WO2017169839A1 - 2-ヒドラジノベンゾチアゾール誘導体の製造方法 - Google Patents
2-ヒドラジノベンゾチアゾール誘導体の製造方法 Download PDFInfo
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- WO2017169839A1 WO2017169839A1 PCT/JP2017/010629 JP2017010629W WO2017169839A1 WO 2017169839 A1 WO2017169839 A1 WO 2017169839A1 JP 2017010629 W JP2017010629 W JP 2017010629W WO 2017169839 A1 WO2017169839 A1 WO 2017169839A1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 78
- JYSUYJCLUODSLN-UHFFFAOYSA-N 1,3-benzothiazol-2-ylhydrazine Chemical class C1=CC=C2SC(NN)=NC2=C1 JYSUYJCLUODSLN-UHFFFAOYSA-N 0.000 title abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 399
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 5
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 5
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 5
- -1 pentafluorosulfuranyl group Chemical group 0.000 claims description 84
- 125000001153 fluoro group Chemical group F* 0.000 claims description 73
- 229910052731 fluorine Inorganic materials 0.000 claims description 72
- 125000000217 alkyl group Chemical group 0.000 claims description 60
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 57
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 229910052801 chlorine Inorganic materials 0.000 claims description 41
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 41
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 28
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052740 iodine Inorganic materials 0.000 claims description 28
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 28
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 27
- 125000006850 spacer group Chemical group 0.000 claims description 19
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 18
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 17
- 239000004973 liquid crystal related substance Substances 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 16
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 10
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 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 9
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 125000003118 aryl group Chemical group 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
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003905 agrochemical Substances 0.000 claims description 3
- 239000004566 building material Substances 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000012776 electronic material Substances 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 291
- 238000006243 chemical reaction Methods 0.000 description 119
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 114
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 96
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 74
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 60
- 238000004440 column chromatography Methods 0.000 description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 49
- 238000000746 purification Methods 0.000 description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 46
- 239000000243 solution Substances 0.000 description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 44
- 239000002904 solvent Substances 0.000 description 44
- 239000000741 silica gel Substances 0.000 description 43
- 229910002027 silica gel Inorganic materials 0.000 description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 39
- 239000012299 nitrogen atmosphere Substances 0.000 description 39
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 37
- 238000001816 cooling Methods 0.000 description 36
- 238000001953 recrystallisation Methods 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 229910001868 water Inorganic materials 0.000 description 31
- 239000012267 brine Substances 0.000 description 29
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 description 20
- 235000011152 sodium sulphate Nutrition 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 229920000728 polyester Polymers 0.000 description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 0 COC(C1(*)C(C2)C=CC2C1)=C Chemical compound COC(C1(*)C(C2)C=CC2C1)=C 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000012044 organic layer Substances 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 10
- 230000007704 transition Effects 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000010538 cationic polymerization reaction Methods 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 8
- 238000007342 radical addition reaction Methods 0.000 description 8
- 238000010526 radical polymerization reaction Methods 0.000 description 8
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910000103 lithium hydride Inorganic materials 0.000 description 3
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- BWSPEBBETMTJAS-UHFFFAOYSA-N C=CC(OCCCCCCOc(cc1)ccc1OC(C(CC1)CCC1C(O)=O)=O)=O Chemical compound C=CC(OCCCCCCOc(cc1)ccc1OC(C(CC1)CCC1C(O)=O)=O)=O BWSPEBBETMTJAS-UHFFFAOYSA-N 0.000 description 2
- HKMIIJUEEMKHRJ-UHFFFAOYSA-N CCCCCCNc1nc2ccccc2[s]1 Chemical compound CCCCCCNc1nc2ccccc2[s]1 HKMIIJUEEMKHRJ-UHFFFAOYSA-N 0.000 description 2
- QVKPPRYUGJFISN-UHFFFAOYSA-N CNc1nc(cccc2)c2[s]1 Chemical compound CNc1nc(cccc2)c2[s]1 QVKPPRYUGJFISN-UHFFFAOYSA-N 0.000 description 2
- XIIBIZBWRVJSHS-UHFFFAOYSA-N COCCOCCNc1nc2ccccc2[s]1 Chemical compound COCCOCCNc1nc2ccccc2[s]1 XIIBIZBWRVJSHS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical compound CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 2
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
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- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- 235000011009 potassium phosphates Nutrition 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- AWDMDDKZURRKFG-UHFFFAOYSA-N potassium;propan-1-olate Chemical compound [K+].CCC[O-] AWDMDDKZURRKFG-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 1
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 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
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229940074411 xylene Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/12—Esters of phenols or saturated alcohols
- C08F22/14—Esters having no free carboxylic acid groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
- C09K19/3497—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom the heterocyclic ring containing sulfur and nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
Definitions
- the present invention relates to a method for producing a 2-hydrazinobenzothiazole derivative, a method for producing a compound using the 2-hydrazinobenzothiazole derivative, a polymerizable composition containing the compound, a polymerizable liquid crystal composition, and the polymerizable liquid crystal
- the present invention relates to an optical anisotropic body using the composition.
- Patent Document 1 a method of reacting 2-hydrazinobenzothiazole with an alkyl halide in the presence of potassium carbonate, cesium carbonate or lithium bis (trimethylsilyl) amide has been used (Patent Document 1). To Patent Document 3). However, the isolation yield of the target product is not always sufficient in the conventional method.
- the conventional method for producing a 2-hydrazinobenzothiazole derivative has not only a low isolation yield, but also a problem that the resulting target compound tends to be colored due to an anion of 2-hydrazinobenzothiazole.
- the present invention provides a method for producing a 2-hydrazinobenzothiazole derivative that can solve the above problems. Also provided are a method for producing a compound using the 2-hydrazinobenzothiazole derivative obtained by the production method, and a composition containing the compound. Also provided is a polymerizable composition containing a compound obtained by the production method, which is useful for producing a film-like polymer that hardly undergoes discoloration and orientation deterioration when irradiated with ultraviolet light for a long period of time. To do.
- the present inventors have developed a novel method for producing 2-hydrazinobenzothiazole derivatives. That is, the present invention relates to a compound represented by the general formula (IB) and a general formula (I) in the presence of at least one compound selected from the group consisting of metal amides, metal hydrides, metal alkoxides, and organic alkali metals.
- a method for producing a compound represented by the general formula (IC), comprising a step of reacting the compound represented by -A) with the compound represented by the general formula (IC).
- the production method of the present invention it is possible to produce a 2-hydrazinobenzothiazole derivative with a high yield and with reduced coloring. Since the compound obtained by the production method of the present invention can be prevented from being colored, it is particularly useful as a raw material for products that are not allowed even with slight coloring or discoloration. When an optical material or the like is produced using a compound obtained by the production method of the present invention as a raw material, coloring, discoloration, and the like are hardly caused, and high transparency is ensured.
- the optically anisotropic body obtained from the polymerizable liquid crystal composition containing the compound produced by the production method of the present invention is less likely to be discolored when irradiated with ultraviolet light for a long period of time, and the orientation is not likely to deteriorate.
- the compound produced by the production method of the present invention is useful for optical materials such as an optical compensation film.
- the present invention relates to a method for producing a 2-hydrazinobenzothiazole derivative, a method for producing a compound using the 2-hydrazinobenzothiazole derivative, a polymerizable composition containing the compound, a resin using the compound, and a resin additive , Oil, filter, adhesive, adhesive, fats and oils, ink, pharmaceuticals, cosmetics, detergents, building materials, packaging materials, liquid crystal materials, organic EL materials, organic semiconductor materials, electronic materials, display elements, electronic devices, communication equipment, Automotive parts, aircraft parts, machine parts, agricultural chemicals and foods, products using them, polymerizable liquid crystal compositions, polymers obtained by polymerizing the polymerizable liquid crystal compositions, and optical anisotropy using the polymers Provide the body.
