JP6443708B2 - Method for producing E-olefin compound - Google Patents
Method for producing E-olefin compound Download PDFInfo
- Publication number
- JP6443708B2 JP6443708B2 JP2018513677A JP2018513677A JP6443708B2 JP 6443708 B2 JP6443708 B2 JP 6443708B2 JP 2018513677 A JP2018513677 A JP 2018513677A JP 2018513677 A JP2018513677 A JP 2018513677A JP 6443708 B2 JP6443708 B2 JP 6443708B2
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- Japan
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- general formula
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 70
- 150000001875 compounds Chemical group 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 125000002947 alkylene group Chemical group 0.000 claims description 25
- 125000001153 fluoro group Chemical group F* 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- -1 methanesulfonyloxymethyl group Chemical group 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 14
- 150000003464 sulfur compounds Chemical class 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 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 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 claims description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000005997 bromomethyl group Chemical group 0.000 claims description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000004973 liquid crystal related substance Substances 0.000 description 18
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000006317 isomerization reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ATKJLMWDXASAJA-UHFFFAOYSA-N benzenesulfonylsulfanylbenzene Chemical compound C=1C=CC=CC=1S(=O)(=O)SC1=CC=CC=C1 ATKJLMWDXASAJA-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- CXJVMJWCNFOERL-UHFFFAOYSA-N benzenesulfonylsulfonylbenzene Chemical compound C=1C=CC=CC=1S(=O)(=O)S(=O)(=O)C1=CC=CC=C1 CXJVMJWCNFOERL-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical group C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZIXXRXGPBFMPFD-UHFFFAOYSA-N 1-chloro-4-[(4-chlorophenyl)disulfanyl]benzene Chemical compound C1=CC(Cl)=CC=C1SSC1=CC=C(Cl)C=C1 ZIXXRXGPBFMPFD-UHFFFAOYSA-N 0.000 description 1
- PZQGLCGLPMWYBT-UHFFFAOYSA-N 1-methoxy-4-[(4-methoxyphenyl)disulfanyl]benzene Chemical compound C1=CC(OC)=CC=C1SSC1=CC=C(OC)C=C1 PZQGLCGLPMWYBT-UHFFFAOYSA-N 0.000 description 1
- TZOVOULUMXXLOJ-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)disulfanyl]benzene Chemical compound C1=CC(C)=CC=C1SSC1=CC=C(C)C=C1 TZOVOULUMXXLOJ-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- YYYOQURZQWIILK-UHFFFAOYSA-N 2-[(2-aminophenyl)disulfanyl]aniline Chemical compound NC1=CC=CC=C1SSC1=CC=CC=C1N YYYOQURZQWIILK-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- XBNOMKROXZGMFW-UHFFFAOYSA-N 3-[(3-hydroxyphenyl)disulfanyl]phenol Chemical compound OC1=CC=CC(SSC=2C=C(O)C=CC=2)=C1 XBNOMKROXZGMFW-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 1
- GAMSSMZJKUMFEY-UHFFFAOYSA-N 4-[(4-carboxyphenyl)disulfanyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1SSC1=CC=C(C(O)=O)C=C1 GAMSSMZJKUMFEY-UHFFFAOYSA-N 0.000 description 1
- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N C1CC=CCC1 Chemical compound C1CC=CCC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- RHJITQJBHCWZLJ-UHFFFAOYSA-N CC(C1)C1NC Chemical compound CC(C1)C1NC RHJITQJBHCWZLJ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 235000013557 nattō Nutrition 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/08—Isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/05—Alcohols containing rings other than six-membered aromatic rings
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Description
本発明は医薬、農薬、液晶材料等の化成品の製造中間体及び原体として有用なE−オレフィン化合物の製造方法に関する。 The present invention relates to a method for producing an E-olefin compound useful as a production intermediate and a raw material for chemical products such as pharmaceuticals, agricultural chemicals, and liquid crystal materials.
E−オレフィン化合物は、医薬、農薬、液晶材料の分野において優れた特性を示すことが多く、有用な化合物である。特に、液晶材料においては、E−オレフィン化合物は対応する飽和化合物よりも高い透明点、比較的低い粘度及び大きな弾性定数を示すことが知られており、極めて重要な化合物である。一般的にE−オレフィン化合物は、E−オレフィン化合物及び対応するZ−オレフィン化合物を含む組成物を、アリールスルフィン酸類を触媒として用いた異性化反応により、組成物中のE−オレフィン化合物の比率を高める工程を経て製造されている(非特許文献1、2)。また、アリールスルフィン酸は不安定であることが知られているため、一般的には対応するアリールスルフィン酸塩として購入・保管し、使用する際に反応系内にて塩酸等の酸と反応させ、新鮮なアリールスルフィン酸を生成させて使用している。この際、E−オレフィン化合物及び対応するZ−オレフィン化合物を含む組成物、スルフィン酸塩、酸及び溶媒を室温にて混合した後、所定の反応温度に加熱するという工程が一般的に用いられている(特許文献1、非特許文献1及び非特許文献2)。 E-olefin compounds are useful compounds because they often exhibit excellent properties in the fields of pharmaceuticals, agricultural chemicals, and liquid crystal materials. In particular, in liquid crystal materials, E-olefin compounds are known to exhibit higher clearing points, relatively lower viscosities, and larger elastic constants than the corresponding saturated compounds, and are extremely important compounds. Generally, an E-olefin compound is obtained by subjecting a composition containing an E-olefin compound and a corresponding Z-olefin compound to an isomerization reaction using an arylsulfinic acid as a catalyst, to determine the ratio of the E-olefin compound in the composition. It is manufactured through a process of increasing (Non-Patent Documents 1 and 2). In addition, since arylsulfinic acid is known to be unstable, it is generally purchased and stored as the corresponding arylsulfinate and reacted with an acid such as hydrochloric acid in the reaction system when used. , Fresh arylsulfinic acid is produced and used. At this time, a process of mixing a composition containing an E-olefin compound and a corresponding Z-olefin compound, a sulfinate, an acid and a solvent at room temperature and then heating to a predetermined reaction temperature is generally used. (Patent Literature 1, Non-Patent Literature 1 and Non-Patent Literature 2).
ところで、従来の異性化反応における酸性且つ高温という条件では、酸に弱い官能基、例えばエステル基、2−テトラヒドロピラニル基等を有する化合物を基質として用いると加水分解してしまうため、目的の異性化体を収率良く得ることが難しい。このため、従来の異性化反応の条件では、適用可能な基質が限られている。 By the way, under the conditions of acidity and high temperature in the conventional isomerization reaction, if a compound having a functional group that is weak against an acid, such as an ester group or 2-tetrahydropyranyl group, is used as a substrate, hydrolysis occurs. It is difficult to obtain a compound with good yield. For this reason, applicable substrates are limited under the conditions of conventional isomerization reactions.
そこで本発明は、広範なZ−オレフィン化合物を基質として適用可能な、E−オレフィン化合物の製造方法を提供することを目的とする。 Then, an object of this invention is to provide the manufacturing method of an E-olefin compound which can apply a wide Z-olefin compound as a substrate.
本発明者らは鋭意検討した結果、分子中に1つ又は2つ以上のZ体を表すオレフィン構造を有するオレフィン誘導体に硫黄化合物及びラジカル開始剤を作用させ、Z体を表すオレフィン構造の少なくとも1つをE体を表すオレフィン構造に異性化させる、異性化体の製造方法により、酸を用いなくとも、Z−オレフィン構造をE−オレフィン構造に異性化できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have made a sulfur compound and a radical initiator act on an olefin derivative having an olefin structure representing one or two or more Z isomers in the molecule, thereby at least one of the olefin structures representing the Z isomer. By isomerizing the olefin into an olefin structure representing the E isomer, it was found that a Z-olefin structure could be isomerized to an E olefin structure without using an acid, and the present invention was completed. It was.
