyl alcohol, methanol, ethanol, propanol, 1,4-dioxane, tetrahydrofuran, tert-butyl methyl ether, and water are even more preferable. . The reaction solvent may be a single solvent or a mixture of two or more of the above solvents.
また、溶媒の一部又は全部に若しくは添加物として酸を用いることも可能である。酸としては、有機酸であっても無機酸であっても良いが、ブレンステッド酸である場合が好ましい。具体例としては、塩酸、臭化水素酸、硫酸、硝酸、オルトリン酸、ピロリン酸、アルキルスルホン酸、アリールスルホン酸、ホスホン酸、カルボン酸、過塩素酸、リンモリブデン酸、ケイタングステン酸、バナドモリブデン酸、ヘテロポリ酸、ベンゼンスルホン酸、p−トルエンスルホン酸、ナフタレンスルホン酸、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、t−ブチルスルホン酸、2−ヒドロキシプロパンスルホン酸、トリフルオロメタンスルホン酸、トリクロロメタンスルホン酸、ベンゼンホスホン酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、トリフルオロ酢酸、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、ピバリン酸、吉草酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、シュウ酸、シクロヘキサンカルボン酸、安息香酸、フタル酸、イソフタル酸、テレフタル酸、アクリル酸、メタクリル酸、プロピオール酸、クロトン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、オレイン酸、アスパラギン酸、グルタミン酸、ポリリン酸、固体酸等が挙げられるが、目的物の精製のしやすさの観点から、塩酸、臭化水素酸、硫酸、硝酸、アルキルスルホン酸、アリールスルホン酸、カルボン酸、ベンゼンスルホン酸、p−トルエンスルホン酸、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、t−ブチルスルホン酸、2−ヒドロキシプロパンスルホン酸、トリフルオロメタンスルホン酸、トリクロロメタンスルホン酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、トリフルオロ酢酸、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、ピバリン酸、吉草酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、シュウ酸、シクロヘキサンカルボン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、オレイン酸、アスパラギン酸、グルタミン酸、固体酸がより好ましく、塩酸、臭化水素酸、硫酸、硝酸、アルキルスルホン酸、カルボン酸、ベンゼンスルホン酸、p−トルエンスルホン酸、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、t−ブチルスルホン酸、2−ヒドロキシプロパンスルホン酸、トリフルオロメタンスルホン酸、トリクロロメタンスルホン酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、トリフルオロ酢酸、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、ピバリン酸、シュウ酸、マレイン酸、フマル酸、固体酸がさらに好ましく、塩酸、臭化水素酸、硫酸、硝酸、カルボン酸、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、t−ブチルスルホン酸、2−ヒドロキシプロパンスルホン酸、トリフルオロメタンスルホン酸、トリクロロメタンスルホン酸、クロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、トリフルオロ酢酸、ギ酸、酢酸、プロピオン酸がさらにより好ましく、塩酸、硫酸、トリフルオロメタンスルホン酸、トリフルオロ酢酸、ギ酸、酢酸がさらにより好ましく、塩酸、硫酸、ギ酸、酢酸が特に好ましい。溶媒の一部又は全部に若しくは添加物として酸を用いても用いなくても構わないが、反応速度及び収率の観点から、溶媒に酸を任意の割合で加えるか、溶媒として酸のみを用いる場合が好ましく、後処理の容易さの観点から、硫酸等の強酸を用いる場合には、溶媒に酸を任意の割合で加える場合がより好ましく、溶媒100体積部に対し酸を0.0001体積部から100体積部の割合で加える場合がさらに好ましく、溶媒100体積部に対し酸を0.001体積部から50体積部の割合で加える場合がさらにより好ましく、溶媒100体積部に対し酸を0.01体積部から10体積部の割合で加える場合がさらにより好ましく、溶媒100体積部に対し酸を0.1体積部から10体積部の割合で加える場合が特に好ましく、酢酸等の弱酸を用いる場合には、溶媒と酸との体積比が溶媒:酸=100:0.1から0:100即ち溶媒として酸を用いる場合が好ましく、溶媒と酸との体積比が溶媒:酸=100:1から0:100即ち溶媒として酸のみを用いる場合がより好ましく、溶媒と酸との体積比が溶媒:酸=10:1から0:100即ち溶媒として酸のみを用いる場合がさらに好ましく、溶媒と酸との体積比が溶媒:酸=5:1から0:100即ち溶媒として酸のみを用いる場合がさらにより好ましく、溶媒と酸との体積比が0:100即ち溶媒として酸のみを用いる場合が特に好ましい。さらに具体的には、溶媒に対し硫酸又は塩酸を0.01体積%から10体積%加えるか、溶媒に対しギ酸又は酢酸を10体積%以上若しくはギ酸又は酢酸のみを溶媒とする場合が好ましく、溶媒に対し硫酸又は塩酸を0.1体積%から5体積%加えるか、溶媒に対しギ酸又は酢酸を50体積%以上若しくはギ酸又は酢酸のみを溶媒とする場合がより好ましい。 It is also possible to use an acid for part or all of the solvent or as an additive. The acid may be an organic acid or an inorganic acid, but is preferably a Bronsted acid. Specific examples include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, orthophosphoric acid, pyrophosphoric acid, alkylsulfonic acid, arylsulfonic acid, phosphonic acid, carboxylic acid, perchloric acid, phosphomolybdic acid, silicotungstic acid, vanado Molybdic acid, heteropoly acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t-butylsulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, Trichloromethanesulfonic acid, benzenephosphonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid Acid, myristic acid, palmitic Acid, stearic acid, oxalic acid, cyclohexanecarboxylic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, acrylic acid, methacrylic acid, propiolic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, oleic acid , Aspartic acid, glutamic acid, polyphosphoric acid, solid acid, etc., but from the viewpoint of ease of purification of the target product, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, alkylsulfonic acid, arylsulfonic acid, carboxylic acid , Benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t-butylsulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, chloroacetic acid, dichloro Acetic acid, trichloroacetic acid, trifluoro Acetic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oxalic acid, cyclohexanecarboxylic acid, maleic acid , Fumaric acid, citraconic acid, mesaconic acid, oleic acid, aspartic acid, glutamic acid, solid acid are more preferable, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, alkylsulfonic acid, carboxylic acid, benzenesulfonic acid, p-toluenesulfone Acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t-butylsulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, Formic acid, acetic acid, propionic acid , Butyric acid, isobutyric acid, pivalic acid, oxalic acid, maleic acid, fumaric acid, solid acid are more preferable, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, carboxylic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, t-Butylsulfonic acid, 2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, acetic acid, propionic acid are even more preferred, hydrochloric acid, sulfuric acid Trifluoromethanesulfonic acid, trifluoroacetic