- the metal amide is preferably selected from alkali metal amides and alkaline earth metal amides, more preferably selected from lithium amide, sodium amide, magnesium amide, potassium amide, calcium amide, cesium amide and lithium diisopropylamide, In particular, from the viewpoint of ease of handling, it is even more preferable to be selected from lithium amide, sodium amide and potassium amide, and the metal hydride is preferably selected from alkali metal hydride and alkaline earth metal hydride, lithium hydride , Sodium hydride, water More preferably selected from magnesium hydride, potassium hydride, calcium hydride, cesium hydride, lithium aluminum hydride and lithium borohydride, and particularly from the viewpoint of easy handling, lithium hydride, sodium hydride and hydrogen More preferably, the metal alkoxide is selected from
- borohydride, lithium triethylborohydride and lithium bis (fluorosulfonyl) imide alkyllithium, aryllithium, lithium hydride More preferably selected from tri-tert-butoxyaluminum, lithium tri-sec-butylborohydride, lithium triethylborohydride and lithium bis (fluorosulfonyl) imide, alkyllithium having 1 to 8 carbon atoms and carbon atoms It is even more preferable that the number is selected from aryl lithium having 6 to 12, and selected from methyl lithium, ethyl lithium, propyl lithium, butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium, hexyl lithium and phenyl lithium.
- the organic alkali metal is preferably one in which an organic group consisting only of C, O, N, and H as a constituent atom is bonded to the alkali metal, and from the viewpoint of yield, it is preferably a compound having a carbon-alkali metal bond. .
- W 2 may be any hydrogen atom in the group substituted by a fluorine atom, and each of —CH 2 — or two or more —CH 2 — that are not adjacent to each other may be substituted.
- W 2 may be any hydrogen atom in the group substituted by a fluorine atom, and each of —CH 2 — or two or more —CH 2 — that are not adjacent to each other may be substituted.
- W 2 may be substituted with any hydrogen atom in the group by a fluorine atom, one —CH 2 — or two or more non-adjacent ones.
- —CH 2 — is each independently —O—, —S—, —CO—, —COO—, —OCO—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —CH ⁇ CH—.
- a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by —CF ⁇ CF— or —C ⁇ C—, or P W — (Sp W —X W ) kW — W 2 represents a group in which any hydrogen atom in the group may be substituted with a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — Carbon atoms each independently substituted by —O—, —CO—, —COO—, —OCO— Linear or branched alkyl group containing from 1 to 20, or, P W - (Sp W -X W) kW - is more preferably a group represented by, W 2 is any hydrogen atom in the radicals May be substituted with a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — may be independently substituted with —O—.
- W 2 represents one —CH 2 —, or two or more non-adjacent —CH 2 — may be each independently substituted by —O—. It is particularly preferable to represent a linear alkyl group having 1 to 12 carbon atoms. More specifically, in the general formula (IA), the group represented by W 2 is represented by the following formulas (W2-a-1) to (W2-a-6)
- k2a represents an integer of 2 to 20
- k2b represents an integer of 1 to 6
- k2c represents an integer of 3 to 20
- k2d represents an integer of 1 to 6
- k2a preferably represents an integer of 4 to 12, and preferably represents an integer of 4 to 8, from the viewpoint of liquid crystallinity, reverse wavelength dispersion, and solubility in a solvent. More preferably, it is particularly preferable that 6 is represented.
- k2b preferably represents an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 2.
- k2b preferably represents an integer of 1 to 4, more preferably represents an integer of 1 to 3, and particularly preferably represents 1 or 2.
- k2c is more preferably an integer of 3 to 12, more preferably an integer of 3 to 8, and further preferably an integer of 3 to 8. It is particularly preferred to represent an integer from 4 to 6.
- k2d is more preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and more preferably 2. It is particularly preferred.
- formula (W2-a-1) to formula (W2-a-6) formula (W2-a-1), formula (W2-a-3), formula (W2-a-4) or formula ( A group represented by W2-a-6) is more preferred.
- P W represents a group represented by P W — (Sp W —X W ) kW —
- P W represents a polymerizable group, preferably by radical polymerization, radical addition polymerization, cationic polymerization, or anionic polymerization.
- a preferred polymerizable group represents the same as P 1 below
- Sp W represents a spacer group, but a preferred spacer group represents the same as Sp 1 below, and there are a plurality of Sp W.
- X W represents —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 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 -
- X W may be different even each identical in the presence of two or more, -O -, - S -, - OCH 2 -, - CH 2 O—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO— or a single bond is preferable.
- kW represents an integer of 0 to 10, but when added to a liquid crystal composition, it is preferably an integer of 0 to 5 from the viewpoint of liquid crystallinity, and represents an integer of 1 to 3. It is more preferable to represent 1.
- W 2 is P W - (Sp W -X W ) kW - may represent a group represented by the following formula (P3-1), formula (P3-2) or formula (P3-3)
- P 3 represents a polymerizable group, preferably represents a group that is polymerized by radical polymerization, radical addition polymerization, cationic polymerization, or anionic polymerization, and a preferable polymerizable group represents the same as P 1 below
- k3a Represents an integer of 2 to 20
- k3b preferably represents an integer of 1 to 6.
- k3a is more preferably an integer of 2 to 12 and particularly preferably an integer of 2 to 8 from the viewpoint of liquid crystallinity.
- k3b is more preferably an integer of 1 to 3, and particularly preferably 1 or 2, from the viewpoint of liquid crystallinity.
- LG 2 represents a leaving group.
- LG 2 is not particularly limited as long as it is a group capable of leaving by the reaction of the compound represented by the general formula (IB) and the compound represented by the general formula (IA).
- LG 2 represents a group selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carbonyloxy group, an alkoxy group, a sulfonyloxy group, or a diazonium group from the viewpoints of ease of availability, availability of raw materials, and reactivity.
- fluorine atom chlorine atom, bromine atom, iodine atom, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxy group, aryloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkyldiazonium group or aryldiazonium group
- a group selected from the group consisting of chlorine atom and bromine from the viewpoint of yield and reaction rate.
- L W1 represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, a dimethylamino group, a diethylamino group, a diisopropylamino group, or a group Any hydrogen atom therein may be substituted with a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — may each independently represent —O—, —S—, — A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- L W1 is a fluorine atom, a chlorine atom, a nitro group, a cyano group, a dimethylamino group, or one —CH 2 — or two or more that are not adjacent to each other.
- -CH 2 of - preferably represent a linear alkyl group having 12 good 1 -C be replaced by the each independently -O- or -S-, a fluorine atom, a chlorine atom, a nitro group, It is particularly preferred to represent a cyano group, a dimethylamino group, a methyl group or a methoxy group.
- r represents an integer of 0 to 4. From the viewpoint of ease of synthesis and availability of raw materials, r preferably represents an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
- the compound represented by the general formula (IA) is used in an amount of 0.01 molar equivalent to 100 mol with respect to the compound represented by the general formula (IB). It is preferable to use molar equivalents, more preferably 0.1 molar equivalents to 10 molar equivalents, more preferably 0.5 molar equivalents to 3 molar equivalents, and more preferably 0.8 molar equivalents to 1.5 molar equivalents. Is particularly preferred.
- the base is preferably used in an amount of 0.01 to 100 molar equivalents, more preferably 0.1 to 10 molar equivalents relative to the compound represented by the general formula (IB). It is more preferable to use 5 to 3 molar equivalents, and particularly preferable to use 0.8 to 1.5 molar equivalents.
- the order of addition of the compounds when the reactivity between the compound represented by the general formula (IA) and the base is high, the compound represented by the general formula (IB) and the base are mixed and then mixed. It is preferable to add a compound represented by (IA). In that case, a base may be added to the compound represented by the general formula (IB), or a compound represented by the general formula (IB) may be added to the base. On the other hand, when the reactivity between the compound represented by the general formula (IA) and the base is low, the order of addition of the compound is not particularly limited.