かかる製造方法により、Z−オレフィン構造をE−オレフィン構造に異性化できる理由は必ずしも明らかでないが、本発明者らは、硫黄化合物及びラジカル開始剤が反応することで硫黄ラジカルが生成し、この硫黄ラジカルがオレフィンに作用することにより異性化が促進され、熱力学的に安定なE−オレフィン構造を有する異性化体が主として得られるものと考えている。 Although the reason why the Z-olefin structure can be isomerized to the E-olefin structure by such a production method is not necessarily clear, the present inventors generate sulfur radicals by reacting a sulfur compound and a radical initiator. It is thought that isomerization is promoted by the action of radicals on the olefin, and isomers having a thermodynamically stable E-olefin structure are mainly obtained.
また本発明は、分子中に1つ又は2つ以上のZ体を表すオレフィン構造を有するオレフィン誘導体にS−S結合含有化合物を加熱下で作用させ、Z体を表すオレフィン構造の少なくとも1つをE体を表すオレフィン構造に異性化させる、異性化体の製造方法であってもよい。かかる製造方法によっても、硫黄ラジカルを発生させることができるので、硫黄化合物及びラジカル開始剤を作用させた場合と同様に、Z−オレフィン構造をE−オレフィン構造に異性化することができる。 In the present invention, an S—S bond-containing compound is allowed to act on an olefin derivative having an olefin structure representing one or more Z isomers in the molecule under heating, and at least one of the olefin structures representing the Z isomer is converted. It may be a method for producing an isomer by isomerization to an olefin structure representing E form. Also by this manufacturing method, since a sulfur radical can be generated, the Z-olefin structure can be isomerized to an E-olefin structure in the same manner as when a sulfur compound and a radical initiator are allowed to act.
本発明によれば、広範なZ−オレフィン化合物を基質として適用可能な、E−オレフィン化合物の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of an E-olefin compound which can apply a wide Z-olefin compound as a substrate can be provided.
本発明は、分子中に1つ又は2つ以上のZ体を表すオレフィン構造を有するオレフィン誘導体に硫黄化合物及びラジカル開始剤を作用させ、Z体を表すオレフィン構造の少なくとも1つをE体を表すオレフィン構造に異性化させる、異性化体の製造方法である。なお、本明細書中、分子中に1つ又は2つ以上のZ体を表すオレフィン構造を有するオレフィン誘導体を「Z−オレフィン誘導体」ともいい、Z−オレフィン誘導体におけるZ体を表すオレフィン構造の少なくとも1つがE体を表すオレフィン構造により置換されたオレフィン誘導体を「E−オレフィン誘導体」ともいい、これらの誘導体の両方を含む組成物を「E/Z−オレフィン組成物」ともいう。上記異性化体はE−オレフィン誘導体に相当する。 In the present invention, a sulfur compound and a radical initiator are allowed to act on an olefin derivative having an olefin structure representing one or more Z isomers in the molecule, and at least one of the olefin structures representing the Z isomer represents an E isomer. This is a method for producing an isomer by isomerization to an olefin structure. In the present specification, an olefin derivative having an olefin structure representing one or more Z isomers in a molecule is also referred to as “Z-olefin derivative”, and at least of the olefin structure representing the Z isomer in the Z-olefin derivative. An olefin derivative substituted with an olefin structure, one of which represents an E form, is also referred to as an “E-olefin derivative”, and a composition containing both of these derivatives is also referred to as an “E / Z-olefin composition”. The above isomers correspond to E-olefin derivatives.
オレフィン誘導体は、E体及びZ体の立体異性体が存在するものであればよく、オレフィンの炭素−炭素二重結合における両方の炭素原子がそれぞれ1つ又は2つの置換基を有する二置換オレフィン、三置換オレフィン又は四置換オレフィンを用いることができる。その中で、オレフィンの炭素−炭素二重結合における両方の炭素原子がそれぞれ1つの置換基を有する二置換オレフィン、すなわち構造中に「−CH=CH−」を有するオレフィン誘導体が好ましい。本発明においては、Z−オレフィン誘導体を単独で原料として用いてもよく、E/Z−オレフィン組成物を原料として用いてもよい。E/Z−オレフィン組成物は、Z−オレフィン誘導体の含有量が例えば10質量%以上であることが好ましく、20質量%以上であることが好ましく、30質量%以上であることが好ましく、40質量%以上であることが好ましく、50質量%以上であることが好ましく、60質量%以上であることが好ましく、70質量%以上であることが好ましく、80質量%以上であることが好ましく、90質量%以上であることが好ましい。通常、オレフィン誘導体を製造すると、E−オレフィン誘導体及びZ−オレフィン誘導体が混ざったE/Z−オレフィン組成物が得られるので、これを原料として用いることができる。 The olefin derivative only needs to have an E-form and a Z-form stereoisomer, and both carbon atoms in the carbon-carbon double bond of the olefin each have one or two substituents, Tri-substituted olefins or tetra-substituted olefins can be used. Among them, disubstituted olefins in which both carbon atoms in the carbon-carbon double bond of the olefin each have one substituent, that is, olefin derivatives having “—CH═CH—” in the structure are preferable. In the present invention, a Z-olefin derivative may be used alone as a raw material, or an E / Z-olefin composition may be used as a raw material. In the E / Z-olefin composition, the content of the Z-olefin derivative is preferably 10% by mass or more, preferably 20% by mass or more, preferably 30% by mass or more, and 40% by mass. % Or more, preferably 50% by weight or more, preferably 60% by weight or more, preferably 70% by weight or more, preferably 80% by weight or more, 90% by weight % Or more is preferable. Usually, when an olefin derivative is produced, an E / Z-olefin composition in which an E-olefin derivative and a Z-olefin derivative are mixed can be obtained, which can be used as a raw material.
本発明において製造される異性化体(E−オレフィン誘導体)は、通常E/Z−オレフィン組成物として得られる。原料と生成物の双方がE/Z−オレフィン組成物である場合には、組成物中のE−オレフィン誘導体の比率が向上したこと、すなわちZ−オレフィン誘導体におけるZ体を表すオレフィン構造の少なくとも一部がE体を表すオレフィン構造に変換されたことをもって、異性化体が製造されたものとする。 The isomerized product (E-olefin derivative) produced in the present invention is usually obtained as an E / Z-olefin composition. When both the raw material and the product are E / Z-olefin compositions, the ratio of the E-olefin derivative in the composition is improved, that is, at least one of the olefin structures representing the Z form in the Z-olefin derivative. It is assumed that an isomer is produced when a part is converted to an olefin structure representing E form.
オレフィン誘導体は、例えばアルキル基(該アルキル基中の1つ又は2つ以上のCH2基は、酸素原子が直接隣接しないように、−O−、−CH=CH−、−CO−、−OCO−、−COO−又は−C≡C−で置換されてよく、該アルキル基中の1つ又は2つ以上の水素原子は任意にハロゲン原子に置換されていてもよい。)等の炭素骨格を基本とした鎖状構造を有する化合物、又は、シクロへキシレン基(この基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は−O−又は−S−に置き換えられてもよい。)、フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。)、ナフチレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。)等の炭素骨格を基本とした環状構造を有する化合物であることが好ましい。オレフィン誘導体中に、1つの「−CH=CH−」を有していてもよく、2つ以上の「−CH=CH−」を有していてもよい。The olefin derivative may be, for example, an alkyl group (one or two or more CH 2 groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO so that the oxygen atom is not directly adjacent to the olefin derivative. -, -COO- or -C≡C-, and one or two or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom). compounds having a basic, an acyclic structure or xylene group (the one present in the group -CH 2 cycloheteroalkyl - or nonadjacent two or more -CH 2 - is -O- or -S ), A phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, Hydrogen atoms present therein may be replaced by fluorine atoms), A tylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, and a hydrogen atom present in this group is replaced by a fluorine atom) It is preferably a compound having a cyclic structure based on a carbon skeleton. In the olefin derivative, one “—CH═CH—” may be contained, or two or more “—CH═CH—” may be contained.