acid, formic acid and acetic acid are even more preferred, and hydrochloric acid, sulfuric acid, formic acid and acetic acid are particularly preferred. An acid may or may not be used as a part or all of the solvent or as an additive, but from the viewpoint of reaction rate and yield, an acid is added to the solvent at an arbitrary ratio, or only the acid is used as the solvent. In the case where a strong acid such as sulfuric acid is used from the viewpoint of ease of post-treatment, it is more preferable to add an acid in an arbitrary ratio to the solvent, and 0.0001 part by volume of the acid with respect to 100 parts by volume of the solvent. To 100 volume parts is more preferable, and the case where the acid is added at a ratio of 0.001 volume part to 50 volume parts with respect to 100 volume parts of the solvent is still more preferable, and the acid is added to 0.1 volume with respect to 100 volume parts of the solvent. It is even more preferable to add at a ratio of 01 to 10 parts by volume, particularly preferable to add an acid at a ratio of 0.1 to 10 parts by volume with respect to 100 parts by volume of solvent, and a weak acid such as acetic acid. When the volume ratio of the solvent to the acid is solvent: acid = 100: 0.1 to 0: 100, that is, the case where an acid is used as the solvent is preferable, and the volume ratio of the solvent to the acid is preferably solvent: acid = 100: 1 to 0: 100, that is, the case where only the acid is used as the solvent is more preferable, and the volume ratio of the solvent to the acid is more preferably the solvent: acid = 10: 1 to 0: 100, that is, the case where only the acid is used as the solvent. It is even more preferable that the volume ratio of acid is solvent: acid = 5: 1 to 0: 100, that is, only the acid is used as the solvent, and the volume ratio of solvent to acid is 0: 100, that is, the case where only the acid is used as the solvent. Particularly preferred. More specifically, it is preferable to add 0.01% to 10% by volume of sulfuric acid or hydrochloric acid to the solvent, or 10% by volume or more of formic acid or acetic acid or only formic acid or acetic acid to the solvent. More preferably, 0.1% to 5% by volume of sulfuric acid or hydrochloric acid is added to the solvent, or 50% by volume or more of formic acid or acetic acid or only formic acid or acetic acid is used as the solvent.
以下、実施例を挙げて本発明を更に記述するが、本発明はこれらの実施例に限定されるものではない。以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。水素圧は、大気圧を0MPaとした場合の圧力を意味する。以下に本願発明の製法及び比較例の製法によって製造した化合物について記述するが、わかりやすくするために、本願発明の製法によって製造した化合物を(I−1)のように末尾に数字のみを付記し、比較例の製法によって製造した化合物を(I−1a)のように末尾にアルファベットを付記する。 EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. “%” In the compositions of the following examples and comparative examples means “% by mass”. The hydrogen pressure means a pressure when the atmospheric pressure is 0 MPa. In the following, the compounds produced by the production method of the present invention and the production method of the comparative example will be described. However, for the sake of clarity, the compound produced by the production method of the present invention is appended with a numeral at the end as in (I-1). The compound produced by the production method of the comparative example is suffixed with an alphabet as in (I-1a).
化合物の純度はGC又はUPLCによって分析した。分析条件は以下の通りである。
(GC分析条件)
カラム:Agilent Technologies,J&W Column DB−1HT,15m×0.25mm×0.10μm
温度プログラム:100℃(1分間)−(20℃/分間)−250℃−(10℃/分間)−380℃−(7℃/分間)−400℃(2.64分間)
注入口温度:350℃
検出器温度:400℃
(UPLC分析条件)
カラム:Waters ACQUITY UPLC BEH C18,2.1×100mm,1.7μm
溶出溶媒:アセトニトリル/水(90:10)
流速:0.5mL/min
検出器:UV,210nm
カラムオーブン:40℃
(実施例1)式(I−1)で表される化合物の製造
The purity of the compound was analyzed by GC or UPLC. The analysis conditions are as follows.
(GC analysis conditions)
Column: Agilent Technologies, J & W Column DB-1HT, 15 m × 0.25 mm × 0.10 μm
Temperature program: 100 ° C (1 minute)-(20 ° C / minute)-250 ° C-(10 ° C / minute)-380 ° C-(7 ° C / minute)-400 ° C (2.64 minutes)
Inlet temperature: 350 ° C
Detector temperature: 400 ° C
(UPLC analysis conditions)
Column: Waters ACQUITY UPLC BEH C 18 , 2.1 × 100 mm, 1.7 μm
Elution solvent: acetonitrile / water (90:10)
Flow rate: 0.5 mL / min
Detector: UV, 210nm
Column oven: 40 ° C
Example 1 Production of Compound Represented by Formula (I-1)
撹拌装置を備えたフラスコに、式(I−1−1)で表される化合物 5.00g(24.2ミリモル)、式(I−1−2)で表される化合物 2.11g(12.1ミリモル)、トリフルオロ酢酸無水物 5.09g(24.2ミリモル)を加え混合した。5時間撹拌した後、ジクロロメタンで希釈し、分液処理、カラムクロマトグラフィー(シリカゲル)及び分散洗浄(ヘキサン)によって精製することにより、式(I−1−3)で表される化合物 5.31g(9.64ミリモル)を得た。 In a flask equipped with a stirrer, 5.00 g (24.2 mmol) of the compound represented by the formula (I-1-1) and 2.11 g of the compound represented by the formula (I-1-2) (12.12). 1 mmol) and 5.09 g (24.2 mmol) of trifluoroacetic anhydride were added and mixed. After stirring for 5 hours, the mixture was diluted with dichloromethane and purified by liquid separation treatment, column chromatography (silica gel), and dispersion washing (hexane) to obtain 5.31 g of a compound represented by the formula (I-1-3) ( 9.64 mmol).