- the reaction temperature is preferably from ⁇ 100 ° C. to 200 ° C., more preferably from ⁇ 50 ° C. to 150 ° C., and further preferably from ⁇ 20 ° C. to 120 ° C. from the viewpoint of yield and reaction rate. Even more preferably, it is 0 ° C to 100 ° C.
- reaction solvent an organic solvent, water, an ionic liquid, a supercritical fluid may be used alone, a plurality may be used as a mixture, a two-phase system may be used, or a solventless reaction may be performed. good. From the viewpoint of yield, a reaction solvent having low reactivity with metal amide, metal hydride, metal alkoxide, or organic alkali metal is preferable.
- the organic solvent include ether, aliphatic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, alcohol, ester and the like.
- phase transfer catalyst When performing the reaction in a two-phase system of an organic solvent and water, a phase transfer catalyst can be added.
- the phase transfer catalyst include benzalkonium chloride, benzyltrimethylammonium bromide, polyoxyethylene (10) octylphenyl ether [Triton X-100], polyoxyethylene (20) sorbitan monolaurate [Tween 20], poly Oxyethylene (20) sorbitan monopalmitate [Tween 40], polyoxyethylene (20) sorbitan monostearate [Tween 60] polyoxyethylene (23) lauryl ether [Brij35], sorbitan monopalmitate [Span 40], etc. Can be mentioned.
- the amount of the reaction solvent is not particularly limited as long as the heat of reaction generated by the reaction can be sufficiently released, but if the amount of the solvent is too small, the heat of reaction accumulates in the reaction system and a by-product tends to be generated. End up. On the other hand, when there is too much quantity of a solvent, the density
- the amount of solvent is from 0.1 ml to 100 ml per gram of compound, and the amount of solvent is from 1 ml to 20 ml per gram of compound represented by formula (IB). It is more preferable that the amount of the solvent is 2 to 10 ml with respect to 1 gram of the compound represented by the general formula (IB).
- the yield of the compound represented by the general formula (IC) is 70% or more with respect to the substance amount of the compound represented by the general formula (IB) as a raw material. It can be further set to 80% or more, and can be further set to 90% or more. Further, the degree of coloration of the reaction solution after the reaction is usually derived from a by-product accompanying the reaction between the compound represented by the general formula (IB) and the compound represented by the general formula (IA). Therefore, according to the present invention, the yield of the product can be increased, and coloring of the reaction solution can be suppressed. According to the production method of the present invention, since the product purification step can be simplified or omitted, the productivity of the production step can be improved.
- the compound derived from the compound represented by the general formula (IC) is preferably a compound represented by the general formula (I).
- R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any group in the group
- a hydrogen atom may be substituted with a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH 2 —
- R 1 represents a group other than the group represented by P 1- (Sp 1 -X 1 ) k1- , from the viewpoint of liquid crystallinity and ease of synthesis, R 1 represents a hydrogen atom, a fluorine atom, a chlorine atom, Alternatively, one —CH 2 — or two or more non-adjacent —CH 2 — are each independently replaced by —O—, —COO—, —OCO—, —O—CO—O—.
- R 1 represents a group represented by P 1 — (Sp 1 -X 1 ) k1 —
- P 1 present in R 1 represents a polymerizable group, preferably radical polymerization, radical addition polymerization, Represents a group that is polymerized by cationic polymerization and anionic polymerization, and is represented by the following formulas (P-1) to (P-20):
- formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-5), formula (P ⁇ 7), formula (P-11), formula (P-13), formula (P-15) or formula (P-18) are preferred, and formula (P-1), formula (P-2), formula (P-18) P-3), formula (P-7), formula (P-11) or formula (P-13) is more preferred, and formula (P-1), formula (P-2) or formula (P-3) is more preferred. More preferred is formula (P-1) or (P-2).
- Sp 1 present in R 1 represents a spacer group, and when a plurality of Sp 1 are present, they may be the same or different.
- the spacer group one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, — CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—
- Sp 1 may be the same or different from each other when there are a plurality of Sp 1 from the viewpoint of availability of raw materials and ease of synthesis, and each is independently independent of one —CH 2 — or adjacent to each other.
- Two or more —CH 2 — are each independently —O—, —COO—, —OCO—, —OCO—O—, —CO—NH—, —NH—CO—, —CH ⁇ CH— or —
- It preferably represents an alkylene group having 1 to 20 carbon atoms which may be replaced by C ⁇ C—, and when there are a plurality thereof, they may be the same or different, and each independently represents one — CH 2 — or two or more non-adjacent —CH 2 — each independently represents an alkylene group having 1 to 10 carbon atoms which may be replaced by —O—, —COO—, or —OCO—.
- X 1 present in R 1 is —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 ⁇ 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-, —CH ⁇ CH—, —N ⁇ N—, —CH ⁇ N—N ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or a single bond, 1 they may be the same or different when there are
- X 1 s when there are a plurality of X 1 s , they may be the same or different, and —O—, —S—, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO— or a single bond is preferable.
- K1 present in R 1 represents an integer of 0 to 10, but preferably represents an integer of 0 to 5 from the viewpoint of liquid crystallinity when added to a liquid crystal composition or solubility in a solvent.
- the integer of 3 is more preferable, and 1 is particularly preferable.
- R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any group in the group
- a hydrogen atom may be substituted with a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — are each 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—
- R 1 represents a group other than the group represented by P 1- (Sp 1 -X 1 ) k1-
- the preferred structure of R 2 is the same as the preferred structure of R 1 .
- R 2 represents a group represented by — (X 2 —Sp 2 ) k2 —P 2
- preferred structures of P 2 , Sp 2 , X 2 and k2 present in R 2 are P 1 , Sp, respectively. 1 , the same as the preferred structure of X 1 and k 1 .
- a 1 and A 2 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, Naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl Represents a group, these groups may be unsubstituted or substituted by one or more substituents L, and when a plurality of A 1 are present, they may be the same or different; When two or more 2 exist, they may be the same or different.
- a 1 and A 2 may be the same or different when there are a plurality, and are each independently unsubstituted? Or preferably represents a 1,4-phenylene group, 1,4-cyclohexylene group or naphthalene-2,6-diyl group which may be substituted by one or more substituents L. Or may be different, and each of the following formulas (A-1) to (A-11)
- each L is independently a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group.
- Methylamino group dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one —CH 2 — or two or more —CH 2 — that are not adjacent to each other 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—, —CH ⁇ CH—, —CF ⁇ CF— or — C ⁇ C- Accordingly, it represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, and any hydrogen atom in the alkyl group may be substituted
- KL represents an integer of 0 to 10, and when a plurality of kL are present in the compound, they may be the same or different. From the viewpoint of liquid crystallinity and ease of synthesis, when there are a plurality of L, they may be the same or different, and a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, or a methylamino group , A dimethylamino group, a diethylamino group, a diisopropylamino group, or any hydrogen atom may be substituted with a fluorine atom, and one —CH 2 — or two or more non-adjacent —CH 2 — are each Independently selected from —O—, —S—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- the chlorine atom or any hydrogen atom represents a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, It may be the same or different, and particularly preferably represents a fluorine atom, a chlorine atom, or a linear alkyl group or linear alkoxy group having 1 to 8 carbon atoms.
- Z 1 and Z 2 are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —CO—, —COO—. , —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —OCO—NH—, —NH—COO—, — NH—CO—NH—, —NH—O—, —O—NH—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —, —OCO—
- Z 1 and Z 2 may be the same or different when there are a plurality of them, and each independently represents —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, —CH 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—, —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or a single bond is preferable, and when there are a plurality thereof, they may be the same or different, each independently -OCH 2 -,
- Z 1 and Z 2 directly bonded to M each independently represent —OCH 2 — or —CH 2 O—, and Z 1 and Z 2 not directly bonded to M each independently represent —OCH 2 —, It is particularly preferable to represent —CH 2 O—, —COO—, —OCO— or a single bond.
- m1 and m2 each independently represent an integer from 0 to 6, but m1 + m2 represents an integer from 0 to 6. From the viewpoints of solubility in a solvent, liquid crystallinity, and discoloration and orientation when irradiated with ultraviolet light, it is preferable that m1 and m2 each independently represent an integer of 1 to 3, and each independently 1 or 2 Is particularly preferred.
