JP5556991B2 - Polymerizable compound and production intermediate of the compound - Google Patents
Polymerizable compound and production intermediate of the compound Download PDFInfo
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- JP5556991B2 JP5556991B2 JP2009169978A JP2009169978A JP5556991B2 JP 5556991 B2 JP5556991 B2 JP 5556991B2 JP 2009169978 A JP2009169978 A JP 2009169978A JP 2009169978 A JP2009169978 A JP 2009169978A JP 5556991 B2 JP5556991 B2 JP 5556991B2
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- 150000001875 compounds Chemical class 0.000 title claims description 123
- 238000004519 manufacturing process Methods 0.000 title description 26
- 239000004973 liquid crystal related substance Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 40
- -1 pyridine-2,5-diyl group Chemical group 0.000 claims description 35
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 230000003287 optical effect Effects 0.000 claims description 17
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 75
- 238000006243 chemical reaction Methods 0.000 description 65
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 239000002904 solvent Substances 0.000 description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 239000012044 organic layer Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000741 silica gel Substances 0.000 description 16
- 229910002027 silica gel Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000000746 purification Methods 0.000 description 13
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 11
- 0 [*-]c(cc1)ccc1-c(cc1)ccc1Br Chemical compound [*-]c(cc1)ccc1-c(cc1)ccc1Br 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000004988 Nematic liquid crystal Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 5
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 4
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NITWSHWHQAQBAW-QPJJXVBHSA-N (E)-4-coumaric acid methyl ester Chemical compound COC(=O)\C=C\C1=CC=C(O)C=C1 NITWSHWHQAQBAW-QPJJXVBHSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 2
- KWCPPCKBBRBYEE-UHFFFAOYSA-N 3-chloropropyl prop-2-enoate Chemical compound ClCCCOC(=O)C=C KWCPPCKBBRBYEE-UHFFFAOYSA-N 0.000 description 2
- FLPSQLAEXYKMGQ-UHFFFAOYSA-N 4-(6-prop-2-enoyloxyhexoxy)benzoic acid Chemical compound OC(=O)C1=CC=C(OCCCCCCOC(=O)C=C)C=C1 FLPSQLAEXYKMGQ-UHFFFAOYSA-N 0.000 description 2
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- YYXFJSDMOVHLMJ-UHFFFAOYSA-N (4-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(O)C=C1 YYXFJSDMOVHLMJ-UHFFFAOYSA-N 0.000 description 1
- BFHKYHMIVDBCPC-UHFFFAOYSA-N 1,3,5,7-tetrahydro-[1,3]oxazolo[3,4-c][1,3]oxazol-7a-ylmethanol Chemical compound C1OCN2COCC21CO BFHKYHMIVDBCPC-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- QSVXXQNLMJMOPL-UHFFFAOYSA-N 1-bromo-2-fluoro-4-phenylbenzene Chemical group C1=C(Br)C(F)=CC(C=2C=CC=CC=2)=C1 QSVXXQNLMJMOPL-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical class C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 1
- AYFJBMBVXWNYLT-UHFFFAOYSA-N 2-bromo-6-methoxynaphthalene Chemical compound C1=C(Br)C=CC2=CC(OC)=CC=C21 AYFJBMBVXWNYLT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HTRNHWBOBYFTQF-UHFFFAOYSA-N 4-bromo-2-fluoro-1-phenylbenzene Chemical group FC1=CC(Br)=CC=C1C1=CC=CC=C1 HTRNHWBOBYFTQF-UHFFFAOYSA-N 0.000 description 1
- AUZPKZGIOYCYNV-UHFFFAOYSA-N 6-chlorohexyl prop-2-enoate Chemical compound ClCCCCCCOC(=O)C=C AUZPKZGIOYCYNV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- IRBOCKVFXURLNE-AATRIKPKSA-N C=C/C(/Cl)=C1\[IH]CC1 Chemical compound C=C/C(/Cl)=C1\[IH]CC1 IRBOCKVFXURLNE-AATRIKPKSA-N 0.000 description 1