200mLのオートクレーブに式(I−1−3)で表される化合物 5.31g(9.64ミリモル)、テトラヒドロフラン 50mL、濃硫酸 0.25mL及び5%Pdカーボン(50%含水) 0.27gを加え、水素圧 0.1MPa、室温で3時間撹拌した。触媒をセライトを用いて除去した後、溶媒を留去した。得られた粗生成物をトルエンに溶解させ、食塩水で洗浄した。有機層をカラムクロマトグラフィー(シリカゲル)で精製した後、再結晶(アセトン)することにより、目的の式(I−1)で表される化合物 4.28gを得た。純度99.78%であった。不純物として下記式(I−1i) To a 200 mL autoclave was added 5.31 g (9.64 mmol) of a compound represented by the formula (I-1-3), 50 mL of tetrahydrofuran, 0.25 mL of concentrated sulfuric acid, and 0.27 g of 5% Pd carbon (containing 50% water). The mixture was stirred at room temperature for 3 hours at a hydrogen pressure of 0.1 MPa. After removing the catalyst using celite, the solvent was distilled off. The obtained crude product was dissolved in toluene and washed with brine. The organic layer was purified by column chromatography (silica gel) and then recrystallized (acetone) to obtain 4.28 g of the target compound represented by the formula (I-1). The purity was 99.78%. As an impurity, the following formula (I-1i)
で表されるシクロヘキサノン骨格を有する核還元体0.03%を含有していた。
1H NMR(CDCl3)δ 1.34(m,8H),1.43(s,36H),1.59(m,4H),2.50(t,4H),5.00(s,2H),6.97(s,4H)ppm.
13C NMR(CDCl3)δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5,151.6ppm
LRMS(EI) m/z 522(100)
(比較例1)式(I−1a)で表される化合物の製造
It contained 0.03% of a nuclear reductant having a cyclohexanone skeleton represented by:
1 H NMR (CDCl 3 ) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13 C NMR (CDCl 3 ) δ 29.5, 29.6, 30.3, 32.0, 34.2, 36.0, 124.7, 133.5, 135.5, 151.6 ppm
LRMS (EI) m / z 522 (100)
(Comparative Example 1) Production of compound represented by formula (I-1a)
撹拌装置を備えたフラスコに水30mL、亜鉛粉末30g及び塩化水銀(II)1gを加え、30分間撹拌した。水をデカンテーションし、亜鉛アマルガムを水で洗浄した。反応容器に式(I−1−3)で表される化合物 8.26g(15.0ミリモル)、エタノール 120mL、亜鉛アマルガムを加えた。撹拌しながら、濃塩酸 30mL、水 30mLの混合水溶液を滴下した。12時間加熱還流し、トルエン 100mLを加えた。5分間撹拌した後、固体を濾過した。有機層を水で3回洗浄し、硫酸ナトリウムで乾燥した。クロマトグラフィー(シリカゲル)及び再結晶(アセトン)することにより、目的の式(I−1a)で表される化合物 3.20gを得た。純度99.75%であった。不純物として式(I−1i)で表されるシクロヘキサノン骨格を有する核還元体は検出されなかった。
1H NMR(CDCl3)δ 1.34(m,8H),1.43(s,36H),1.59(m,4H),2.50(t,4H),5.00(s,2H),6.97(s,4H)ppm.
13C NMR(CDCl3)δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5,151.6ppm
LRMS(EI) m/z 522(100)
(比較例2)式(I−1b)で表される化合物の製造
To a flask equipped with a stirrer, 30 mL of water, 30 g of zinc powder and 1 g of mercury (II) chloride were added, and stirred for 30 minutes. The water was decanted and the zinc amalgam was washed with water. To the reaction vessel, 8.26 g (15.0 mmol) of a compound represented by the formula (I-1-3), 120 mL of ethanol, and zinc amalgam were added. While stirring, a mixed aqueous solution of 30 mL of concentrated hydrochloric acid and 30 mL of water was added dropwise. The mixture was heated to reflux for 12 hours, and 100 mL of toluene was added. After stirring for 5 minutes, the solid was filtered. The organic layer was washed 3 times with water and dried over sodium sulfate. Chromatography (silica gel) and recrystallization (acetone) gave 3.20 g of the compound represented by the target formula (I-1a). The purity was 99.75%. A nuclear reductant having a cyclohexanone skeleton represented by the formula (I-1i) as an impurity was not detected.
1 H NMR (CDCl 3 ) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13 C NMR (CDCl 3 ) δ 29.5, 29.6, 30.3, 32.0, 34.2, 36.0, 124.7, 133.5, 135.5, 151.6 ppm
LRMS (EI) m / z 522 (100)
(Comparative Example 2) Production of compound represented by formula (I-1b)
撹拌装置を備えた反応容器に式(I−1−3)で表される化合物9.68g(17.6ミリモル)及び2−プロパノール 500mLを加えた。水素化ホウ素ナトリウム 2.0g(53ミリモル)を加え、室温で22時間撹拌した。水素化ホウ素ナトリウム 0.8g(21ミリモル)を追加しさらに1時間撹拌した。2N塩酸及び氷に、反応液を注いだ。析出した固体を濾過した。クロマトグラフィー(シリカゲル)及び再結晶(アセトン)することにより、目的の式(I−1b)で表される化合物 2.23gを得た。純度99.73%であった。不純物として式(I−1i)で表されるシクロヘキサノン骨格を有する核還元体は検出されなかった。
1H NMR(CDCl3)δ 1.34(m,8H),1.43(s,36H),1.59(m,4H),2.50(t,4H),5.00(s,2H),6.97(s,4H)ppm.
13C NMR(CDCl3)δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5,151.6ppm
LRMS(EI) m/z 522(100)
(実施例2)式(I−2)で表される化合物の製造
To a reaction vessel equipped with a stirrer, 9.68 g (17.6 mmol) of a compound represented by the formula (I-1-3) and 500 mL of 2-propanol were added. 2.0 g (53 mmol) of sodium borohydride was added and stirred at room temperature for 22 hours. 0.8 g (21 mmol) of sodium borohydride was added, and the mixture was further stirred for 1 hour. The reaction solution was poured into 2N hydrochloric acid and ice. The precipitated solid was filtered. Chromatography (silica gel) and recrystallization (acetone) gave 2.23 g of the compound represented by the target formula (I-1b). The purity was 99.73%. A nuclear reductant having a cyclohexanone skeleton represented by the formula (I-1i) as an impurity was not detected.