- M represents a trivalent aromatic group which may be substituted. From the viewpoint of ease of synthesis and availability of raw materials, M represents the following formula (M-1) to formula (M-6)
- L M is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group , dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, or one -CH 2 - or nonadjacent two or more -CH 2 - are each independently - O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—.
- L M is P LM - (Sp LM -X LM) kLM - may represent a group represented by where represents the P LM polymerizable group, preferably radical polymerization, radical addition polymerization, the polymerization is radical by cationic polymerization and anionic polymerization
- Sp LM represents a spacer group, and a preferred spacer group is the same as the above Sp 1, and when there are a plurality of Sp LMs, they may be the same or different.
- KLM represents an integer of 0 to 10, they may be the same or different if L M there are a plurality in the compound. From the viewpoint of liquid crystallinity and ease of synthesis, when a plurality of LMs are present, they may be the same or different, and each of them may be a fluorine atom, chlorine atom, pentafluorosulfuranyl group, nitro group, cyano group.
- methylamino group, dimethylamino group, diethylamino group, or any of the hydrogen atoms may be substituted by a fluorine atom, one -CH 2 - or nonadjacent two or more -CH 2 - are each Independently selected from —O—, —S—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- a linear or branched alkyl group having 1 to 20 carbon atoms that may be substituted by a group to be substituted, and when there are a plurality of them, they may be the same or different from each other, a fluorine atom, Chlorine atom, nitro group, cyano group, , Arbitrary hydrogen atom may be substituted by a fluorine atom, one -CH 2 - or nonadjacent two or more -CH 2 - are each independently -O -, - COO- or -OCO It is more preferable to represent a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by a group selected from-, and when there are a plurality thereof, they may be the same or different , A fluorine atom, a chlorine atom, a nitro group, a cyano group, or an arbitrary hydrogen atom represents a linear or branched alkyl group or alkoxy group having 1
- a plurality of them when a plurality of them are present, they may be the same or different, and particularly preferably represents a fluorine atom, a chlorine atom, a nitro group, a cyano group, a methyl group or a methoxy group.
- Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, methyl
- An amino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or 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—
- a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted is represented, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom.
- Y may be a hydrogen atom, or any hydrogen atom in the group may be substituted with a fluorine atom, one —CH 2 — or two or more non-adjacent ones.
- —CH 2 — each independently represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with —O—, —COO— or —OCO—. More preferably, it represents a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms, and Y particularly preferably represents a hydrogen atom.
- the compound represented by the general formula (I) may be a polymerizable compound or a non-polymerizable compound. However, when used as an optical film material, the compound represented by the general formula (I) is polymerized. It is preferable that it is an organic compound. In that case, it is more preferable that at least one of R 1 and R 2 has a group represented by P 1 or P 2 , and both R 1 and R 2 have a group represented by P 1 or P 2. It is particularly preferable to do this.
- R 21 is a hydrogen atom, a fluorine atom, a chlorine atom, or one —CH 2 — or two or more non-adjacent —CH 2 — are each independently —O—, —COO—, —OCO—, Represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted by —O—CO—O—, and A 11 , A 21 , A 13 , A 22 , A 23 , A 15 and A 25 are Each independently represents a 1,4-phenylene group or a 1,4-cyclohexylene group, but these groups may be unsubstituted or substituted by one or more substituents L 1 , A 12 , a 14,
- the compounds represented by the general formula (I) are represented by the following general formula (I-ia-i), general formula (I-ib-i) and general formula (I-ii-i).
- 1,4-cyclohexylene group wherein the 1,4-phenylene group may be unsubstituted or substituted by one or more substituents L 11 , where L 11 is a fluorine atom, a chlorine atom, or, one of -CH 2 - Two or more -CH 2 - not adjacent to - are each independently -O -, - CO -, - COO- or -OCO- by linear 20 good 1 -C be substituted or Represents a branched alkyl group, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and when a plurality of L 11 are present in the compound, they may be the same or different; Z 111 , Z 121 , Z 131 , Z 141 , Z 151 , Z 161 , Z 241 and Z 251 each independently represent —OCH 2 —, —CH 2 O—, —COO— or —OCO—, 211
- Y 1 represents a hydrogen atom. It is preferable that it is a compound represented by this.
- W 111 and W 121 represent a hydrogen atom or a methyl group
- Sp 111 and Sp 121 represent an alkylene group having 2 to 8
- R 212 represents a linear alkyl group having 1 to 8 carbon atoms or a straight chain. It represents an alkoxy group
- W 2 preferably represents a compound represented by the general formula (I).
- Examples of the compound represented by the general formula (I) include the following formulas (I-ia-i-1-1) to (I-ii-i-2-2)
- W 111 and W 121 represent a hydrogen atom or a methyl group
- Sp 111 and Sp 121 represent an alkylene group having 2 to 8
- R 212 represents a linear alkyl group having 1 to 8 carbon atoms or a straight chain.
- k2a1 represents an integer of 2 to 10
- k2b1 represents 1 or 2
- k2c1 represents an integer of 3 to 8
- k2d1 represents 1 or 2. Is more preferable.
- W 111 , W 121 and W 131 represent a hydrogen atom or a methyl group
- Sp 111 and Sp 121 represent an alkylene group of 2 to 8
- k2c1 represents an integer of 3 to 8
- k2d1 represents 1 or 2 is preferred
- the compound represented by the general formula (I) includes the compound represented by the above general formula (IC) and the following general formula (ID):
- R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen atom in the group.
- —CH 2 — or two or more non-adjacent —CH 2 — may each independently represent —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 ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO— CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—C H 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —C H 2 CH 2 —, —CH 2 CH 2
- R 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or any hydrogen atom in the group is a fluorine atom.
- a 1 and A 2 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl.
- L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, Mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group,
- L is P L- (Sp L -X L) kL - may represent a group represented by wherein P L represents a polymerizable group, preferably represents a radical polymerization, a radical addition polymerization, be polymerized by cationic polymerization and anionic polymerization group, Sp L each represents a spacer group, preferably the spacer group represents the same as the Sp 1, they if Sp L there are a plurality may be different even in the same, X L is -O -, - S-,
- Z 1 and Z 2 are each independently —O—, —S—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 —, —CO—, —COO—, —OCO—, —CO —S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —OCO—NH—, —NH—COO—, —NH—CO—NH—, —NH—O—, —O—NH—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 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
- the compound represented by the general formula (I) includes the first step of obtaining the compound represented by the general formula (IC) by the production method of the present invention and the obtained general formula (IC). It is preferably produced by a production method comprising a second step of reacting a compound represented by formula (ID) with a compound represented by formula (ID) to obtain a compound represented by formula (I).
- the compound represented by the general formula (I) obtained by the production method is particularly preferable as a raw material for optically anisotropic products because it has a low degree of coloring and a low impurity content derived from the first step.
- the compound represented by the general formula (ID) may be a polymerizable compound or a non-polymerizable compound, but the compound represented by the general formula (ID) is a polymerizable compound. It is preferable. In that case, it is more preferable that at least one of R 1 and R 2 has a group represented by P 1 or P 2 , and both R 1 and R 2 have a group represented by P 1 or P 2. It is particularly preferable to do this.
- the compound represented by the general formula (I-ia), the general formula (I-ib), and the general formula (I-ii) includes the compound represented by the general formula (IC) and the following: General formula (ID-ia), general formula (ID-ib) and general formula (ID-ii)
- R 21 , A 11 , A 12 , A 13, A 14, A 15 , A 16, A 21, A 22, A 23, A 24, A 25, Z 11, Z 12, Z 13, Z 14, Z 15, Z 16, Z 21, Z 22 , Z 23 , Z 24 and Z 25 are R 21 , A 11 , A 12 , A 13 , A 14 , A in general formula (I-ia), general formula (I-ib) and general formula (I-ii).