- IHDHQLYPXVKKDR-UHFFFAOYSA-N CC(C)(C)[ClH]C(C=C)=[ClH] Chemical compound CC(C)(C)[ClH]C(C=C)=[ClH] IHDHQLYPXVKKDR-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000005419 hydroxybenzoic acid derivatives Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Epoxy Compounds (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は重合性化合物、及び当該化合物を含有する液晶組成物、更に当該液晶組成物の硬化物である光学異方体又は液晶デバイスに関するものであり、当該重合性化合物の製造中間体である水酸基を有する芳香族化合物に関する。 The present invention relates to a polymerizable compound, a liquid crystal composition containing the compound, and an optical anisotropic body or a liquid crystal device that is a cured product of the liquid crystal composition, and a hydroxyl group that is a production intermediate of the polymerizable compound. It relates to an aromatic compound having
近年、情報化社会の進展に伴い液晶ディスプレイに必須な偏向板、位相差板などに用いられる光学補償フィルムの重要性は益々高まっており、高耐久性化、高機能化が求められている。この光学補償フィルムには重合性の液晶組成物の重合体を使用する例が報告されている。光学補償フィルム等に用いる光学異方体は光学特性だけでなく化合物の重合速度、溶解性、融点、ガラス転移点、重合物の透明性、機械的強度、表面硬度及び耐熱性なども重要な因子となる。更に液晶媒体に重合性化合物を添加して表示特性を向上させる例が報告されている。 In recent years, with the progress of the information society, the importance of optical compensation films used for deflecting plates, retardation plates and the like essential for liquid crystal displays is increasing, and high durability and high functionality are required. An example in which a polymer of a polymerizable liquid crystal composition is used for this optical compensation film has been reported. Optical anisotropic materials used for optical compensation films, etc. are not only optical properties but also important factors such as compound polymerization rate, solubility, melting point, glass transition point, polymer transparency, mechanical strength, surface hardness and heat resistance. It becomes. Furthermore, an example in which a display compound is improved by adding a polymerizable compound to a liquid crystal medium has been reported.
重合性の液晶組成物を構成する化合物として従来は、１，４−フェニレン基をエステル結合によって連結した構造を有する化合物（特許文献１参照）や、フルオレン基を有する化合物（特許文献２参照）が提案されている。しかしながら、当該引用文献記載の重合性化合物は溶解性が低い等の問題があった。一方、溶解性を向上させるために構造を非対称とした重合性化合物が開示されているが（特許文献３参照）、従来の重合性化合物と比較して溶解性の点で改善がなされているものの十分でなく、また耐熱性や機械強度が低い等の問題があった。このため更なる性能の改善が求められている。 Conventionally, as a compound constituting a polymerizable liquid crystal composition, a compound having a structure in which 1,4-phenylene groups are linked by an ester bond (see Patent Document 1) and a compound having a fluorene group (see Patent Document 2) are used. Proposed. However, the polymerizable compound described in the cited document has problems such as low solubility. On the other hand, a polymerizable compound having an asymmetric structure has been disclosed in order to improve the solubility (see Patent Document 3), but the solubility is improved as compared with a conventional polymerizable compound. There were problems such as insufficient heat resistance and low mechanical strength. For this reason, further improvement in performance is required.
また、これらの要求を改善するため重合性化合物の構造は複雑化し、その製造は困難なものとなってきた。このため、これら重合性化合物を効率的に製造するための有用な中間体の開発についても切望されていた。 Moreover, in order to improve these requirements, the structure of the polymerizable compound has become complicated and its production has become difficult. For this reason, development of the useful intermediate for manufacturing these polymeric compounds efficiently was also earnestly desired.
本発明が解決しようとする課題は、重合性の液晶組成物を構成した場合に他の重合性化合物及び液晶化合物と優れた溶解性を有し、前記重合性の液晶組成物を硬化させた場合に優れた耐熱性及び機械強度を示す重合性化合物を提供することであり、併せてこれら重合性化合物の効率的な製造を可能とする中間体を提供することである。 The problem to be solved by the present invention is that when a polymerizable liquid crystal composition is constituted, the polymerizable liquid crystal composition has excellent solubility with other polymerizable compounds and liquid crystal compounds, and the polymerizable liquid crystal composition is cured. It is to provide a polymerizable compound exhibiting excellent heat resistance and mechanical strength, and to provide an intermediate that enables efficient production of these polymerizable compounds.
本願発明者らは重合性化合物における種々の置換基の検討を行った結果、特定の構造を有する重合性化合物が前述の課題を解決できることを見出し本願発明を完成するに至った。 As a result of studying various substituents in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-described problems, and have completed the present invention.