1 H NMR (CDCl 3 ) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13 C NMR (CDCl 3 ) δ 29.5, 29.6, 30.3, 32.0, 34.2, 36.0, 124.7, 133.5, 135.5, 151.6 ppm
LRMS (EI) m / z 522 (100)
Example 2 Production of Compound Represented by Formula (I-2)
撹拌装置を備えたフラスコに、式(I−1−1)で表される化合物 5.00g(24.2ミリモル)、式(I−2−1)で表される化合物 3.15g(24.2ミリモル)、トリフルオロ酢酸無水物 5.09g(24.2ミリモル)を加え混合した。5時間撹拌した後、ジクロロメタンで希釈し、分液処理、カラムクロマトグラフィー(シリカゲル)によって精製することにより、式(I−2−2)で表される化合物 6.46g(20.3ミリモル)を得た。 In a flask equipped with a stirrer, 5.00 g (24.2 mmol) of the compound represented by the formula (I-1-1) and 3.15 g (24. 2 mmol) and 5.09 g (24.2 mmol) of trifluoroacetic anhydride were added and mixed. After stirring for 5 hours, the mixture was diluted with dichloromethane and purified by liquid separation treatment and column chromatography (silica gel) to obtain 6.46 g (20.3 mmol) of the compound represented by the formula (I-2-2). Obtained.
200mLのオートクレーブに式(I−2−2)で表される化合物 6.46g(20.3ミリモル)、テトラヒドロフラン 30mL、酢酸 60mL及び5%Pdカーボン(50%含水) 0.32gを加え、水素圧 0.5MPa、室温で3時間撹拌した。触媒をセライトを用いて除去した後、テトラヒドロフランを留去した。得られた粗生成物をトルエンに溶解させ、食塩水で洗浄した。有機層をカラムクロマトグラフィー(シリカゲル)で精製することにより、目的の式(I−2)で表される化合物 5.06gを得た。純度99.58%であった。不純物として下記式(I−2i) To a 200 mL autoclave was added 6.46 g (20.3 mmol) of the compound represented by formula (I-2-2), 30 mL of tetrahydrofuran, 60 mL of acetic acid and 0.32 g of 5% Pd carbon (containing 50% water), and the hydrogen pressure The mixture was stirred at 0.5 MPa and room temperature for 3 hours. After removing the catalyst using Celite, the tetrahydrofuran was distilled off. The obtained crude product was dissolved in toluene and washed with brine. The organic layer was purified by column chromatography (silica gel) to obtain 5.06 g of the target compound represented by the formula (I-2). The purity was 99.58%. The following formula (I-2i) as an impurity
で表されるシクロヘキサノン骨格を有する核還元体0.32%を含有していた。
1H NMR(CDCl3)δ 0.89(t,3H),1.31(m,8H),1.44(s,18H),1.58(m,2H),2.51(t,2H),5.01(s,2H),6.97(s,2H)ppm.
13C NMR(CDCl3)δ 14.1,22.6,29.2,29.6,30.3,31.8,32.0,34.2,36.0,124.8,133.5,135.5,151.6ppm
LRMS(EI) m/z 304(100)
(比較例3)式(I−2a)で表される化合物の製造
And 0.32% of a nuclear reductant having a cyclohexanone skeleton represented by the formula:
1 H NMR (CDCl 3 ) δ 0.89 (t, 3H), 1.31 (m, 8H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13 C NMR (CDCl 3 ) δ 14.1, 22.6, 29.2, 29.6, 30.3, 31.8, 32.0, 34.2, 36.0, 124.8, 133. 5,135.5,151.6ppm
LRMS (EI) m / z 304 (100)
(Comparative Example 3) Production of compound represented by formula (I-2a)
比較例1と同様の方法によって製造し、カラムクロマトグラフィー(シリカゲル)によって精製を行い、式(I−2a)で表される化合物を合成した。純度99.83%であった。不純物として式(I−2i)で表されるシクロヘキサノン骨格を有する核還元体は検出されなかった。
1H NMR(CDCl3)δ 0.89(t,3H),1.31(m,8H),1.44(s,18H),1.58(m,2H),2.51(t,2H),5.01(s,2H),6.97(s,2H)ppm.
13C NMR(CDCl3)δ 14.1,22.6,29.2,29.6,30.3,31.8,32.0,34.2,36.0,124.8,133.5,135.5,151.6ppm
LRMS(EI) m/z 304(100)
(比較例4)式(I−2b)で表される化合物の製造
A compound produced by the same method as in Comparative Example 1 was purified by column chromatography (silica gel) to synthesize a compound represented by the formula (I-2a). The purity was 99.83%. A nuclear reductant having a cyclohexanone skeleton represented by the formula (I-2i) as an impurity was not detected.
1 H NMR (CDCl 3 ) δ 0.89 (t, 3H), 1.31 (m, 8H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13 C NMR (CDCl 3 ) δ 14.1, 22.6, 29.2, 29.6, 30.3, 31.8, 32.0, 34.2, 36.0, 124.8, 133. 5,135.5,151.6ppm
LRMS (EI) m / z 304 (100)
(Comparative Example 4) Production of compound represented by formula (I-2b)
撹拌装置及び温度計を備えた反応容器に式(I−2−2)で表される化合物 3.10g(9.74ミリモル)、トリフルオロ酢酸 30mLを加えた。氷冷しながらシアノ水素化ホウ素ナトリウム 2.06g(39.0ミリモル)を加えた。3時間撹拌した後、塩酸に注いだ。トルエンを加え、重曹水及び食塩水で洗浄した。硫酸マグネシウムで乾燥した後、溶媒を留去した。カラムクロマトグラフィー(シリカゲル)で精製することにより、目的の式(I−2b)で表される化合物 2.02gを得た。純度99.79%であった。不純物として式(I−2i)で表されるシクロヘキサノン骨格を有する核還元体は検出されなかった。
1H NMR(CDCl3)δ 0.89(t,3H),1.31(m,8H),1.44(s,18H),1.58(m,2H),2.51(t,2H),5.01(s,2H),6.97(s,2H)ppm.
13C NMR(CDCl3)δ 14.1,22.6,29.2,29.6,30.3,31.8,32.0,34.2,36.0,124.8,133.5,135.5,151.6ppm
LRMS(EI) m/z 304(100)
(実施例3)式(I−3)で表される化合物の製造
To a reaction vessel equipped with a stirrer and a thermometer, 3.10 g (9.74 mmol) of the compound represented by the formula (I-2-2) and 30 mL of trifluoroacetic acid were added. While cooling with ice, 2.06 g (39.0 mmol) of sodium cyanoborohydride was added. After stirring for 3 hours, it was poured into hydrochloric acid. Toluene was added and washed with an aqueous sodium bicarbonate solution and brine. After drying with magnesium sulfate, the solvent was distilled off. By purification by column chromatography (silica gel), 2.02 g of the compound represented by the target formula (I-2b) was obtained. The purity was 99.79%. A nuclear reductant having a cyclohexanone skeleton represented by the formula (I-2i) as an impurity was not detected.