- P 1 , P 2 , Sp 1 , Sp 2 , X 1 , X 2 , k 1 and k 2 represent the same meaning as in general formula (I), and R 211 , A 111 , A 121 , A 131 , A 141 , A 151 , A 161 , A 211 , A 221 , A 231 , A 241 , A 251 , Z 111 , Z 121 , Z 131 , Z 141 , Z 151 , Z 161 , Z 211 , Z 221 , Z 231 , Z 241 , Z 251 , M 1 and Y 1 represent R 211 in the general formula (ID-ia-i), the general formula (ID-ib-i) and the general formula (ID-ii-i).
- the acid may be an inorganic acid or an organic acid.
- the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid and the like.
- the organic acid include acetic acid, formic acid, oxalic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, p-toluenesulfonic acid pyridinium, ( ⁇ ) -10-camphorsulfonic acid, and the like.
- p-toluenesulfonic acid monohydrate p-toluenesulfonic acid pyridinium, ( ⁇ ) -10-camphorsulfonic acid and the like are preferable.
- the amount of the acid added is preferably 0.001 equivalents to 10 equivalents, more preferably 0.001 equivalents to 1 equivalent, relative to the compound represented by formula (ID). Particularly preferred is 0.01 equivalent to 0.5 equivalent.
- the reaction temperature in the above reaction is preferably from ⁇ 100 ° C. to 200 ° C., more preferably from ⁇ 50 ° C. to 150 ° C., and from ⁇ 20 ° C. to 120 ° C. from the viewpoint of yield and reaction rate. Is more preferable, it is still more preferable that it is 0 degreeC to 80 degreeC, and it is especially preferable that it is room temperature to 50 degreeC.
- reaction solvent alcohol or ether is preferably used, and a mixed solvent of alcohol and ether is more preferably used. More specifically, the above-mentioned thing is mentioned.
- the reaction product can be purified as necessary after the reaction.
- the purification method include chromatography, filtration, recrystallization, distillation, sublimation, reprecipitation, adsorption, centrifugation, liquid separation treatment, and dispersion washing.
- 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.
- an inert gas such as nitrogen gas or argon gas.
- a compound represented by the following formula (C-11) to formula (C-22) was produced by the same method as described above.
- a compound represented by the formula (I-1-1) was produced by the method described in WO2012 / 147904A1.
- a reaction vessel 3.00 g of the compound represented by the formula (I-1-1), 0.97 g of the compound represented by the formula (C-2) produced in Example 2, p-toluenesulfonic acid monohydrate 0.10 g, 20 mL of tetrahydrofuran and 10 mL of 2-propanol were added, and the mixture was stirred with heating at 50 ° C. for 6 hours. Diluted with 100 mL of dichloromethane and washed with brine.
- a compound represented by the formula (I-5-1) was produced by the method described in WO2014 / 010325A1.
- a reaction vessel purged with nitrogen, 3.0 g of the compound represented by the formula (I-5-1), 0.8 g of the compound represented by the formula (C-1) produced in Example 1, ( ⁇ ) -10- 0.5 g of camphor sulfonic acid, 30 mL of tetrahydrofuran and 15 mL of ethanol were added, and the mixture was heated and stirred at 50 ° C. After the solvent was distilled off, methanol was added and the precipitated solid was filtered.
- a compound represented by the formula (I-10-4) was produced by the method described in WO2011 / 068138A1. Under a nitrogen atmosphere, 5.0 g of the compound represented by the formula (I-10-3), 4.4 g of the compound represented by the formula (I-10-4), N, N-dimethylaminopyridine 2 g, 40 mL dichloromethane was added. While cooling with ice, 2.9 g of diisopropylcarbodiimide was added dropwise and stirred. The precipitate was filtered, and the filtrate was washed with 5% hydrochloric acid and brine. Purification by column chromatography (alumina, dichloromethane) and recrystallization (dichloromethane / methanol) gave 7.2 g of a compound represented by the formula (I-10-5).
- Example 7 The compound of formula (C) prepared in Example 7 was prepared in the same manner as in Example 14 except that the compound represented by formula (I-9-13) was replaced with the compound represented by formula (I-14-2). Using the compound represented by -7), the compound represented by the formula (I-14) was produced. Transition temperature (temperature rise 5 ° C./min): C 89-95 N 145 I 1 H NMR (CDCl 3 ) ⁇ 1.24 (m, 4H), 1.65 (m, 4H), 1.91 (m, 2H), 2.05-2.25 (m, 12H), 2.
- Example 20 the compound represented by the formula (I-15-1) is converted into the compound represented by the formula (I-17-1), and the compound represented by the formula (C-1) is converted into the compound represented by the formula (I-17-1).
- a compound represented by formula (I-17) was produced by the same method except that the compound represented by formula (C-7) was replaced.
- 1 H NMR (CDCl 3 ) ⁇ 0.92 (t, 3H), 1.05-1.83 (m, 32H), 1.93 (t, 5H), 2.33 (m, 4H), 2.
- the compound represented by formula (I-18-6) was prepared in the same manner as in Example 15 except that the compound represented by formula (I-10-1) was replaced with the compound represented by formula (I-18-1). The resulting compound was prepared.
- Example 1 The compound of formula (C) prepared in Example 1 was prepared in the same manner as in Example 20 except that the compound represented by formula (I-15-4) was replaced with the compound represented by formula (I-18-8). Using the compound represented by -1), a compound represented by the formula (I-18) was produced.
- Transition temperature (temperature increase 5 ° C./min, temperature decrease 5 ° C./min): C 101-105 (N 82) I 1 H NMR (CDCl 3 ) ⁇ 0.92 (t, 3H), 1.08-1.91 (m, 26H), 2.06 (d, 2H), 2.24 (d, 2H), 2.
- the polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film.
- the obtained coating film was rubbed.
- the rubbing treatment was performed using a commercially available rubbing apparatus.
- Each produced film was irradiated with 100 J light at 50 mW / cm 2 and 25 ° C. using a xenon lamp irradiation tester (Suntest XLS manufactured by Atlas Co., Ltd.). About each obtained film, the discoloration and the change of orientation were evaluated, respectively. The evaluation results are shown in the table below.
- ⁇ discoloration> The yellowness (YI) of the film before and after light irradiation was measured to determine the yellowing degree ( ⁇ YI). For yellowness, the absorption spectrum of the polymer was measured with JASCO UV / VIS Spectrophotometer V-560, and yellowness (YI) was calculated with the attached color diagnostic program.
- the yellowing degree ( ⁇ YI) means the difference between the yellowness before light irradiation and the yellowness after light irradiation.
- the film containing the compound produced by the production method of the present invention of Example 31 to Example 55 was irradiated with ultraviolet light for a long time compared to the film containing the compound produced by the production method of the comparative example. It can be seen that discoloration and orientation change hardly occur later.
- a 2-hydrazinobenzothiazole derivative having a substituent such as an alkyl group on the nitrogen atom as an intermediate is produced by the production method of the comparative example, the color of the reaction solution during the reaction in the N-alkylation reaction step It is considered that a large by-product of the conjugated system was generated because of the dark brown to dark blue coloration.
- the compound produced by the production method of the present invention is useful as a constituent member of the polymerizable composition.
- the optical anisotropic body using the composition containing the compound of this invention is useful for uses, such as an optical film.