一般式（Ｉ） Formula (I)
（ただし、Ｒ１は以下の式（Ｒ−１）から式（Ｒ−１５） (However, R 1 is the following formula (R-1) to formula (R-15)
の何れかを表し、Ｓ１は、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子、−ＣＯＯ−、−ＯＣＯ−又は−ＯＣＯＯ−に置き換えられても良い炭素数１〜１２のアルキレン基、又は単結合を表し、Ｚ１は、ＯＨ、Ｃｌ、ＯＣａＨ２ａ＋１（ａは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとして炭素原子が酸素原子に置き換えられても良い。）を表し、Ｌ１は−Ｏ−、−ＣＯＯ−、単結合、又はＯＣｂＨ２ｂ（ｂは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）を表し、Ｌ２は―ＣＨ＝ＣＨ−ＣＯ−又は―ＣＨ２ＣＨ２−ＣＯ−を表し、Ｍ１は、１，４−フェニレン基、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、１，４−シクロヘキシレン基又は４，４‘−ビフェニル基を表し、Ｍ２、及びＭ３は、お互い独立して１，４−フェニレン基、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、及びテトラヒドロナフタレン−２，６−ジイル基を表し、Ｍ１、Ｍ２及びＭ３は、お互い独立して無置換であるか又はアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲノ基、シアノ基、又はニトロ基に置換されていても良く、ｍは０、１及び２を表すが、ｍが２を表す場合、複数存在するＭ２は同一であっても異なっていても良く、ただしＭ３が１，４−フェニレン基の場合は、ｍは１又は２を表す。）で表わされる重合性化合物を提供し、更に一般式（Ｉ）で表される化合物を製造する際の重要中間体として、一般式（ＩＩ） And S 1 represents an alkylene group having 1 to 12 carbon atoms in which the methylene group may be replaced by an oxygen atom, —COO—, —OCO—, or —OCOO—, assuming that oxygen atoms are not directly bonded to each other. Or Z 1 is OH, Cl, OC a H 2a + 1 (a represents a natural number of 1 to 12, the carbon chain may be linear or branched, L 1 represents —O—, —COO—, a single bond, or OC b H 2b (b represents a natural number of 1 to 12). And the carbon chain may be linear or branched, and the methylene group may be replaced by an oxygen atom as an oxygen atom is not directly bonded to each other.), L 2 represents —CH═ CH—CO— or —CH 2 CH 2 Represents -CO-, M 1 is 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,4-cyclohexylene Group, or 4,4′-biphenyl group, and M 2 and M 3 are each independently 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene. -2,6-diyl group and tetrahydronaphthalene-2,6-diyl group, M 1 , M 2 and M 3 are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group A group, a halogeno group, a cyano group, or a nitro group, and m represents 0, 1 and 2, but when m represents 2, a plurality of M 2 may be the same or different. At best, however M 3 is 1, - For a phenylene group, m represents 1 or 2. As an important intermediate in the production of the compound represented by the general formula (I).
（ただし式中Ｚ２は、ＯＨ、Ｃｌ又はＯＣｃＨ２ｃ＋１（ｃは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）を表し、Ｓ２は、単結合、又はＣｄＨ２ｄ（ｄは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとして炭素原子が酸素原子に置き換えられても良い。）を表し、Ｌ３は−Ｏ−、−ＣＯＯ−、単結合、又はＯＣｅＨ２ｅ（ｅは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）を表し、Ｌ４は、―ＣＨ＝ＣＨ−ＣＯ−又は―ＣＨ２ＣＨ２−ＣＯ−を表し、Ｍ４及びＭ５は、お互い独立して１，４−フェニレン基、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、又はテトラヒドロナフタレン−２，６−ジイル基を表し、Ｍ４及びＭ５は、お互い独立して無置換であるか又はアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲノ基、シアノ基、又はニトロ基に置換されていても良く、ｎは０、１及び２を表すが、ｎが２を表す場合、複数存在するＭ４は同一であっても異なっていても良く、ただしＭ５が１，４−フェニレン基の場合は、ｎは１又は２を表す。）で表される水酸基を有する芳香族化合物を提供する。 (Wherein Z 2 is OH, Cl or OC c H 2c + 1 (c represents a natural number of 1 to 12, the carbon chain may be linear or branched, and oxygen atoms are directly bonded to each other) The methylene group may be replaced by an oxygen atom as a non-operating group), S 2 is a single bond, or C d H 2d (d represents a natural number of 1 to 12, and the carbon chain is linear. May be branched, or a carbon atom may be replaced by an oxygen atom assuming that oxygen atoms are not directly bonded to each other.), L 3 represents —O—, —COO—, a single bond, or OC e H 2e (e represents a natural number of 1 to 12, the carbon chain may be linear or branched, and the methylene group may be replaced by an oxygen atom as a combination of oxygen atoms not directly bonded to each other. L 4 represents —CH═CH—C. Represents O— or —CH 2 CH 2 —CO—, and M 4 and M 5 each independently represent 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, Represents a naphthalene-2,6-diyl group or a tetrahydronaphthalene-2,6-diyl group, and M 4 and M 5 are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group, It may be substituted with a halogeno group, a cyano group, or a nitro group, and n represents 0, 1 and 2, but when n represents 2, a plurality of M 4 may be the same or different. However, when M 5 is a 1,4-phenylene group, n represents 1 or 2. This provides an aromatic compound having a hydroxyl group represented by:
本願発明の水酸基を有する芳香族化合物から誘導される重合性化合物は、液晶相温度範囲が広く、他の液晶化合物との優れた溶解性を有する重合性化合物の中間体として有用である。又、本願発明の水酸基を有する芳香族化合物から誘導される重合性化合物を用いた重合性成物からなる光学異方体は、耐熱性が高く、偏向板、位相差板等の用途や、高分子安定化液晶デバイスに有用である。またこれら重合性化合物は一般式（Ｉ）で表される化合物から容易に製造することができる。 The polymerizable compound derived from the aromatic compound having a hydroxyl group of the present invention has a wide liquid crystal phase temperature range and is useful as an intermediate of a polymerizable compound having excellent solubility with other liquid crystal compounds. In addition, an optical anisotropic body made of a polymerizable composition using a polymerizable compound derived from an aromatic compound having a hydroxyl group of the present invention has high heat resistance, and is used for a polarizing plate, a retardation plate, etc. Useful for molecularly stabilized liquid crystal devices. These polymerizable compounds can be easily produced from the compound represented by formula (I).
一般式（Ｉ）において、Ｒ１は重合性基を表すが、重合性基の具体的な例としては、下記に示す構造が挙げられる。 In the general formula (I), R 1 represents a polymerizable group, and specific examples of the polymerizable group include the structures shown below.
これらの重合基はラジカル重合、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硬化する。特に重合方法として紫外線重合を行う場合には、式（Ｒ−１）、式（Ｒ−２）、式（Ｒ−４）、式（Ｒ−５）、式（Ｒ−７）、式（Ｒ−１１）、式（Ｒ−１３）又は式（Ｒ−１５）が好ましく、式（Ｒ−１）、式（Ｒ−２）、式（Ｒ−７）、式（Ｒ−１１）又は式（Ｒ−１３）がより好ましく、式（Ｒ−１）、式（Ｒ−２）がより好ましい。 These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferable, and formula (R-1) and formula (R-2) are more preferable.
Ｓ１はスペーサー基又は単結合を表すが、スペーサー基としては、炭素数１〜８のアルキレン基又は単結合が好ましく、該アルキレン基は酸素原子同士が直接結合しないものとしてメチレン基が酸素原子、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良い。優れた重合性を要求される場合には単結合が好ましく、柔軟な分子構造が要求される場合には炭素数２〜６のアルキレン基が特に好ましい。 S 1 represents a spacer group or a single bond. As the spacer group, an alkylene group having 1 to 8 carbon atoms or a single bond is preferable, and the alkylene group is a group in which oxygen atoms are not directly bonded to each other. It may be replaced by -COO-, -OCO-, or -OCOO-. A single bond is preferable when excellent polymerizability is required, and an alkylene group having 2 to 6 carbon atoms is particularly preferable when a flexible molecular structure is required.