1 H NMR (CDCl 3 ) δ 0.89 (t, 3H), 1.31 (m, 8H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13 C NMR (CDCl 3 ) δ 14.1, 22.6, 29.2, 29.6, 30.3, 31.8, 32.0, 34.2, 36.0, 124.8, 133. 5,135.5,151.6ppm
LRMS (EI) m / z 304 (100)
Example 3 Production of Compound Represented by Formula (I-3)
撹拌装置を備えたフラスコに、式(I−1−1)で表される化合物 5.00g(24.2ミリモル)、式(I−3−1)で表される化合物 6.46g(24.2ミリモル)、トリフルオロ酢酸無水物 5.09g(24.2ミリモル)を加え混合した。5時間撹拌した後、ジクロロメタンで希釈し、分液処理、カラムクロマトグラフィー(シリカゲル)によって精製することにより、式(I−3−2)で表される化合物 8.93g(19.6ミリモル)を得た。 In a flask equipped with a stirrer, 5.00 g (24.2 mmol) of the compound represented by the formula (I-1-1) and 6.46 g (24. 2 mmol) and 5.09 g (24.2 mmol) of trifluoroacetic anhydride were added and mixed. After stirring for 5 hours, the mixture was diluted with dichloromethane and purified by liquid separation treatment and column chromatography (silica gel) to obtain 8.93 g (19.6 mmol) of the compound represented by the formula (I-3-2). Obtained.
200mLのオートクレーブに式(I−3−2)で表される化合物 8.93g(19.6ミリモル)、テトラヒドロフラン 89mL、濃硫酸 0.89mL及び5%Pdカーボン(50%含水) 0.45gを加え、水素圧 0.2MPa、室温で2時間撹拌した。触媒をセライトを用いて除去した後、溶媒を留去した。得られた粗生成物をトルエンに溶解させ、食塩水で洗浄した。有機層をカラムクロマトグラフィー(シリカゲル)で精製することにより、目的の式(I−3)で表される化合物 6.92gを得た。純度99.45%であった。不純物として下記式(I−3i) To a 200 mL autoclave was added 8.93 g (19.6 mmol) of the compound represented by the formula (I-3-2), 89 mL of tetrahydrofuran, 0.89 mL of concentrated sulfuric acid, and 0.45 g of 5% Pd carbon (containing 50% water). The mixture was stirred at room temperature for 2 hours at a hydrogen pressure of 0.2 MPa. After removing the catalyst using celite, the solvent was distilled off. The obtained crude product was dissolved in toluene and washed with brine. The organic layer was purified by column chromatography (silica gel) to obtain 6.92 g of the target compound represented by the formula (I-3). The purity was 99.45%. The following formula (I-3i) as an impurity
で表されるシクロヘキサノン骨格を有する核還元体0.32%を含有していた。
1H NMR(CDCl3)δ 0.95〜1.59(m,29H),2.50(t,4H),5.00(s,2H),6.97(s,4H)ppm.
13C NMR(CDCl3)δ 14.4,20.5,26.8,26.8,29.3,29.4,30.9,30.9,31.6,34.7,37.1,37.3,38.3,41.6,41.6,124.7,133.5,135.5,151.6ppm
LRMS(EI) m/z 440(100)
(実施例4)式(I−4)で表される化合物の製造
And 0.32% of a nuclear reductant having a cyclohexanone skeleton represented by the formula:
1 H NMR (CDCl 3 ) δ 0.95 to 1.59 (m, 29H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13 C NMR (CDCl 3 ) δ 14.4, 20.5, 26.8, 26.8, 29.3, 29.4, 30.9, 30.9, 31.6, 34.7, 37. 1,37.3,38.3,41.6,41.6,124.7,133.5,135.5,151.6ppm
LRMS (EI) m / z 440 (100)
Example 4 Production of Compound Represented by Formula (I-4)
実施例1と同様の方法によって、式(I−4)で表される化合物を合成した。純度99.65%であった。不純物として下記式(I−4i) A compound represented by the formula (I-4) was synthesized by the same method as in Example 1. The purity was 99.65%. The following formula (I-4i) as an impurity
で表されるシクロヘキサノン骨格を有する核還元体0.21%を含有していた。
1H NMR(CDCl3)δ 1.43(s,36H),1.59(m,4H),2.50(t,4H),5.00(s,2H),6.97(s,4H)ppm.
13C NMR(CDCl3)δ 30.3,32.0,34.2,36.0,124.7,133.5,135.5,151.6ppm
LRMS(EI) m/z 466(100)
(実施例5)式(I−5)で表される化合物の製造
It contained 0.21% of a nuclear reductant having a cyclohexanone skeleton represented by:
1 H NMR (CDCl 3 ) δ 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13 C NMR (CDCl 3 ) δ 30.3, 32.0, 34.2, 36.0, 124.7, 133.5, 135.5, 151.6 ppm
LRMS (EI) m / z 466 (100)
Example 5 Production of Compound Represented by Formula (I-5)
滴下ロート、温度計及び撹拌装置を備えた反応容器にマグネシウム 0.54g(22.2ミリモル)、テトラヒドロフラン 2mLを加え、式(I−5−2)で表される化合物 3.10g(20.5ミリモル)をテトラヒドロフラン 6mLに溶解させた溶液を徐々に滴下しグリニャール試薬を調製した。滴下ロート、温度計及び撹拌装置を備えた反応容器に式(I−5−1)で表される化合物 5.00g(17.1ミリモル)、テトラヒドロフラン 10mLを加え溶解させた。グリニャール試薬を徐々に滴下した。3時間撹拌した後、塩酸及びトルエンを加え分液処理した。有機層をカラムクロマトグラフィー(シリカゲル)により精製し、式(I−5−3)で表される化合物 3.64g(10.9ミリモル)を得た。 To a reaction vessel equipped with a dropping funnel, a thermometer and a stirrer, 0.54 g (22.2 mmol) of magnesium and 2 mL of tetrahydrofuran were added, and 3.10 g (20.5) of a compound represented by the formula (I-5-2) A solution obtained by dissolving (mmol) in 6 mL of tetrahydrofuran was gradually added dropwise to prepare a Grignard reagent. In a reaction vessel equipped with a dropping funnel, a thermometer and a stirrer, 5.00 g (17.1 mmol) of the compound represented by the formula (I-5-1) and 10 mL of tetrahydrofuran were added and dissolved. Grignard reagent was gradually added dropwise. After stirring for 3 hours, hydrochloric acid and toluene were added for liquid separation. The organic layer was purified by column chromatography (silica gel) to obtain 3.64 g (10.9 mmol) of the compound represented by the formula (I-5-3).