Abstract
Description
R2は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、シアノ基、ニトロ基、イソシアノ基、チオイソシアノ基、又は、基中の任意の水素原子がフッ素原子に置換されても良く、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-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基、若しくはR2は-(X2-Sp2)k2-P2で表される基(式中、P2は重合性基を表し、好ましくはラジカル重合、ラジカル付加重合、カチオン重合及びアニオン重合により重合する基を表し、Sp2はスペーサー基を表すが、Sp2が複数存在する場合それらは同一であっても異なっていても良く、X2は-O-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、X2が複数存在する場合それらは同一であっても異なっていても良く、k2は0から10の整数を表す。)を表し、
A1及びA2は各々独立して1,4-フェニレン基、1,4-シクロヘキシレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、ナフタレン-1,4-ジイル基、テトラヒドロナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基又は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1つ以上の置換基Lによって置換されても良く、A1が複数存在する場合それらは同一であっても異なっていても良く、A2が複数存在する場合それらは同一であっても異なっていても良く、Lはフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、又は、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-、-CH=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良く、若しくは、LはPL-(SpL-XL)kL-で表される基を表しても良く、ここでPLは重合性基を表し、好ましくはラジカル重合、ラジカル付加重合、カチオン重合及びアニオン重合により重合する基を表し、SpLはスペーサー基を表すが、好ましいスペーサー基は上記Sp1と同一のものを表し、SpLが複数存在する場合それらは同一であっても異なっていても良く、XLは-O-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、XLが複数存在する場合それらは同一であっても異なっていても良く、kLは0から10の整数を表すが、化合物内にkLが複数存在する場合それらは同一であっても異なっていても良く、
Z1及びZ2は各々独立して-O-、-S-、-OCH2-、-CH2O-、-CH2CH2-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH-O-、-O-NH-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-、-N=CH-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、Z1が複数存在する場合それらは同一であっても異なっていても良く、Z2が複数存在する場合それらは同一であっても異なっていても良く、m1及びm2は各々独立して0から6の整数を表すが、m1+m2は0から6の整数を表し、Mは置換されていても良い三価の芳香族基を表し、Yは水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基又は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-、-CH=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良いが、ただし、一般式(I-D)で表される化合物には-O-O-結合を含まない。)で表される化合物との反応によって製造されることが好ましい。
(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)、アセトニトリル/水(85:15)、0.1%ギ酸-アセトニトリル/水(90:10)又は0.1%ギ酸-アセトニトリル/水(70:30)
流速:0.4mL/min
検出器:UV(PDA)
カラムオーブン:40℃
(実施例1)式(C-1)で表される化合物の製造
(比較例1)特許文献3に記載の方法による式(C-1R)で表される化合物の製造
(実施例2)式(C-2)で表される化合物の製造
(比較例2)特許文献3に記載の方法による式(C-2R)で表される化合物の製造
(実施例3)式(C-3)で表される化合物の製造
(比較例3)特許文献3に記載の方法による式(C-3R)で表される化合物の製造
(実施例4)式(C-4)で表される化合物の製造
(比較例4)特許文献3に記載の方法による式(C-4R)で表される化合物の製造
(実施例5)式(C-5)で表される化合物の製造
(比較例5)特許文献1に記載の方法による式(C-5R)で表される化合物の製造
(実施例6)式(C-6)で表される化合物の製造
(比較例6)特許文献1に記載の方法による式(C-6R)で表される化合物の製造
(実施例7)式(C-7)で表される化合物の製造
(実施例8)式(C-8)で表される化合物の製造
(実施例9)式(C-9)で表される化合物の製造
(実施例10)式(C-10)で表される化合物の製造
(実施例12)式(I-1)で表される化合物の製造
(比較例7)式(I-1R)で表される化合物の製造
(比較例8)式(I-5R)で表される化合物の製造
転移温度(昇温5℃/分):C 85 N 128 I
1H NMR(CDCl3)δ 1.22-1.28(m,4H),1.44-1.47(m,8H),1.60-1.82(m,12H),1.90(m,2H),2.07(t,4H),2.24(d,4H),2.53(m,2H),3.30(s,3H),3.50(t,2H),3.66(t,2H),3.85-3.89(m,6H),3.93(t,4H),4.17(t,4H),4.53(t,2H),5.82(d,2H),6.13(q,2H),6.40(d,2H),6.83-6.90(m,6H),6.95-6.98(m,4H),7.14(t,1H),7.32(t,1H),7.52(t,1H),7.67(t,2H),8.33(s,1H)ppm.
(実施例15)式(I-10)で表される化合物の製造
LCMS:1186[M+1]
(実施例16)式(I-11)で表される化合物の製造
1H NMR(CDCl3)δ 1.24(m,4H),1.48-1.93(m,30H),2.08(t,4H),2.23(m,4H),2.54(m,2H),3.86(dd,4H),3.94(t,4H),4.17(t,4H),4.53(t,2H),4.65(t,2H),5.82(dd,3H),6.12(dd,3H),6.40(dd,3H),6.88(m,6H),6.97(dd,4H),7.16(t,1H),7.34(t,1H),7.54(d,1H),7.66(d,1H),7.70(d,1H),8.36(s,1H)ppm.
LCMS:1212[M+1]
(実施例17)式(I-12)で表される化合物の製造
1H NMR(CDCl3)δ 1.07(q,2H),1.24(q,2H),1.47-1.90(m,24H),2.09(m,4H),2.22(d,2H),2.39(t,1H),2.53(t,1H),3.56(t,2H),3.60-3.66(m,4H),3.73(t,2H),3.74(d,2H),3.85(d,2H),3.90(t,2H),3.94(td,4H),4.00(t,2H),4.17(td,4H),5.82(d,2H),6.13(dd,2H),6.40(d,2H),6.80-6.99(m,6H),6.98(d,4H),7.16(t,1H),7.33(t,1H),7.55(m,2H),7.67(d,1H),8.40(s,1H)ppm.
LCMS:1190[M+1]
(実施例18)式(I-13)で表される化合物の製造
転移温度(昇温速度5℃/分)C 71 N 115 I
1H NMR(CDCl3)δ 1.19-1.29(m,4H),1.41-1.82(m,22H),1.91(m,2H),2.08(m,4H),2.24(m,4H),2.53(m,2H),3.62(m,3H),3.67(m,2H),3.84-3.90(m,5H),3.94(t,4H),4.15-4.19(m,6H),4.53(t,2H),5.76(dd,1H),5.82(dd,2H),6.08(dd,1H),6.12(dd,2H),6.37(dd,1H),6.40(dd,2H),6.84-6.90(m,6H),6.95-6.98(m,4H),7.14(t,1H),7.32(t,1H),7.53(d,1H),7.65(d,1H),7.69(d,1H),8.34(s,1H)ppm.
LCMS:1244[M+1]
(実施例19)式(I-14)で表される化合物の製造
転移温度(昇温5℃/分):C 89-95 N 145 I
1H NMR(CDCl3)δ 1.24(m,4H),1.65(m,4H),1.91(m,2H),2.05-2.25(m,12H),2.55(m,2H),3.30(s,3H),3.51(m,2H),3.67(m,2H),3.84-3.89(m,6H),4.05(t,4H),4.36(t,4H),4.54(t,2H),5.84(dd,2H),6.13(dd,2H),6.41(dd,2H),6.84-6.89(m,6H),6.97-7.00(m,4H),7.14(t,1H),7.33(t,1H),7.52(d,1H),7.67(dd,2H),8.34(s,1H)ppm.
(実施例20)式(I-15)で表される化合物の製造
転移温度(昇温5℃/分):C 117-122 N 146 I
1H NMR(CDCl3)δ 0.91(m,6H),1.10(q,2H),1.23-1.56(m,18H),1.68-1.81(m,9H),1.94(t,4H),2.32(m,4H),2.56-2.70(m,3H),3.94(t,2H),4.18(t,2H),4.29(t,2H),5.82(dd,1H),6.13(dd,1H),6.40(dd,1H),6.89(d,2H),6.99(m,3H),7.16(t,1H),7.23(dd,1H),7.34(t,1H),7.66-7.72(m,3H),7.90(d,1H)ppm.
MS(m/z):878[M++1]
(実施例21)式(I-16)で表される化合物の製造
転移温度(昇温5℃/分):C 106 N 125 I
1H NMR(CDCl3)δ 0.92(t,3H),1.05-1.83(m,22H),1.93(t,5H),2.33(m,4H),2.55(m,2H),2.71(m、1H),3.30(s,3H),3.62(m,2H),3.85(t,2H),3.94(t,2H),4.17(t,2H),4.48(t,2H),5.82(dd,1H),6.12(dd,1H),6.40(dd,1H),6.88(d,2H),6.99(m,3H),7.17(t,1H),7.23(dd,1H),7.34(t,1H),7.66(d,1H),7.71(d,1H),7.89(d,1H),8.02(s,1H)ppm.