オレフィン誘導体が2つ以上の「−CH=CH−」を有している場合、全ての「−CH=CH−」がE体を表すオレフィン誘導体、一部の「−CH=CH−」がE体を表し、残りの「−CH=CH−」がZ体を表すオレフィン誘導体、及び全ての「−CH=CH−」がZ体を表すオレフィン誘導体のように、それぞれの「−CH=CH−」がE体又はZ体を表す複数の異性体が存在する。本発明において、Z−オレフィン誘導体は、オレフィン誘導体中の1つ又は2つ以上の「−CH=CH−」がZ体を表す化合物であり、「−CH=CH−」が全てZ体を表す化合物であっても、1つ又は2つ以上のE体を表す「−CH=CH−」を含む化合物であってもよい。また、E−オレフィン誘導体は、オレフィン誘導体中の少なくとも1つの「−CH=CH−」がE体を表す化合物であり、「−CH=CH−」が全てE体を表す化合物であっても、1つ又は2つ以上のZ体を表す「−CH=CH−」を含む化合物であってもよいが、「−CH=CH−」が全てE体を表す化合物であることが好ましい。なお、異性化体であるE−オレフィン誘導体は、異性化体の原料としたZ−オレフィン誘導体よりも、E体を表す「−CH=CH−」を少なくとも1つ多く有する。 When the olefin derivative has two or more “—CH═CH—”, all “—CH═CH—” represents an olefin derivative, and some “—CH═CH—” represents E Olefin derivatives in which the remaining “—CH═CH—” represents the Z form, and all “—CH═CH—” represents the Z form, and each “—CH═CH— There exist a plurality of isomers in which "" represents E form or Z form. In the present invention, the Z-olefin derivative is a compound in which one or more “—CH═CH—” in the olefin derivative represents a Z form, and “—CH═CH—” all represents a Z form. Even if it is a compound, the compound containing "-CH = CH-" showing one or two or more E bodies may be sufficient. Further, the E-olefin derivative is a compound in which at least one “—CH═CH—” in the olefin derivative represents an E isomer, and “—CH═CH—” all represents a E isomer, Although it may be a compound containing “—CH═CH—” representing one or more Z isomers, it is preferable that all “—CH═CH—” represent E isomers. In addition, the E-olefin derivative which is an isomer has at least one “—CH═CH—” representing the E isomer more than the Z-olefin derivative used as a raw material of the isomer.
構造中に1つ以上の環状構造を有するZ−オレフィン誘導体は、一般式(1) The Z-olefin derivative having one or more cyclic structures in the structure is represented by the general formula (1)
S1は炭素原子数1〜4のアルキレン基であり、
R3は塩素原子、臭素原子、ヨウ素原子、ヒドロキシル基、シアノ基、カルボキシ基、メタンスルホニルオキシ基、p−トルエンスルホニルオキシ基又はトリフルオロメタンスルホニルオキシ基を表し、
A1及びA2は各々独立して
(a)1,4−シクロへキシレン基(この基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は−O−又は−S−に置き換えられてもよい。)
(b)1,4−フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。)
(c)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−ジイル基又はデカヒドロナフタレン−2,6−ジイル基(ナフタレン−2,6−ジイル基又は1,2,3,4−テトラヒドロナフタレン−2,6−ジイル基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、ナフタレン−2,6−ジイル基又は1,2,3,4−テトラヒドロナフタレン−2,6−ジイル基中に存在する水素原子はフッ素原子に置換されてもよい。)
からなる群より選ばれる基であり、
Z1及びZ2は各々独立して単結合又は炭素原子数1〜10の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して−O−、−S−、−COO−、−OCO−、−CO−、−CH=CH−又は−C≡C−に置き換えられてもよく、Z1及びZ2中に存在する水素原子はフッ素原子に置換されてもよく、
m1及びn1は各々独立して0から5の整数を表すが、m1+n1は1から5を表し、
Y1は
S 1 is an alkylene group having 1 to 4 carbon atoms,
R 3 represents a chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, carboxy group, methanesulfonyloxy group, p-toluenesulfonyloxy group or trifluoromethanesulfonyloxy group,
A 1 and A 2 are each independently (a) a 1,4-cyclohexylene group (one —CH 2 — present in this group or two or more non-adjacent —CH 2 — is — (It may be replaced by O- or -S-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N = and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═; (The hydrogen atom present in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be substituted with a fluorine atom.)
A group selected from the group consisting of:
Z 1 and Z 2 each independently represent a single bond or a linear alkylene group having 1 to 10 carbon atoms, one —CH 2 — present in the alkylene group or two not adjacent to each other The above -CH 2 -may be independently replaced by -O-, -S-, -COO-, -OCO-, -CO-, -CH = CH- or -C≡C-, Hydrogen atoms present in 1 and Z 2 may be substituted with fluorine atoms,
m 1 and n 1 each independently represents an integer from 0 to 5, while m 1 + n 1 represents 1 to 5,
Y 1 is
を表し、
A1及びA2が複数存在する場合は、それらは同一であっても異なっていてもよく、Z1及びZ2が複数存在する場合は、それらは同一であっても異なっていてもよい。]
で表される化合物であることが好ましい。
Represents
When a plurality of A 1 and A 2 are present, they may be the same or different, and when a plurality of Z 1 and Z 2 are present, they may be the same or different. ]
It is preferable that it is a compound represented by these.
一般式(1)で表されるZ−オレフィン誘導体に対応するE−オレフィン誘導体(以下、「一般式(1)で表される化合物のE体」ともいう。)は、一般式(1)中のY1がThe E-olefin derivative corresponding to the Z-olefin derivative represented by the general formula (1) (hereinafter also referred to as “E-form of the compound represented by the general formula (1)”) is represented by the following formula (1): Y 1 of
を表すものである。
Is expressed.
一般式(1)で表される化合物のE体は、例えば液晶表示素子用の液晶組成物として用いられる化合物及び該化合物を合成するための中間体として有用である。液晶組成物は、応答速度を向上させる観点から粘度が低いことが好ましく、また広い温度範囲にてネマチック層を維持するために、個々の成分が他の成分との高い混和性を有することが好ましい。また、液晶組成物の種類は液晶パネルの表示方式に合わせて選択することができる。例えば、液晶パネルが、VA(Vertical Alignment)方式又はPSA(Polymer-SustainedAlignment)方式である場合には、誘電率異方性(Δε)の値が負の液晶組成物が使用され、IPS(In-Plane-Switching)方式である場合には、Δεの値が正又は負の液晶組成物が使用される。 The E form of the compound represented by the general formula (1) is useful as, for example, a compound used as a liquid crystal composition for a liquid crystal display element and an intermediate for synthesizing the compound. The liquid crystal composition preferably has a low viscosity from the viewpoint of improving the response speed, and each component preferably has high miscibility with other components in order to maintain the nematic layer in a wide temperature range. . The type of liquid crystal composition can be selected according to the display method of the liquid crystal panel. For example, when the liquid crystal panel is a VA (Vertical Alignment) method or a PSA (Polymer-Sustained Alignment) method, a liquid crystal composition having a negative dielectric anisotropy (Δε) value is used, and IPS (In- In the case of a plane-switching method, a liquid crystal composition having a positive or negative value of Δε is used.
一般式(1)において、A1及びA2は各々独立して、液晶組成物の粘度を低下させるためにはトランス−1,4−シクロヘキシレン基、無置換のナフタレン−2,6−ジイル基又は無置換の1,4−フェニレン基であることが好ましく、他の液晶成分との混和性を高くするためには、トランス−1,4−シクロヘキシレン基又は無置換の1,4−フェニレン基であることが好ましい。In the general formula (1), A 1 and A 2 are each independently a trans-1,4-cyclohexylene group or an unsubstituted naphthalene-2,6-diyl group in order to reduce the viscosity of the liquid crystal composition. Or an unsubstituted 1,4-phenylene group. In order to increase the miscibility with other liquid crystal components, a trans-1,4-cyclohexylene group or an unsubstituted 1,4-phenylene group is preferable. It is preferable that
一般式(1)で表される化合物のE体を用いてΔεが正の化合物を製造する場合、A1及びA2は各々独立して、Δεを大きくするためにはIn the case of producing a compound with a positive Δε using the E form of the compound represented by the general formula (1), A 1 and A 2 are each independently for increasing Δε.
一般式(1)で表される化合物のE体を用いてΔεが負の化合物を製造する場合、A1及びA2はそれぞれ独立して下記の構造が好ましい。When a compound having a negative Δε is produced using the E form of the compound represented by the general formula (1), A 1 and A 2 each independently preferably have the following structure.