200mLのオートクレーブに式(I−5−3)で表される化合物 3.64g(10.9ミリモル)、エタノール36mL、酢酸36mL及び5%Pdカーボン(50%含水) 0.18gを加え、水素圧 0.5MPa、40℃で2時間撹拌した。触媒をセライトを用いて除去した後、トルエンを加え食塩水で洗浄した。有機層をカラムクロマトグラフィー(シリカゲル)で精製することにより、目的の式(I−5)で表される化合物 2.77gを得た。純度99.58%であった。不純物として下記式(I−5i) To a 200 mL autoclave was added 3.64 g (10.9 mmol) of the compound represented by the formula (I-5-3), 36 mL of ethanol, 36 mL of acetic acid and 0.18 g of 5% Pd carbon (containing 50% water), and the hydrogen pressure The mixture was stirred at 0.5 MPa and 40 ° C. for 2 hours. After removing the catalyst using Celite, toluene was added and the mixture was washed with brine. The organic layer was purified by column chromatography (silica gel) to obtain 2.77 g of the target compound represented by the formula (I-5). The purity was 99.58%. The following formula (I-5i) as an impurity
で表されるシクロヘキサノン骨格を有する核還元体0.37%を含有していた。
1H NMR(CDCl3)δ 0.89(t,3H),1.31(m,10H),1.44(s,18H),1.58(m,2H),2.51(t,2H),5.01(s,2H),6.97(s,2H)ppm.
13C NMR(CDCl3)δ 14.1,22.6,29.2,29.6,29.6,30.3,31.8,32.0,34.2,36.0,124.8,133.5,135.5,151.6ppm
LRMS(EI) m/z 318(100)
(比較例5)式(I−5a)で表される化合物の製造
And 0.37% of a nuclear reductant having a cyclohexanone skeleton represented by the formula:
1 H NMR (CDCl 3 ) δ 0.89 (t, 3H), 1.31 (m, 10H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13 C NMR (CDCl 3 ) δ 14.1, 22.6, 29.2, 29.6, 29.6, 30.3, 31.8, 32.0, 34.2, 36.0, 124. 8,133.5,135.5,151.6ppm
LRMS (EI) m / z 318 (100)
(Comparative Example 5) Production of compound represented by formula (I-5a)
比較例2と同様の方法によって、式(I−5a)で表される化合物を合成した。純度99.81%であった。不純物として式(I−5i)で表されるシクロヘキサノン骨格を有する核還元体は検出されなかった。
1H NMR(CDCl3)δ 0.89(t,3H),1.31(m,10H),1.44(s,18H),1.58(m,2H),2.51(t,2H),5.01(s,2H),6.97(s,2H)ppm.
13C NMR(CDCl3)δ 14.1,22.6,29.2,29.6,29.6,30.3,31.8,32.0,34.2,36.0,124.8,133.5,135.5,151.6ppm
LRMS(EI) m/z 318(100)
(比較例6)式(I−1c)で表される化合物の製造
A compound represented by formula (I-5a) was synthesized in the same manner as in Comparative Example 2. The purity was 99.81%. A nuclear reductant having a cyclohexanone skeleton represented by the formula (I-5i) as an impurity was not detected.
1 H NMR (CDCl 3 ) δ 0.89 (t, 3H), 1.31 (m, 10H), 1.44 (s, 18H), 1.58 (m, 2H), 2.51 (t, 2H), 5.01 (s, 2H), 6.97 (s, 2H) ppm.
13 C NMR (CDCl 3 ) δ 14.1, 22.6, 29.2, 29.6, 29.6, 30.3, 31.8, 32.0, 34.2, 36.0, 124. 8,133.5,135.5,151.6ppm
LRMS (EI) m / z 318 (100)
(Comparative Example 6) Production of compound represented by formula (I-1c)
撹拌装置、ディーンスターク装置、冷却器及び温度計を備えた反応容器に、式(I−1−3)で表される化合物 3.00g(5.45ミリモル)、ヒドラジン一水和物 2.18g(43.5ミリモル)、水酸化ナトリウム 1.09g(27.3ミリモル)、エチレングリコール 15mLを加え、200℃で8時間水を除去しながら加熱還流した。GCによって分析を行ったが、式(I−1c)で表される化合物は生成しなかった。
(比較例7)式(I−1d)で表される化合物の製造
In a reaction vessel equipped with a stirrer, a Dean-Stark device, a condenser and a thermometer, 3.00 g (5.45 mmol) of the compound represented by the formula (I-1-3) and 2.18 g of hydrazine monohydrate. (43.5 mmol), 1.09 g (27.3 mmol) of sodium hydroxide and 15 mL of ethylene glycol were added, and the mixture was heated to reflux while removing water at 200 ° C. for 8 hours. Analysis by GC did not produce the compound represented by formula (I-1c).