(実施例22)式(I-17)で表される化合物の製造
1H NMR(CDCl3)δ 0.92(t,3H),1.05-1.83(m,32H),1.93(t,5H),2.33(m,4H),2.55(m,2H),2.71(m、1H),3.30(s,3H),3.62(m,2H),3.85(t,2H),3.94(t,2H),4.17(t,2H),4.48(t,2H),5.82(dd,1H),6.12(dd,1H),6.40(dd,1H),6.88(d,2H),6.99(m,3H),7.17(t,1H),7.23(dd,1H),7.34(t,1H),7.66(d,1H),7.71(d,1H),7.89(d,1H),8.02(s,1H)ppm.
MS(m/z):978[M++1]
(実施例23)式(I-18)で表される化合物の製造
転移温度(昇温5℃/分):C 131 I
1H NMR(CDCl3)δ 0.88-0.94(m,6H),1.10(m,2H),1.22-1.52(m,13H),1.72(m,6H),1.94(t,4H),2.32(m,4H),2.53-2.62(m,3H),3.69-3.77(m,6H),3.86(t,2H),4.12(t,2H),4.27-4.34(m,4H),5.83(dd,1H),6.16(dd,1H),6.43(dd,1H),6.91(d,2H),6.97-7.02(m,3H),7.16(t,1H),7.23(dd,1H),7.33(t,1H),6.66-7.72(m,3H),7.90(d,1H)ppm.
LCMS:910[M+1]
(実施例24)式(I-19)で表される化合物の製造
転移温度(昇温5℃/分):C 90 S 218 N 265 I
1H NMR(CDCl3)δ 0.88(m,6H),1.01-1.19(m,8H),1.32-1.45(m,6H),1.71-1.76(m,6H),1.88-1.99(m,3H),2.17(m,12H),2.31(m,4H),2.53(m,2H),2.67(m,1H),3.70-3.76(m,6H),3.85(t,2H),4.11(t,2H),4.31(m,4H),5.82(d,2H),6.15(q,2H),6.43(d,2H),6.92(m,5H),7.14-7.26(m,2H),7.33(t,1H),7.68(m,3H),7.88(s,1H)ppm.
(実施例25)式(I-20)で表される化合物の製造
転移温度(昇温5℃/分、降温5℃/分):C 101-105(N 82)I
1H NMR(CDCl3)δ 0.92(t,3H),1.08-1.91(m,26H),2.06(d,2H),2.24(d,2H),2.51(m,2H),3.30(s,3H),3.51(dd,2H),3.67(dd,2H),3.87(quin,4H),3.94(t,2H),4.17(t,2H),4.54(t,2H),5.82(dd,1H),6.12(dd,1H),6.40(dd,1H),6.86(m,3H),6.97(m,2H),7.16(m,2H),7.32(t,1H),7.65(d,1H),7.70(d,1H),7.82(d,1H),8.36(s,1H)ppm.
(実施例26)式(I-21)で表される化合物の製造
転移温度(昇温5℃/分):C 67-100 I
1H NMR(CDCl3)δ 1.00(t,3H),1.28(m,2H),1.45-1.81(m,12H),1.97(br,1H),2.13(m,2H),2.26(m,2H),2.57(tt,1H),2.65(t,2H),3.27(s,3H),3.37(m,2H),3.50(m,2H),3.70(t,2H),3.95(q,4H),4.17(t,2H),4.33(t,2H),5.82(dd,1H),6.12(dd,1H),6.40(dd,1H),6.87(d,2H),6.98(m,3H),7.15(t,1H),7.25(m,5H),7.32(t,1H),7.64(m,2H),7.69(d,1H),7.91(s,1H)ppm.
(実施例27)式(I-22)で表される化合物の製造
LCMS:1062[M+1]
(実施例28)式(I-23)で表される化合物の製造
LCMS:1116[M+1]
(実施例29)式(I-24)で表される化合物の製造
LCMS:1146[M+1]
(実施例30)式(I-25)で表される化合物の製造
転移温度(昇温5℃/分):C 63 N 112 I
1H NMR(CDCl3)δ 1.24(m,4H),1.42-1.83(m,20H),1.91(m,2H),2.08(m,4H),2.24(m,4H),2.53(m,2H),3.74(t,2H),3.85(dd,4H),3.91-3.96(m,6H),4.17(t,4H),4.25(t,2H),4.53(t,2H),5.67(dd,1H),5.82(dd,2H),5.95(dd,1H),6.12(dd,2H),6.29(dd,1H),6.41(dd,2H),6.82-6.90(m,6H),6.96-6.99(m,4H),7.15(t,1H),7.33(t,1H),7.53(d,1H),7.67(dd,2H),8.38(s,1H)ppm.
LCMS:1200[M+1](実施例31~実施例55及び比較例9~比較例16)フィルムの作製
フィルムを作製するために、WO2012/002140A1号公報記載の化合物(X-1):20%、特表2002-542219号公報記載の化合物(X-2):20%及び特開2005-015473号公報記載の化合物(X-3):60%からなる液晶組成物を母体液晶(X)とした。
〈変色〉
光照射前と光照射後のフィルムの黄色度(YI)を各々測定し、黄変度(ΔYI)を求めた。黄色度はJASCO UV/VIS Spectrophotometer V-560で重合体の吸収スペクトルを測定し、付属のカラー診断プログラムで黄色度(YI)を計算した。計算式は、
YI=100(1.28X-1.06Z)/Y
(式中、YIは黄色度、X、Y、ZはXYZ表色系における三刺激値を表す(JIS K7373)。)である。また、黄変度(ΔYI)は光照射前の黄色度と光照射後の黄色度との差を意味する。
〈配向性の変化〉
偏光顕微鏡観察によって配向性を評価した。具体的には、各フィルムの表面において10mm×10mmの領域を任意に選択し、当該領域内において、欠陥が全く認められないフィルムをA、最も多く欠陥が認められたフィルムをEとし、配向欠陥の程度に準じてA、B、C、D、Eの5段階で評価した。ここで、Bは欠陥がごく僅か、Cは欠陥が少しあり、Dは欠陥がやや多い、ということができる。
Claims (12)
- 金属アミド、金属ヒドリド、金属アルコキシド及び有機アルカリ金属からなる群から選択される少なくとも一種の化合物の存在下、下記一般式(I-B)
下記一般式(I-A)
LG2は脱離する基を表す。)で表される化合物とを反応させる工程を含む、下記一般式(I-C)
- 一般式(I-A)において、LG2がフッ素原子、塩素原子、臭素原子、ヨウ素原子、カルボニルオキシ基、アルコキシ基、スルホニルオキシ基又はジアゾニウム基を表す、請求項1に記載の製造方法。
- 請求項1又は請求項2記載の製造方法によって下記一般式(I-C)
第1工程で得られた一般式(I-C)で表される化合物と下記一般式(I-D)
R2は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、シアノ基、ニトロ基、イソシアノ基、チオイソシアノ基、又は、基中の任意の水素原子がフッ素原子に置換されても良く、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-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基、若しくはR2は-(X2-Sp2)k2-P2で表される基(式中、P2は重合性基を表し、Sp2はスペーサー基を表すが、Sp2が複数存在する場合それらは同一であっても異なっていても良く、X2は-O-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、X2が複数存在する場合それらは同一であっても異なっていても良く、k2は0から10の整数を表す。)を表し、
A1及びA2は各々独立して1,4-フェニレン基、1,4-シクロヘキシレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、ナフタレン-1,4-ジイル基、テトラヒドロナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基又は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1つ以上の置換基Lによって置換されても良く、A1が複数存在する場合それらは同一であっても異なっていても良く、A2が複数存在する場合それらは同一であっても異なっていても良く、Lはフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、又は、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-、-CH=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良く、若しくは、LはPL-(SpL-XL)kL-で表される基を表しても良く、ここでPLは重合性基を表し、SpLはスペーサー基を表すが、SpLが複数存在する場合それらは同一であっても異なっていても良く、XLは-O-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、XLが複数存在する場合それらは同一であっても異なっていても良く、kLは0から10の整数を表すが、化合物内にkLが複数存在する場合それらは同一であっても異なっていても良く、
Z1及びZ2は各々独立して-O-、-S-、-OCH2-、-CH2O-、-CH2CH2-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH-O-、-O-NH-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-、-N=CH-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、Z1が複数存在する場合それらは同一であっても異なっていても良く、Z2が複数存在する場合それらは同一であっても異なっていても良く、m1及びm2は各々独立して0から6の整数を表すが、m1+m2は0から6の整数を表し、Mは置換されていても良い三価の芳香族基を表し、Yは水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基又は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-、-CH=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良いが、ただし、一般式(I-D)で表される化合物には-O-O-結合を含まない。)とを反応させて下記一般式(I)