液晶表示素子とした際の長期信頼性を向上させるには、液晶組成物は窒素原子を含有しないことが好ましい。 In order to improve long-term reliability when a liquid crystal display element is formed, the liquid crystal composition preferably does not contain a nitrogen atom.
一般式(1)においてR1及びR2は、液晶組成物の粘度を低下させるためには、炭素原子数1〜12のアルキル基、炭素原子数2〜12のアルケニル基、炭素原子数1〜12のアルコキシ基又は炭素原子数2〜12のアルケニルオキシ基であることが好ましく、炭素原子数1〜8のアルキル基又は炭素原子数2〜8のアルケニル基であることがより好ましく、炭素原子数1〜5のアルキル基又は炭素原子数2〜5のアルケニル基であることが特に好ましい。また、直鎖状であることが好ましい。また、R1及びR2の少なくとも一方は、メタンスルホニルオキシ基、p−トルエンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、ヒドロキシル基、トリフルオロメトキシ基、カルボキシ基であることが好ましい。In general formula (1), R 1 and R 2 are each an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 1 to 1 carbon atoms in order to reduce the viscosity of the liquid crystal composition. It is preferably a 12 alkoxy group or an alkenyloxy group having 2 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, Particularly preferred is an alkyl group having 1 to 5 or an alkenyl group having 2 to 5 carbon atoms. Moreover, it is preferable that it is linear. At least one of R 1 and R 2 is preferably a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group, a hydroxyl group, a trifluoromethoxy group, or a carboxy group.
Δεが正の化合物を製造する場合、R1又はR2のいずれか一方は、Δεを大きくするためにはフッ素原子、シアノ基、トリフルオロメチル基又はトリフルオロメトキシ基であることが好ましく、粘度を低下させるためにはフッ素原子であることが好ましい。When producing a compound in which Δε is positive, either R 1 or R 2 is preferably a fluorine atom, a cyano group, a trifluoromethyl group or a trifluoromethoxy group in order to increase Δε. In order to reduce this, it is preferably a fluorine atom.
一般式(1)においてZ1及びZ2は、各々独立して、液晶組成物の粘度を低下させるとともに他の液晶成分との混和性を高くするためには−CH2O−、−OCH2−、−CF2O−、−OCF2−、−CH2CH2−、−CF=CF−、−C≡C−又は単結合であることが好ましく、−CF2O−、−OCF2−、−CH2CH2−又は単結合であることが更に好ましく、単結合であることが特に好ましく、大きなΔεを示すためには単結合又は−CF2O−であることが好ましい。Y1と直接結合するZ1及びZ2は、炭素原子数1〜10の直鎖状のアルキレン基又は単結合を表すことが好ましく、炭素原子数1〜4の直鎖状のアルキレン基又は単結合を表すことが好ましい。In the general formula (1), Z 1 and Z 2 are each independently —CH 2 O— or —OCH 2 for decreasing the viscosity of the liquid crystal composition and increasing the miscibility with other liquid crystal components. —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF═CF—, —C≡C— or a single bond are preferred, and —CF 2 O—, —OCF 2 — , —CH 2 CH 2 — or a single bond is more preferable, a single bond is particularly preferable, and a single bond or —CF 2 O— is preferable in order to exhibit a large Δε. Z 1 and Z 2 directly bonded to Y 1 preferably represent a linear alkylene group having 1 to 10 carbon atoms or a single bond, and a linear alkylene group having 1 to 4 carbon atoms or a single bond. Preferably it represents a bond.
一般式(1)で表される化合物は、以下の一般式(1a)、一般式(1b)、一般式(1c)、一般式(1d)又は一般式(1e)で表される化合物からなる群より選ばれる化合物であることが好ましい。 The compound represented by the general formula (1) is composed of a compound represented by the following general formula (1a), general formula (1b), general formula (1c), general formula (1d), or general formula (1e). A compound selected from the group is preferred.
R1a1は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して、−CH=CH−、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R1a2は炭素原子数1から8のアルキル基を表し、当該アルキル基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して、−CH=CH−、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
W1a1は単結合又は炭素原子数1から4の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して−O−、−S−、−COO−、−OCO−、−CO−、又は−C≡C−に置き換えられてもよく、W1a1中に存在する水素原子はフッ素原子に置換されてもよく、
Y1a2は単結合又は−CH=CH−を表し、
n1a1は1から5の整数を表す。]
R 1a1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH 2 — or two or more non-adjacent —CH 2 — present in the alkyl group are each independently —CH 2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1a2 represents an alkyl group having 1 to 8 carbon atoms, and one —CH 2 — present in the alkyl group or two or more non-adjacent —CH 2 — are each independently —CH 2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
W 1a1 represents a linear alkylene group having 4 to single bond or a carbon atoms, one -CH 2 present in the alkylene group - or nonadjacent two or more -CH 2 - is Each may be independently replaced with -O-, -S-, -COO-, -OCO-, -CO-, or -C≡C-, and the hydrogen atom present in W 1a1 is replaced with a fluorine atom. May be,
Y 1a2 represents a single bond or —CH═CH—,
n 1a1 represents an integer of 1 to 5. ]
R1b1及びR1b2は各々独立して炭素原子数1から8のアルキル基を表し、当該アルキル基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して、−CH=CH−、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
W1b1及びW1b2は各々独立して単結合又は炭素原子数1から4の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して−O−、−S−、−COO−、−OCO−、−CO−、又は−C≡C−に置き換えられてもよく、W1b1及びW1b2中に存在する水素原子はフッ素原子に置換されてもよく、
Y1b2及びY1b3は各々独立して単結合又は−CH=CH−を表し、
m1b1及びn1b1は各々独立して0から5の整数を表すが、m1b1+n1b1は1から5を表す。]
R 1b1 and R 1b2 are each independently an alkyl group having 1 to 8 carbon atoms, said alkyl group being present on one -CH 2 - or nonadjacent two or more -CH 2 - is Each independently may be replaced by —CH═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO—;
W 1b1 and W 1b2 represent each independently a single bond or a linear alkylene group having a carbon number of 1 to 4, one -CH 2 present in the alkylene group - two of or nonadjacent more -CH 2 - are each independently -O -, - S -, - COO -, - OCO -, - CO-, or -C≡C- may be replaced by, W 1b1 and W in 1b2 A hydrogen atom present in may be substituted with a fluorine atom,
Y 1b2 and Y 1b3 each independently represent a single bond or —CH═CH—,
m 1b1 and n 1b1 each independently represent an integer of 0 to 5, while m 1b1 + n 1b1 represents 1 to 5. ]
A1c3は
A 1c3
R1c1は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して、−CH=CH−、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R1c2はフッ素原子、トリフルオロメトキシ基又はシアノ基を表し、
n1c1は1から5の整数を表す。]
R 1c1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH 2 — or two or more non-adjacent —CH 2 — present in the alkyl group are each independently —CH 2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1c2 represents a fluorine atom, a trifluoromethoxy group or a cyano group,
n 1c1 represents an integer of 1 to 5. ]
R1d1は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して、−CH=CH−、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R1d2は炭素原子数1から8のアルキル基を表し、当該アルキル基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して、−CH=CH−、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
W1d1は単結合又は炭素原子数1から4の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して−O−、−S−、−COO−、−OCO−、−CO−、又は−C≡C−に置き換えられてもよく、W1d1中に存在する水素原子はフッ素原子に置換されてもよく、
Y1d2は単結合又は−CH=CH−を表し、
n1d1及びn1d2は各々独立して0から4の整数を表す。]
R 1d1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH 2 — or two or more non-adjacent —CH 2 — present in the alkyl group are each independently —CH 2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1d2 represents an alkyl group having 1 to 8 carbon atoms, and one —CH 2 — or two or more non-adjacent —CH 2 — present in the alkyl group are each independently —CH 2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
W 1d1 represents a linear alkylene group having 4 to single bond or a carbon atoms, one -CH 2 present in the alkylene group - or nonadjacent two or more -CH 2 - is Each independently may be replaced by —O—, —S—, —COO—, —OCO—, —CO—, or —C≡C—, and the hydrogen atom present in W 1d1 is replaced with a fluorine atom. May be,
Y 1d2 represents a single bond or —CH═CH—,
n 1d1 and n 1d2 each independently represent an integer of 0 to 4. ]
R1e1は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH2−又は隣接していない2個以上の−CH2−は各々独立して、−CH=CH−、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R1e2はヒドロキシル基、ヒドロキシメチル基、ブロモメチル基、クロロメチル基、メタンスルホニルオキシメチル基、トルエンスルホニルオキシメチル基、塩素原子、臭素原子、ヨウ素原子、トリフルオロメタンスルホニルオキシ基又は
R 1e1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH 2 — present in the alkyl group or two or more non-adjacent —CH 2 — are each independently —CH 2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1e2 is a hydroxyl group, hydroxymethyl group, bromomethyl group, chloromethyl group, methanesulfonyloxymethyl group, toluenesulfonyloxymethyl group, chlorine atom, bromine atom, iodine atom, trifluoromethanesulfonyloxy group or
n1e1は1から4の整数を表す。]
n 1e1 represents an integer of 1 to 4. ]
好ましい化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of preferred compounds are shown below, but the present invention is not limited thereto.