(Comparative Example 7) Production of compound represented by formula (I-1d)
撹拌装置、温度計及び滴下ロートを備えた反応容器に、式(I−1d−1)で表される化合物100.00g(0.455モル)、ヨウ化銅(I)1.73g(9.08ミリモル)、テトラヒドロフラン300mL、2−アミノエタノール100mL、水150mLを加えた。反応容器内を窒素ガスで置換した後、テトラキス(トリフェニルホスフィン)パラジウム(0)5.25g(4.54ミリモル)を加え加熱還流させた。式(I−1d−2)で表される化合物24.13g(0.227g)をテトラヒドロフラン48mLに溶解させた溶液を30分間かけて滴下した。その後、3時間加熱還流させた。酢酸エチル400mL及び10%塩酸600mLを加え分液処理した後、有機層を食塩水400mLで5回洗浄した。カラムクロマトグラフィー(アルミナ)により精製を行い、濃縮乾固させることにより式(I−1d−3)で表される化合物を含む褐色固体68.41gを得た。 In a reaction vessel equipped with a stirrer, a thermometer and a dropping funnel, 100.00 g (0.455 mol) of the compound represented by the formula (I-1d-1) and 1.73 g of copper (I) iodide (9. 08 mmol), 300 mL of tetrahydrofuran, 100 mL of 2-aminoethanol, and 150 mL of water were added. After replacing the inside of the reaction vessel with nitrogen gas, 5.25 g (4.54 mmol) of tetrakis (triphenylphosphine) palladium (0) was added and heated to reflux. A solution prepared by dissolving 24.13 g (0.227 g) of the compound represented by the formula (I-1d-2) in 48 mL of tetrahydrofuran was added dropwise over 30 minutes. Thereafter, the mixture was heated to reflux for 3 hours. After separation by adding 400 mL of ethyl acetate and 600 mL of 10% hydrochloric acid, the organic layer was washed 5 times with 400 mL of brine. Purification by column chromatography (alumina) and concentration to dryness gave 68.41 g of a brown solid containing the compound represented by formula (I-1d-3).
撹拌装置を備えた2Lのオートクレーブに、得られた式(I−1d−3)で表される化合物を含む褐色固体68.41g、5%パラジウムカーボン(50%含水)6.84g、エタノール342mLを加えた。水素圧0.5MPa、50℃で3日間反応させた。触媒を濾過により除去し、溶媒を留去することにより、式(I−1d−4)で表される化合物を含む褐色固体69.81gを得た。 In a 2 L autoclave equipped with a stirrer, 68.41 g of the obtained brown solid containing the compound represented by the formula (I-1d-3), 6.84 g of 5% palladium carbon (containing 50% water), and 342 mL of ethanol were added. added. The reaction was carried out at a hydrogen pressure of 0.5 MPa and 50 ° C. for 3 days. The catalyst was removed by filtration, and the solvent was distilled off to obtain 69.81 g of a brown solid containing the compound represented by the formula (I-1d-4).
撹拌装置、温度計及び滴下ロートを備えた反応容器に、式(I−1d−4)で表される化合物を含む褐色固体5.00g(16.75ミリモル)、tert−ブチルアルコール4.97g(67.05ミリモル)、酢酸10mLを加えた。氷冷しながら濃硫酸6.57g(66.99ミリモル)を滴下した。室温で1週間撹拌したが、目的の式(I−1d)で表される化合物は55%(GC)しか生成していなかった。反応液を氷水に注ぎ、酢酸エチルで抽出、食塩水で洗浄した。濃縮乾固した後、カラムクロマトグラフィー(シリカゲル、ヘキサン)及び再結晶(アセトン)により精製を行い、目的の式(I−1d)で表される化合物2.31gを得た。
1H NMR(CDCl3)δ 1.34(m,8H),1.43(s,36H),1.59(m,4H),2.50(t,4H),5.00(s,2H),6.97(s,4H)ppm.
13C NMR(CDCl3)δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5,151.6ppm
LRMS(EI) m/z 522(100)
(比較例8)式(I−1e)で表される化合物の製造
In a reaction vessel equipped with a stirrer, a thermometer and a dropping funnel, 5.00 g (16.75 mmol) of a brown solid containing a compound represented by the formula (I-1d-4), 4.97 g of tert-butyl alcohol ( 67.05 mmol) and 10 mL of acetic acid was added. While cooling with ice, 6.57 g (66.99 mmol) of concentrated sulfuric acid was added dropwise. The mixture was stirred at room temperature for 1 week, but only 55% (GC) of the target compound represented by the formula (I-1d) was produced. The reaction mixture was poured into ice water, extracted with ethyl acetate, and washed with brine. After concentration to dryness, purification was performed by column chromatography (silica gel, hexane) and recrystallization (acetone) to obtain 2.31 g of the compound represented by the target formula (I-1d).
1 H NMR (CDCl 3 ) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13 C NMR (CDCl 3 ) δ 29.5, 29.6, 30.3, 32.0, 34.2, 36.0, 124.7, 133.5, 135.5, 151.6 ppm
LRMS (EI) m / z 522 (100)
(Comparative Example 8) Production of compound represented by formula (I-1e)
撹拌装置、温度計及びガス導入装置を備えた反応容器に、式(I−1d−4)で表される化合物を含む褐色固体5.00g(16.75ミリモル)、トルエン30mL、濃硫酸0.49g(5.00ミリモル)を加えた。65℃で撹拌しながら、イソブテンを導入し続けた。1週間反応させたが、目的の式(I−1e)で表される化合物は75%(GC)しか生成していなかった。反応液を氷水に注ぎ、酢酸エチルで抽出、食塩水で洗浄した。濃縮乾固した後、カラムクロマトグラフィー(シリカゲル、ヘキサン)及び再結晶(アセトン)により精製を行い、目的の式(I−1e)で表される化合物3.20gを得た。
1H NMR(CDCl3)δ 1.34(m,8H),1.43(s,36H),1.59(m,4H),2.50(t,4H),5.00(s,2H),6.97(s,4H)ppm.
13C NMR(CDCl3)δ 29.5,29.6,30.3,32.0,34.2,36.0,124.7,133.5,135.5,151.6ppm
LRMS(EI) m/z 522(100)
(比較例9)式(I−1f)で表される化合物の製造
In a reaction vessel equipped with a stirrer, a thermometer and a gas introduction device, 5.00 g (16.75 mmol) of a brown solid containing a compound represented by the formula (I-1d-4), 30 mL of toluene, and 0. 49 g (5.00 mmol) was added. While stirring at 65 ° C., isobutene continued to be introduced. The reaction was carried out for 1 week, but only 75% (GC) of the target compound represented by the formula (I-1e) was produced. The reaction mixture was poured into ice water, extracted with ethyl acetate, and washed with brine. After concentration to dryness, purification was performed by column chromatography (silica gel, hexane) and recrystallization (acetone) to obtain 3.20 g of the compound represented by the target formula (I-1e).