(式中、R1、R2、A1、A2、Z1、Z2、m1、m2、M、Y、W2、r、LW1は前記一般式(I-C)又は上記一般式(I-D)と同じ意味を表す。)で表される化合物を得る第2工程とを含む、
一般式(I)で表される化合物の製造方法。 - 請求項1から請求項3いずれか一項に記載の製造方法によって製造された化合物から誘導される下記の一般式(I)
R1は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、シアノ基、ニトロ基、イソシアノ基、チオイソシアノ基、又は、基中の任意の水素原子がフッ素原子に置換されても良く、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-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基、若しくはR1はP1-(Sp1-X1)k1-で表される基(式中、P1は重合性基を表し、Sp1はスペーサー基を表すが、Sp1が複数存在する場合それらは同一であっても異なっていても良く、X1は-O-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、X1が複数存在する場合それらは同一であっても異なっていても良く、k1は0から10の整数を表す。)を表し、
R2は水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、シアノ基、ニトロ基、イソシアノ基、チオイソシアノ基、又は、基中の任意の水素原子がフッ素原子に置換されても良く、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-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基、若しくはR2は-(X2-Sp2)k2-P2で表される基(式中、P2は重合性基を表し、Sp2はスペーサー基を表すが、Sp2が複数存在する場合それらは同一であっても異なっていても良く、X2は-O-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、X2が複数存在する場合それらは同一であっても異なっていても良く、k2は0から10の整数を表す。)を表し、
A1及びA2は各々独立して1,4-フェニレン基、1,4-シクロヘキシレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ナフタレン-2,6-ジイル基、ナフタレン-1,4-ジイル基、テトラヒドロナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基又は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1つ以上の置換基Lによって置換されても良く、A1が複数存在する場合それらは同一であっても異なっていても良く、A2が複数存在する場合それらは同一であっても異なっていても良く、Lはフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基、又は、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-、-CH=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良く、若しくは、LはPL-(SpL-XL)kL-で表される基を表しても良く、ここでPLは重合性基を表し、SpLはスペーサー基を表すが、SpLが複数存在する場合それらは同一であっても異なっていても良く、XLは-O-、-S-、-OCH2-、-CH2O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、XLが複数存在する場合それらは同一であっても異なっていても良く、kLは0から10の整数を表すが、化合物内にkLが複数存在する場合それらは同一であっても異なっていても良く、
Z1及びZ2は各々独立して-O-、-S-、-OCH2-、-CH2O-、-CH2CH2-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH-O-、-O-NH-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-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-、-CH=CH-、-N=N-、-CH=N-、-N=CH-、-CH=N-N=CH-、-CF=CF-、-C≡C-又は単結合を表すが、Z1が複数存在する場合それらは同一であっても異なっていても良く、Z2が複数存在する場合それらは同一であっても異なっていても良く、m1及びm2は各々独立して0から6の整数を表すが、m1+m2は0から6の整数を表し、Mは置換されていても良い三価の芳香族基を表し、Yは水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基又は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-、-CH=CH-、-CF=CF-又は-C≡C-によって置換されても良い炭素原子数1から20の直鎖状又は分岐状アルキル基を表すが、当該アルキル基中の任意の水素原子はフッ素原子に置換されても良いが、ただし、一般式(I)で表される化合物には-O-O-結合を含まない。)で表される化合物。 - 一般式(I)において、存在するSp1及び存在するSp2が各々独立して、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-、-OCO-、-OCO-O-、-CO-NH-、-NH-CO-、-CH=CH-又は-C≡C-に置き換えられても良い炭素原子数1から20のアルキレン基を表す、請求項4又は請求項5に記載の化合物。
- 一般式(I)において、Mが下記の式(M-1)から式(M-6)
- 請求項4から請求項7のいずれか一項に記載の化合物を含有する組成物。
- 請求項4から請求項7のいずれか一項に記載の化合物を含有する液晶組成物。
- 請求項8又は請求項9に記載の組成物を重合することにより得られる重合体。
- 請求項10記載の重合体を用いた光学異方体。
- 請求項4から請求項7のいずれか一項に記載の化合物を用いた樹脂、樹脂添加剤、オイル、フィルター、接着剤、粘着剤、油脂、インキ、医薬品、化粧品、洗剤、建築材料、包装材、液晶材料、有機EL材料、有機半導体材料、電子材料、表示素子、電子デバイス、通信機器、自動車部品、航空機部品、機械部品、農薬及び食品並びにそれらを使用した製品。
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WO2018096938A1 (ja) * | 2016-11-22 | 2018-05-31 | 日本ゼオン株式会社 | 重合性化合物、重合性組成物、高分子、光学フィルム、光学異方体、偏光板、フラットパネル表示装置、有機エレクトロルミネッセンス表示装置、反射防止フィルム、および化合物 |
WO2018173954A1 (ja) * | 2017-03-23 | 2018-09-27 | 日本ゼオン株式会社 | 重合性化合物およびその製造方法、重合性組成物、高分子、光学フィルム、光学異方体、偏光板、表示装置、反射防止フィルム、並びに、化合物およびその使用方法 |
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WO2018096938A1 (ja) * | 2016-11-22 | 2018-05-31 | 日本ゼオン株式会社 | 重合性化合物、重合性組成物、高分子、光学フィルム、光学異方体、偏光板、フラットパネル表示装置、有機エレクトロルミネッセンス表示装置、反射防止フィルム、および化合物 |
JPWO2018096938A1 (ja) * | 2016-11-22 | 2019-10-17 | 日本ゼオン株式会社 | 重合性化合物、重合性組成物、高分子、光学フィルム、光学異方体、偏光板、フラットパネル表示装置、有機エレクトロルミネッセンス表示装置、反射防止フィルム、および化合物 |
WO2018173954A1 (ja) * | 2017-03-23 | 2018-09-27 | 日本ゼオン株式会社 | 重合性化合物およびその製造方法、重合性組成物、高分子、光学フィルム、光学異方体、偏光板、表示装置、反射防止フィルム、並びに、化合物およびその使用方法 |
JPWO2018173954A1 (ja) * | 2017-03-23 | 2020-01-23 | 日本ゼオン株式会社 | 重合性化合物およびその製造方法、重合性組成物、高分子、光学フィルム、光学異方体、偏光板、表示装置、反射防止フィルム、並びに、化合物およびその使用方法 |
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WO2019151263A1 (ja) * | 2018-02-05 | 2019-08-08 | 日本ゼオン株式会社 | 1,1-ジ置換ヒドラジン化合物の製造方法および重合性化合物の製造方法 |
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JP7110708B2 (ja) | 2018-05-08 | 2022-08-02 | 大日本印刷株式会社 | 1,1-ジ置換ヒドラジン化合物の製造方法 |
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US10968189B2 (en) | 2021-04-06 |
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