一般式(1a)の中では以下の一般式(1a−1)〜一般式(1a−23)で表される各化合物が好ましい。 In general formula (1a), each compound represented by the following general formula (1a-1)-general formula (1a-23) is preferable.
一般式(1b)の中では以下の一般式(1b−1)〜一般式(1b−10)で表される各化合物が好ましい。 In general formula (1b), each compound represented by the following general formula (1b-1)-general formula (1b-10) is preferable.
一般式(1c)の中では以下の一般式(1c−1)〜一般式(1c−65)で表される各化合物が好ましい。 In general formula (1c), each compound represented by the following general formula (1c-1)-general formula (1c-65) is preferable.
一般式(1d)の中では以下の一般式(1d−1)〜一般式(1d−35)で表される各化合物が好ましい。 In general formula (1d), each compound represented with the following general formula (1d-1)-general formula (1d-35) is preferable.
一般式(1e)の中では以下の一般式(1e−1)〜一般式(1e−13)で表される各化合物が好ましい。 In general formula (1e), each compound represented by the following general formula (1e-1)-general formula (1e-13) is preferable.
硫黄化合物としては、硫黄原子が1つ以上含まれる化合物であれば特に限定されないが、硫黄ラジカルを発生させやすく反応促進効果に優れる点から、有機硫黄化合物であると好ましく、下記一般式(A)〜(H)で表される化合物群から選ばれる化合物であるとより好ましい。また硫黄化合物は、同様の点から、S−S結合含有化合物であると好ましく、下記一般式(A)、(C)、(D)、(E)及び(F)で表される化合物群から選ばれる化合物であるとより好ましく、下記一般式(A)、(D)及び(F)で表される化合物群から選ばれる化合物であると更に好ましい。なお、S−S結合含有化合物は、S−S結合を1つ有する化合物であっても、S−S結合を2つ以上有する化合物であってもよい。また、S−S結合における2つのS原子は、それぞれ独立に酸化されていないS原子、すなわち−S−であっても、酸化されたS原子、すなわち−S(=O)−又は−S(=O)2−であってもよい。The sulfur compound is not particularly limited as long as it is a compound containing one or more sulfur atoms, but is preferably an organic sulfur compound from the viewpoint of easily generating sulfur radicals and excellent reaction promotion effect, and represented by the following general formula (A) It is more preferable that it is a compound chosen from the compound group represented by-(H). Further, from the same point, the sulfur compound is preferably an SS bond-containing compound, and from the group of compounds represented by the following general formulas (A), (C), (D), (E) and (F) It is more preferable that it is a compound selected, and it is still more preferable that it is a compound selected from the compound group represented by the following general formula (A), (D), and (F). The S—S bond-containing compound may be a compound having one S—S bond or a compound having two or more S—S bonds. Further, the two S atoms in the S—S bond are each independently an unoxidized S atom, ie, —S—, but an oxidized S atom, ie, —S (═O) — or —S ( ═O) 2 —.
Ra及び/又はRbがフェニル基である場合、該フェニル基は、無置換であるか、又は直鎖状又は分岐状の炭素原子数1から8のアルキル基、直鎖状又は分岐状の炭素原子数1から8のアルコキシ基、直鎖状又は分岐状の炭素原子数2から8のアルケニル基、塩素原子、アミノ基あるいはヒドロキシ基等で置換されていることが好ましい。
When R a and / or R b is a phenyl group, the phenyl group is unsubstituted or a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched group. It is preferably substituted with an alkoxy group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a chlorine atom, an amino group, or a hydroxy group.
Ra及び/又はRbがアルキル基又はアルケニル基である場合、該アルキル基又はアルケニル基は直鎖状であっても分岐状であってもよい。また、Ra及び/又はRbがアルキル基又はアルケニル基である場合、該アルキル基又はアルケニル基は、無置換であるか、又は塩素原子、アミノ基あるいはヒドロキシ基等で置換されていることが好ましい。When R a and / or R b are an alkyl group or an alkenyl group, the alkyl group or alkenyl group may be linear or branched. In addition, when R a and / or R b is an alkyl group or an alkenyl group, the alkyl group or alkenyl group may be unsubstituted or substituted with a chlorine atom, an amino group, a hydroxy group, or the like. preferable.
これらの硫黄化合物の具体例としては、ジフェニルジスルフィド、フェニルスルフィド、ベンゼンチオール、(フェニルスルホニル)フェニルスルフィド、ジフェニルジスルホン、ジフェニルスルホキシド、ジフェニルスルホン、ジ−p−トリルジスルフィド、2,2'−ジアミノジフェニルジスルフィド、4,4'−ジアミノジフェニルジスルフィド、4,4'−ジヒドロキシジフェニルジスルフィド、3,3'−ジヒドロキシジフェニルジスルフィド、ビス(p−メトキシフェニル)ジスルフィド、4,4'−ジクロロジフェニルジスルフィド、4,4'−ジフルオロジフェニルジスルフィド、ビス(4−カルボキシフェニル)ジスルフィド、ジメチルジスルフィド、ジエチルジスルフィド、ジプロピルジスルフィド、ジイソプロピルジスルフィド、ジアリルジスルフィド等が挙げられる。これらの中で、ジフェニルジスルフィド、(フェニルスルホニル)フェニルスルフィド又はジフェニルジスルホンが好ましく、ジフェニルジスルフィドがより好ましい。 Specific examples of these sulfur compounds include diphenyl disulfide, phenyl sulfide, benzenethiol, (phenylsulfonyl) phenyl sulfide, diphenyl disulfone, diphenyl sulfoxide, diphenyl sulfone, di-p-tolyl disulfide, and 2,2′-diaminodiphenyl disulfide. 4,4'-diaminodiphenyl disulfide, 4,4'-dihydroxydiphenyl disulfide, 3,3'-dihydroxydiphenyl disulfide, bis (p-methoxyphenyl) disulfide, 4,4'-dichlorodiphenyl disulfide, 4,4 ' -Difluorodiphenyl disulfide, bis (4-carboxyphenyl) disulfide, dimethyl disulfide, diethyl disulfide, dipropyl disulfide, diisopropyl disulfide, diary Disulfide, and the like. Among these, diphenyl disulfide, (phenylsulfonyl) phenyl sulfide or diphenyl disulfone is preferable, and diphenyl disulfide is more preferable.
異性化反応に用いる硫黄化合物の添加量は、例えば、原料であるオレフィン誘導体全量に対して、0.1〜10モル%とすることができる。硫黄化合物の添加量の下限値は、原料であるオレフィン誘導体全量に対して、0.2モル%以上、0.5モル%以上、1%以上又は2%以上であることが好ましい。また、硫黄化合物の添加量の上限値は、原料であるオレフィン誘導体全量に対して、8モル%以下、7モル%以下、6モル%以下又は5モル%以下であることが好ましい。 The addition amount of the sulfur compound used for the isomerization reaction can be, for example, 0.1 to 10 mol% with respect to the total amount of the olefin derivative as the raw material. The lower limit of the amount of sulfur compound added is preferably 0.2 mol% or more, 0.5 mol% or more, 1% or more, or 2% or more with respect to the total amount of the olefin derivative as a raw material. Moreover, it is preferable that the upper limit of the addition amount of a sulfur compound is 8 mol% or less, 7 mol% or less, 6 mol% or less, or 5 mol% or less with respect to the total amount of the olefin derivative which is a raw material.