1 H NMR (CDCl 3 ) δ 1.34 (m, 8H), 1.43 (s, 36H), 1.59 (m, 4H), 2.50 (t, 4H), 5.00 (s, 2H), 6.97 (s, 4H) ppm.
13 C NMR (CDCl 3 ) δ 29.5, 29.6, 30.3, 32.0, 34.2, 36.0, 124.7, 133.5, 135.5, 151.6 ppm
LRMS (EI) m / z 522 (100)
(Comparative Example 9) Production of compound represented by formula (I-1f)
式(I−1−3)で表される化合物5.00g(9.08ミリモル)をエタノール及び水の混合溶媒に懸濁させ、水素化ホウ素ナトリウム0.69g(18.2ミリモル)を加えた。室温で5時間撹拌した後、塩酸を徐々に加えた。酢酸エチルで抽出、食塩水で洗浄した後、溶媒を留去することにより式(I−1−4)で表される化合物を得た。得られた化合物をイソプロピルアルコールに溶解させ、10%Pdカーボン及び濃塩酸を加え、水素圧0.29MPa、80℃で2時間撹拌した。触媒を濾過し溶媒を留去しヘキサン及びトルエンを添加し−5℃で晶析、濾過、乾燥し式(I−1f)で表される化合物を得た。純度96.98%であった。不純物として式(I−1i)で表されるシクロヘキサノン骨格を有する核還元体2.15%を含有していた。
(実施例6〜10及び比較例10〜14)
以下に、実施例1〜5及び比較例1〜5で製造した化合物を母体液晶に添加し評価した結果を記述する。
5.00 g (9.08 mmol) of the compound represented by the formula (I-1-3) was suspended in a mixed solvent of ethanol and water, and 0.69 g (18.2 mmol) of sodium borohydride was added. . After stirring at room temperature for 5 hours, hydrochloric acid was gradually added. After extraction with ethyl acetate and washing with brine, the solvent was distilled off to obtain a compound represented by the formula (I-1-4). The obtained compound was dissolved in isopropyl alcohol, 10% Pd carbon and concentrated hydrochloric acid were added, and the mixture was stirred at 80 ° C. for 2 hours at a hydrogen pressure of 0.29 MPa. The catalyst was filtered, the solvent was distilled off, hexane and toluene were added, crystallization was performed at -5 ° C, filtration and drying to obtain a compound represented by the formula (I-1f). The purity was 96.98%. It contained 2.15% of a nuclear reductant having a cyclohexanone skeleton represented by the formula (I-1i) as an impurity.
(Examples 6 to 10 and Comparative Examples 10 to 14)
Below, the result of having added the compound manufactured in Examples 1-5 and Comparative Examples 1-5 to the base liquid crystal and evaluating it is described.
下記化合物によって構成される液晶組成物を調製し、母体液晶(X)とした。 A liquid crystal composition composed of the following compounds was prepared and used as a base liquid crystal (X).
この母体液晶(X)に、評価対象の化合物を0.1%及び、下記重合性化合物 In this base liquid crystal (X), 0.1% of the compound to be evaluated and the following polymerizable compound
を0.3%添加し溶解させ重合性液晶組成物を調製し、評価対象の重合性液晶組成物とした。この評価対象の重合性液晶組成物を、セルギャップ3.5μmでホメオトロピック配向を誘起するポリイミド配向膜を塗布したITO付きセルに真空注入法で注入した。周波数1kHzで1.8Vの矩形波を印加しながら、高圧水銀灯を用いて320nm以上のUVを10mW/cm2で600秒間照射することにより、評価対象の垂直配向性液晶表示素子(XI)を作製した。液晶のプレチルト角は87.3度で固定されていた。下記表に評価対象の化合物と液晶表示素子の関係を示す。 Was added to dissolve it to prepare a polymerizable liquid crystal composition to obtain a polymerizable liquid crystal composition to be evaluated. The polymerizable liquid crystal composition to be evaluated was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. While applying a rectangular wave of 1.8 V at a frequency of 1 kHz, using a high-pressure mercury lamp, irradiation with UV of 320 nm or more is performed at 10 mW / cm 2 for 600 seconds to produce a vertical alignment liquid crystal display element (XI) to be evaluated. did. The pretilt angle of the liquid crystal was fixed at 87.3 degrees. The following table shows the relationship between the evaluation target compound and the liquid crystal display element.
実施例6〜10及び比較例10〜14の表示素子を電圧印加し、経過時間ごとの外観を確認した。焼き付きが全く見られない場合は◎、焼き付きが見られた場合は焼き付きの程度によって○(焼き付きがごくわずかに発生)、△(焼き付きがやや強く発生)、×(焼き付きが非常に強く発生)とした。結果を下表に示す。
Voltage was applied to the display elements of Examples 6 to 10 and Comparative Examples 10 to 14, and the appearance for each elapsed time was confirmed. ◎ if there is no image sticking, ◎ if there is image sticking, depending on the degree of image sticking, ○ (very little image sticking occurs), △ (some image sticking occurs slightly), and × (very much image sticking occurs). did. The results are shown in the table below.
比較例10〜14の比較化合物を含有する表示素子は、いずれも表示後1000時間以内に焼き付きがやや強く発生し、10000時間以内にほぼ全面にわたり表示不良が見られた。これに対し、本願発明の製造方法によって製造した化合物を含有する表示素子は、表示後10000時間後においても高品位〜良好な表示状態を維持した。 In each of the display elements containing the comparative compounds of Comparative Examples 10 to 14, image sticking occurred somewhat strongly within 1000 hours after display, and display defects were observed over almost the entire surface within 10,000 hours. On the other hand, the display element containing the compound produced by the production method of the present invention maintained a high-quality to good display state even after 10,000 hours after display.
以上の結果から、本願発明の製造方法によって製造された化合物は、特許文献3記載の製法によって製造した場合と比較しシクロヘキサノン構造を有する不純物の含有量が少ない。また、本願発明の製造方法によって製造した化合物を含有する表示素子は焼き付きが起こりにくいことから、本願発明の製造方法によって製造された化合物は、PSA型液晶表示素子用の材料として有用である。また、公知の製造方法と比較して反応時間が短時間であることから、本願発明の製造方法は生産性に優れる。 From the above results, the compound produced by the production method of the present invention has a lower content of impurities having a cyclohexanone structure than that produced by the production method described in Patent Document 3. Moreover, since the display element containing the compound manufactured by the manufacturing method of the present invention is less likely to burn, the compound manufactured by the manufacturing method of the present invention is useful as a material for a PSA type liquid crystal display element. Moreover, since the reaction time is short compared with a well-known manufacturing method, the manufacturing method of this invention is excellent in productivity.
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