ラジカル開始剤としては、従来公知のものを用いることができる。その具体例としては、2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス−(2,4−ジメチルバレロニトリル)、2,2’−アゾビス−(4−メトキシ−2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2−メチルブチロニトリル)、1,1’−アゾビス−(シクロヘキサン−1−カルボニトリル)、ジメチル2,2’−アゾビス(2−メチルプロピオナート)、2,2’−アゾビス(N−ブチル−2−メチルプロピオンアミド)、4,4’−アゾビス(4−シアノペンタン酸)等のアゾ化合物;ベンゾイルペルオキシド、ラウロイルペルオキシド、t−ブチルペルオキシピバレート、1,1’−ビス−(t−ブチルペルオキシ)シクロヘキサン、t−アミルペルオキシ−2−エチルヘキサノエート、t−ヘキシルペルオキシ−2−エチルヘキサノエート等の有機過酸化物が挙げられるが、反応促進効果に優れる点から、アゾ化合物が好ましい。なお、ラジカル開始剤は、異性化反応の反応温度、基質の種類などに合わせて、適切な半減期温度を有するものを適宜選択することができる。 A conventionally well-known thing can be used as a radical initiator. Specific examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4). -Dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis- (cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis (2-methylpropio) Natto), 2,2′-azobis (N-butyl-2-methylpropionamide), 4,4′-azobis (4-cyanopentanoic acid) and the like; benzoyl peroxide, lauroyl peroxide, t-butylperoxypi Valate, 1,1′-bis- (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, t-hexylpe Organic peroxides such as oxy-2-ethylhexanoate, from the viewpoint of excellent reaction acceleration effect, azo compounds are preferred. A radical initiator having an appropriate half-life temperature can be appropriately selected according to the reaction temperature of the isomerization reaction, the type of the substrate, and the like.
異性化反応に用いるラジカル開始剤の添加量は、例えば、原料であるオレフィン誘導体全量に対して、0.1〜10モル%とすることができる。ラジカル開始剤の添加量の下限値は、原料であるオレフィン誘導体全量に対して、0.2モル%以上、0.5モル%以上、1%以上又は2%以上であることが好ましい。また、ラジカル開始剤の添加量の上限値は、原料であるオレフィン誘導体全量に対して、8モル%以下、7モル%以下、6モル%以下又は5モル%以下であることが好ましい。 The addition amount of the radical initiator used for the isomerization reaction can be, for example, 0.1 to 10 mol% with respect to the total amount of the olefin derivative as the raw material. The lower limit of the addition amount of the radical initiator is preferably 0.2 mol% or more, 0.5 mol% or more, 1% or more, or 2% or more with respect to the total amount of the olefin derivative as a raw material. Moreover, it is preferable that the upper limit of the addition amount of a radical initiator is 8 mol% or less, 7 mol% or less, 6 mol% or less, or 5 mol% or less with respect to the olefin derivative whole quantity which is a raw material.
本発明の方法において、硫黄化合物及びラジカル開始剤を作用させる温度は、例えば20℃〜120℃とすることができる。想定される副反応を抑制する観点から、上記温度は20℃〜90℃であることが好ましく、20℃〜70℃であることがより好ましい。 In the method of the present invention, the temperature at which the sulfur compound and the radical initiator are allowed to act can be, for example, 20 ° C to 120 ° C. From the viewpoint of suppressing the assumed side reaction, the temperature is preferably 20 ° C to 90 ° C, and more preferably 20 ° C to 70 ° C.
本発明の方法は、反応を制御するために、溶媒存在下で行うことが好ましい。使用する溶媒としては、例えば、トルエン、ベンゼン、キシレン等の芳香族系溶媒、ヘキサン、ヘプタン、シクロヘキサン等の飽和炭化水素系溶媒、ジクロロメタン、クロロホルム、四塩化炭素、1,2−ジクロロエタン、1,1,2,2−テトラクロロエタン等の塩素系溶媒、テトラヒドロフラン(THF)、ジエチルエーテル、ジイソプロピルエーテル、t−ブチルメチルエーテル等のエーテル系溶媒、メタノール、エタノール等のアルコール系溶媒を好適に用いることができ、トルエン、THF、メタノールが特に好ましい。これらの溶媒は必要に応じて混合して使用してもよい。 The method of the present invention is preferably carried out in the presence of a solvent in order to control the reaction. Examples of the solvent to be used include aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbon solvents such as hexane, heptane and cyclohexane, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and 1,1. Chlorinated solvents such as 1,2,2-tetrachloroethane, ether solvents such as tetrahydrofuran (THF), diethyl ether, diisopropyl ether and t-butyl methyl ether, and alcoholic solvents such as methanol and ethanol can be suitably used. , Toluene, THF, and methanol are particularly preferable. These solvents may be mixed and used as necessary.
本発明の方法は、空気中で行うこともできるが、反応性の向上及び副反応の抑制の観点から、窒素等の不活性雰囲気下で行うことが好ましい。 Although the method of the present invention can be carried out in air, it is preferably carried out in an inert atmosphere such as nitrogen from the viewpoint of improving reactivity and suppressing side reactions.
なお、本発明の方法は、分子中に1つ又は2つ以上のZ体を表すオレフィン構造を有するオレフィン誘導体にS−S結合含有化合物を加熱下で作用させ、Z体を表すオレフィン構造の少なくとも1つをE体を表すオレフィン構造に異性化させる、異性化体の製造方法であってもよい。当該方法においては、ラジカル開始剤を用いずに、且つ加熱下で異性化を行うことを必須要件とすること以外は、上述の方法と同様の条件で反応を行うことができる。加熱温度は、例えば50℃〜120℃とすることができる。 In the method of the present invention, an SS bond-containing compound is allowed to act on an olefin derivative having an olefin structure representing one or more Z isomers in the molecule under heating, so that at least the olefin structure representing the Z isomer is present. A method for producing an isomer may be used in which one isomerizes to an olefin structure representing E form. In this method, the reaction can be carried out under the same conditions as in the above method except that the isomerization under heating is an essential requirement without using a radical initiator. The heating temperature can be, for example, 50 ° C to 120 ° C.
本発明の方法により、Z−オレフィン誘導体の質量に対するE−オレフィン誘導体の質量比率(E体/Z体)を、75/25以上、すなわち、E/Z−オレフィン組成物におけるE−オレフィン誘導体の含有量を75質量%以上に高めることができる。Z−オレフィン誘導体の質量に対するE−オレフィン誘導体の質量比率は、より高いことが好ましく、(E体/Z体)=80/20以上であることが好ましく、85/15以上であることがより好ましい。Z−オレフィン誘導体の質量に対するE−オレフィン誘導体の質量比率(E体/Z体)は、ガスクロマトグラフィーにより定量可能である。 By the method of the present invention, the mass ratio of the E-olefin derivative to the mass of the Z-olefin derivative (E-form / Z-form) is 75/25 or more, that is, the inclusion of the E-olefin derivative in the E / Z-olefin composition The amount can be increased to 75% by mass or more. The mass ratio of the E-olefin derivative to the mass of the Z-olefin derivative is preferably higher, (E isomer / Z isomer) = 80/20 or more is preferable, and 85/15 or more is more preferable. . The mass ratio of the E-olefin derivative to the mass of the Z-olefin derivative (E-form / Z-form) can be quantified by gas chromatography.
異性化反応後のE/Z−オレフィン組成物に残存したZ−オレフィン誘導体を除去し、目的とするE−オレフィン誘導体を得るために、E/Z−オレフィン組成物を更に精製してもよい。精製方法としてはクロマトグラフィー、再結晶、蒸留、昇華、再沈殿、吸着、分液処理等が挙げられる。精製剤を用いる場合、精製剤としてシリカゲル、アルミナ、活性炭、活性白土、セライト、ゼオライト、メソポーラスシリカ、カーボンナノチューブ、カーボンナノホーン、備長炭、木炭、グラフェン、イオン交換樹脂、酸性白土、二酸化ケイ素、珪藻土、パーライト、セルロース、有機ポリマー、多孔質ゲル等が挙げられる。このような精製を繰り返すと、E−オレフィン誘導体の単離収率が低下するという問題があるが、本発明の方法によれば、異性化反応によりZ−オレフィン誘導体の質量に対するE−オレフィン誘導体の質量比率をより高めることができるため、精製の回数を減らすことができ、E−オレフィン誘導体の収率を向上することができる。 In order to remove the Z-olefin derivative remaining in the E / Z-olefin composition after the isomerization reaction and obtain the target E-olefin derivative, the E / Z-olefin composition may be further purified. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel. When such purification is repeated, there is a problem that the isolated yield of the E-olefin derivative is lowered. Since the mass ratio can be further increased, the number of purifications can be reduced, and the yield of the E-olefin derivative can be improved.
以下、例を挙げて本発明を更に詳述するが、本発明はこれらによって限定されるものではない。 Hereinafter, although an example is given and the present invention is explained still in full detail, the present invention is not limited by these.
ガスクロマトグラフィー分析については、以下の条件にて実施した。
サンプル調製:1質量%アセトン溶液
カラム導入量:1μL
装置:GC2010(島津製作所)
カラム: J&WDB-17MS(30m×0.25μm×0.25mm)
キャリアーガス:窒素
カラム圧力:(226 kPa)、カラム流量: 3.19 mL/min、平均速度:58.8 cm/sec
スプリット比: 50:1
インジェクション温度: 300℃、検出器温度:(FID) 320℃
カラム昇温設定: 100℃(1 min)→10℃/min→300℃(14 min)The gas chromatography analysis was performed under the following conditions.
Sample preparation: 1% by mass acetone solution column introduction amount: 1 μL
Equipment: GC2010 (Shimadzu Corporation)
Column: J & WDB-17MS (30m × 0.25μm × 0.25mm)
Carrier gas: Nitrogen column pressure: (226 kPa), column flow rate: 3.19 mL / min, average speed: 58.8 cm / sec
Split ratio: 50: 1
Injection temperature: 300 ° C, detector temperature: (FID) 320 ° C
Column temperature setting: 100 ° C (1 min) → 10 ° C / min → 300 ° C (14 min)
(実施例1) (Example 1)
(実施例2) (Example 2)
式(3)のE/Zオレフィン組成物(3g、E体/Z体=10/90)、ジフェニルジスルフィド(22mg)及びTHF(10mL)を室温にて、窒素で置換した反応容器で混合した後、内温51℃に加熱した。内温51℃にて2,2−アゾビス(2,4−ジメチルバレロニトリル)(25mg)を加えた後、10時間攪拌した。反応液をガスクロマトグラフィーにて分析したところ、E体/Z体=83/17であった。この反応溶液にトルエン(10mL)及び、水(10mL)を加え、分液し、有機層を水(10mL)、飽和食塩水(10mL)の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式(4)のE/Zオレフィン組成物(収率定量的、E体/Z体=83/17)を得た。
After mixing the E / Z olefin composition of formula (3) (3 g, E isomer / Z isomer = 10/90), diphenyl disulfide (22 mg) and THF (10 mL) at room temperature in a reaction vessel substituted with nitrogen. The internal temperature was heated to 51 ° C. 2,2-azobis (2,4-dimethylvaleronitrile) (25 mg) was added at an internal temperature of 51 ° C., followed by stirring for 10 hours. When the reaction liquid was analyzed by gas chromatography, it was E-form / Z-form = 83/17. Toluene (10 mL) and water (10 mL) were added to the reaction solution, and the phases were separated. The organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (4) (quantitative yield, E isomer / Z isomer = 83/17).
(実施例3) Example 3
(実施例4) (Example 4)
(実施例5) (Example 5)
(実施例6) (Example 6)
(比較例1) (Comparative Example 1)
(比較例2) (Comparative Example 2)
以上の結果から明らかであるように、従来の酸性且つ高温という異性化反応条件では適用できなかった基質に関しても、本発明の条件を用いれば、オレフィン異性化反応が可能であり、高い比率で目的とするE−オレフィン誘導体が得られる。 As is clear from the above results, the olefin isomerization reaction can be performed using the conditions of the present invention even for substrates that could not be applied under conventional acidic and high temperature isomerization reaction conditions. An E-olefin derivative is obtained.
Claims (3)
(a)1,4−シクロへキシレン基(この基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は−O−又は−S−に置き換えられてもよい。)
(b)1,4−フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。)
からなる群より選ばれる基であり、
Z 1a2 は単結合又は炭素原子数1〜10の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して−O−、−S−、−COO−、−OCO−、−CO−又は−C≡C−に置き換えられてもよく、Z 1a2 中に存在する水素原子はフッ素原子に置換されてもよいが、一般式(1a)中の−CH=CH−と直接結合するZ 1a2 が単結合を表す場合、該一般式(1a)中の−CH=CH−と直接結合するA 1a2 は上記(a)を表し、
R 1a1 は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R 1a2 は炭素原子数1から8のアルキル基を表し、当該アルキル基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
W 1a1 は単結合又は炭素原子数1から4の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して−O−、−S−、−COO−、−OCO−、−CO−、又は−C≡C−に置き換えられてもよく、W 1a1 中に存在する水素原子はフッ素原子に置換されてもよく、
Y 1a2 は単結合又は−CH=CH−を表すが、W 1a1 が単結合を表し、且つY 1a2 が−CH=CH−を表す場合、該Y 1a2 と直接結合するA 1a2 は上記(a)を表し、
n 1a1 は1から5の整数を表す。]
一般式(1c)
(a)1,4−シクロへキシレン基(この基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は−O−又は−S−に置き換えられてもよい。)
(b)1,4−フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。)
からなる群より選ばれる基であり、
Z 1c2 は単結合又は炭素原子数1〜10の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して−O−、−S−、−COO−、−OCO−、−CO−又は−C≡C−に置き換えられてもよく、Z 1c2 中に存在する水素原子はフッ素原子に置換されてもよいが、一般式(1c)中の−CH=CH−と直接結合するZ 1c2 が単結合を表す場合、該一般式(1c)中の−CH=CH−と直接結合するA 1c2 は上記(a)を表し、
A 1c3 は
R 1c1 は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R 1c2 はフッ素原子、トリフルオロメトキシ基又はシアノ基を表し、
n 1c1 は1から5の整数を表す。]
一般式(1d)
(a)1,4−シクロへキシレン基(この基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は−O−又は−S−に置き換えられてもよい。)
(b)1,4−フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。)
からなる群より選ばれる基であり、
Z 1d2 は単結合又は炭素原子数1〜10の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して−O−、−S−、−COO−、−OCO−、−CO−又は−C≡C−に置き換えられてもよく、Z 1d2 中に存在する水素原子はフッ素原子に置換されてもよいが、一般式(1d)中の−CH=CH−と直接結合するZ 1d2 が単結合を表す場合、該一般式(1d)中の−CH=CH−と直接結合するA 1d2 は上記(a)を表し、
Z 1d3 及びZ 1d4 はそれぞれ独立して単結合又は炭素原子数1〜10の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して−O−、−S−、−COO−、−OCO−、−CO−又は−C≡C−に置き換えられてもよく、Z 1d3 中に存在する水素原子はフッ素原子に置換されてもよく、
R 1d1 は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R 1d2 は炭素原子数1から8のアルキル基を表し、当該アルキル基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
W 1d1 は単結合又は炭素原子数1から4の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して−O−、−S−、−COO−、−OCO−、−CO−、又は−C≡C−に置き換えられてもよく、W 1d1 中に存在する水素原子はフッ素原子に置換されてもよく、
Y 1d2 は単結合又は−CH=CH−を表すが、W 1d1 が単結合を表し、且つY 1d2 が−CH=CH−を表す場合、該Y 1d2 と直接結合するA 1d3 は上記(a)を表し、
n 1d1 及びn 1d2 は各々独立して0から4の整数を表す。]
又は一般式(1e)
(a)1,4−シクロへキシレン基(この基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は−O−又は−S−に置き換えられてもよい。)
(b)1,4−フェニレン基(この基中に存在する1個の−CH=又は隣接していない2個以上の−CH=は−N=に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。)
からなる群より選ばれる基であり、
Z 1e2 は単結合又は炭素原子数1〜10の直鎖状のアルキレン基を表し、該アルキレン基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して−O−、−S−、−COO−、−OCO−、−CO−又は−C≡C−に置き換えられてもよく、Z 1e2 中に存在する水素原子はフッ素原子に置換されてもよいが、一般式(1e)中の−CH=CH−と直接結合するZ 1e2 が単結合を表す場合、該一般式(1e)中の−CH=CH−と直接結合するA 1e2 は上記(a)を表し、
R 1e1 は炭素原子数1から15のアルキル基を表し、当該アルキル基中に存在する1個の−CH 2 −又は隣接していない2個以上の−CH 2 −は各々独立して、−C≡C−、−O−、−S−、−COO−、−OCO−又は−CO−に置き換えられてもよく、
R 1e2 はヒドロキシル基、ヒドロキシメチル基、ブロモメチル基、クロロメチル基、メタンスルホニルオキシメチル基、トルエンスルホニルオキシメチル基、塩素原子、臭素原子、ヨウ素原子、トリフルオロメタンスルホニルオキシ基又は
n 1e1 は1から4の整数を表す。]
で表される分子中に1つ又は2つ以上のZ体を表すオレフィン構造を有するオレフィン誘導体に、一般式(A)、一般式(C)〜一般式(F)
で表される化合物群から選ばれる1種又は2種以上の硫黄化合物及びラジカル開始剤を作用させ、前記Z体を表すオレフィン構造の少なくとも1つをE体を表すオレフィン構造に異性化させる、異性化体の製造方法。 General formula ( 1a)
(A) 1,4-cyclohexylene group (the one present in the group -CH 2 - or nonadjacent two or more -CH 2 - is replaced by -O- or -S- May be good.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N = and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom.)
A group selected from the group consisting of:
Z 1a2 represents a single bond or a linear alkylene group having 1 to 10 carbon atoms, said alkylene group being present in one -CH 2 - or nonadjacent two or more -CH 2 - is Each independently may be replaced by —O—, —S—, —COO— , —OCO— , —CO— or —C≡C—, and the hydrogen atom present in Z 1a2 is replaced by a fluorine atom. However, when Z 1a2 directly bonded to —CH═CH— in General Formula (1a) represents a single bond, A 1a2 directly bonded to —CH═CH— in General Formula (1a) is Represents (a) above,
R 1a1 represents an alkyl group having from 1 to 15 carbon atoms, said alkyl group being present on one -CH 2 - or nonadjacent two or more -CH 2 - are each independently, -C ≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1a2 represents an alkyl group having 1 to 8 carbon atoms, said alkyl group being present on one -CH 2 - or nonadjacent two or more -CH 2 - are each independently, -C ≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
W 1a1 represents a linear alkylene group having 4 to single bond or a carbon atoms, one -CH 2 present in the alkylene group - or nonadjacent two or more -CH 2 - is Each may be independently replaced with -O-, -S-, -COO-, -OCO-, -CO-, or -C≡C-, and the hydrogen atom present in W 1a1 is replaced with a fluorine atom. May be,
Y 1a2 represents a single bond or represents a -CH = CH-, W 1a1 represents a single bond, and if Y 1a2 represents -CH = CH-, A 1a2 to bind directly with the Y 1a2 above (a) Represents
n 1a1 represents an integer of 1 to 5. ]
General formula (1c)
(A) 1,4-cyclohexylene group (the one present in the group -CH 2 - or nonadjacent two or more -CH 2 - is replaced by -O- or -S- May be good.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N = and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom.)
A group selected from the group consisting of:
Z 1c2 represents a single bond or a linear alkylene group having 1 to 10 carbon atoms, said alkylene group being present in one -CH 2 - or nonadjacent two or more -CH 2 - is Each independently may be replaced by —O—, —S—, —COO—, —OCO—, —CO— or —C≡C—, and the hydrogen atom present in Z 1c2 is replaced by a fluorine atom. However, when Z 1c2 directly bonded to —CH═CH— in general formula (1c) represents a single bond, A 1c2 directly bonded to —CH═CH— in general formula (1c) is Represents (a) above,
A 1c3 is
R 1c1 represents an alkyl group having from 1 to 15 carbon atoms, said alkyl group being present on one -CH 2 - or nonadjacent two or more -CH 2 - are each independently, -C ≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1c2 represents a fluorine atom, a trifluoromethoxy group or a cyano group,
n 1c1 represents an integer of 1 to 5. ]
General formula (1d)
(A) 1,4-cyclohexylene group (the one present in the group -CH 2 - or nonadjacent two or more -CH 2 - is replaced by -O- or -S- May be good.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N = and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom.)
A group selected from the group consisting of:
Z 1d2 denotes a single bond or a linear alkylene group having 1 to 10 carbon atoms, said alkylene group being present in one -CH 2 - or nonadjacent two or more -CH 2 - is Each independently may be replaced by —O—, —S—, —COO—, —OCO—, —CO— or —C≡C—, and the hydrogen atom present in Z 1d2 is replaced by a fluorine atom. However, when Z 1d2 directly bonded to —CH═CH— in general formula (1d) represents a single bond, A 1d2 directly bonded to —CH═CH— in general formula (1d) is Represents (a) above,
Z 1d3 and Z 1d4 each independently represents a single bond or a linear alkylene group having 1 to 10 carbon atoms, one -CH 2 present in the alkylene group - two of or nonadjacent The above —CH 2 — may be independently replaced by —O—, —S—, —COO—, —OCO—, —CO— or —C≡C—, and hydrogen present in Z 1d3 The atom may be substituted with a fluorine atom,
R 1d1 is an alkyl group having from 1 to 15 carbon atoms, said alkyl group being present on one -CH 2 - or nonadjacent two or more -CH 2 - are each independently, -C ≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1d2 represents an alkyl group having 1 to 8 carbon atoms, said alkyl group being present on one -CH 2 - or nonadjacent two or more -CH 2 - are each independently, -C ≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
W 1d1 represents a linear alkylene group having 4 to single bond or a carbon atoms, one -CH 2 present in the alkylene group - or nonadjacent two or more -CH 2 - is Each independently may be replaced by —O—, —S—, —COO—, —OCO—, —CO—, or —C≡C—, and the hydrogen atom present in W 1d1 is replaced with a fluorine atom. May be,
Y 1d2 represents a single bond or —CH═CH—, but when W 1d1 represents a single bond and Y 1d2 represents —CH═CH—, A 1d3 directly bonded to Y 1d2 is the above (a) Represents
n 1d1 and n 1d2 each independently represent an integer of 0 to 4. ]
Or general formula (1e)
(A) 1,4-cyclohexylene group (the one present in the group -CH 2 - or nonadjacent two or more -CH 2 - is replaced by -O- or -S- May be good.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N = and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom.)
A group selected from the group consisting of:
Z 1e2 represents a single bond or a linear alkylene group having 1 to 10 carbon atoms, said alkylene group being present in one -CH 2 - or nonadjacent two or more -CH 2 - is Each independently may be replaced by —O—, —S—, —COO— , —OCO— , —CO— or —C≡C—, and the hydrogen atom present in Z 1e2 is replaced by a fluorine atom. However, when Z 1e2 directly bonded to —CH═CH— in General Formula (1e) represents a single bond, A 1e2 directly bonded to —CH═CH— in General Formula (1e) is Represents (a) above,
R 1e1 represents an alkyl group having from 1 to 15 carbon atoms, said alkyl group being present on one -CH 2 - or nonadjacent two or more -CH 2 - are each independently, -C ≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R 1e2 is a hydroxyl group, hydroxymethyl group, bromomethyl group, chloromethyl group, methanesulfonyloxymethyl group, toluenesulfonyloxymethyl group, chlorine atom, bromine atom, iodine atom, trifluoromethanesulfonyloxy group or
n 1e1 represents an integer of 1 to 4. ]
The olefin derivatives having an olefin structure representing one or more Z isomers in the molecule represented by general formula (A), general formula (C) to general formula (F)
1 type or 2 or more types of sulfur compounds chosen from the compound group represented by this, and a radical initiator act, and isomerize at least 1 of the olefin structure showing the said Z body into the olefin structure showing the E body, Method for producing chemicals.
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