Ｌ１は−Ｏ−、−ＣＯＯ−、単結合又はＯＣｂＨ２ｂ（ｂは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）を表し、Ｌ２は、−ＣＨ＝ＣＨ−ＣＯ−、又は−Ｃ２Ｈ４ＣＯ−を表すが、優れた重合性を要求される場合には−ＣＨ＝ＣＨ−ＣＯＯ−が好ましく、優れた相溶性を要求される場合には−Ｃ２Ｈ４−ＣＯＯ−が好ましい。Ｚ１は、ＯＨ、Ｃｌ又はＯＣａＨ２ａ＋１（ａは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良い。）を表すが、ＯＨ、Ｃｌ、ＯＣａＨ２ａ＋１（ａは１から８の自然数を表し、炭素鎖は直鎖状であっても分岐していても良い。）、Ｏ−ｔ−Ｃ４Ｈ９及びＯ−ｓ−Ｃ３Ｈ７が好ましく、ＯＨ、ＯＣａＨ２ａ＋１（ａは１から６の自然数を表し、炭素鎖は直鎖状である。）、Ｏ−ｔ−Ｃ４Ｈ９及びＯ−ｓ−Ｃ３Ｈ７が更に好ましい。
Ｍ１は、無置換であるか又はアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲノ基、シアノ基、又はニトロ基に置換されていても良い１，４−フェニレン基、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、１，４−シクロヘキシレン基、４，４‘−ビフェニル基を表し、Ｍ３、Ｍ４、Ｍ６及びＭ７は、お互い独立して無置換であるか又はアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲノ基、シアノ基、又はニトロ基に置換されていても良い１，４−フェニレン基、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、及びテトラヒドロナフタレン−２，６−ジイル基を表すが、Ｍ２及びＭ３は無置換であるか又はハロゲノ基に置換されていても良い１，４−フェニレン基及びナフタレン−２，６−ジイル基が好ましい。
L 1 is —O—, —COO—, a single bond or OC b H 2b (b represents a natural number of 1 to 12, the carbon chain may be linear or branched, and oxygen atoms may be methylene group as no direct bond may be replaced by an oxygen atom.) represent, L 2 is, -CH = CH-CO-, or -C 2 represents a H 4 CO-, excellent polymerizable preferably -CH = CH-COO- if required, -C 2 H 4 -COO- is preferred if requested excellent compatibility. Z 1 represents OH, Cl or OC a H 2a + 1 (a represents a natural number of 1 to 12, and the carbon chain may be linear or branched), but OH, Cl, OC a H 2a + 1 (a represents a natural number from 1 to 8, and the carbon chain may be linear or branched), Ot—C 4 H 9 and Os—C 3 H 7. OH, OC a H 2a + 1 (a represents a natural number of 1 to 6 and the carbon chain is linear), Ot—C 4 H 9 and Os—C 3 H 7 are further preferable.
M 1 is unsubstituted or is a 1,4-phenylene group, pyridine-2,5- which may be substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogeno group, a cyano group, or a nitro group. Represents a diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 4,4′-biphenyl group, M 3 , M 4 , M 6 and M 7 Are each independently unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogeno group, a cyano group, or a nitro group, a 1,4-phenylene group, pyridine-2, Represents a 5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, and a tetrahydronaphthalene-2,6-diyl group, wherein M 2 and M 3 are unsubstituted or halo A 1,4-phenylene group and a naphthalene-2,6-diyl group which may be substituted with a geno group are preferred.
ｍは０、１及び２を表すが、０及び１が好ましい。 m represents 0, 1 and 2, with 0 and 1 being preferred.
一般式（ＩＩ）において、Ｚ２は、ＯＨ、Ｃｌ又はＯＣｃＨ２ｃ＋１（ｃは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）を表すが、ＯＨ、Ｃｌ、ＯＣｃＨ２ｃ＋１（ｃは１から８の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）、Ｏ−ｔ−Ｃ４Ｈ９及びＯ−ｓ−Ｃ３Ｈ７が好ましく、ＯＨ、ＯＣｃＨ２ｃ＋１（ｃは１から６の自然数を表し、炭素鎖は直鎖状である。）、Ｏ−ｔ−Ｃ４Ｈ９及びＯ−ｓ−Ｃ３Ｈ７が更に好ましい。Ｓ２は、単結合、又はＣｄＨ２ｄ（ｄは１から６の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）が好ましく、Ｌ３は−Ｏ−、−ＣＯＯ−、単結合又はＯＣｅＨ２ｅ（ｅは１から１２の自然数を表し、炭素鎖は直鎖状であっても分岐していても良く、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子に置き換えられても良い。）を表し、Ｌ４は、−ＣＨ＝ＣＨ−ＣＯ−又は−ＣＨ２ＣＨ２−ＣＯ−を表し、優れた重合性を要求される場合には−ＣＨ＝ＣＨ−ＣＯ−が好ましく、相溶性を改善するには−ＣＨ２ＣＨ２−ＣＯ−が好ましい。Ｍ４及びＭ５は、お互い独立して１，４−フェニレン基、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、及びテトラヒドロナフタレン−２，６−ジイル基を表し、Ｍ１及びＭ２は、お互い独立して無置換であるか又はアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲノ基、シアノ基、又はニトロ基に置換されていても良いが、お互い独立して無置換であるか又はハロゲノ基に置換されていても良い１，４−フェニレン基、ピリミジン−２，５−ジイル基及びナフタレン−２，６−ジイル基が好ましく、無置換であるか又はハロゲノ基に置換されていても良い１，４−フェニレン基及びナフタレン−２，６−ジイル基が更に好ましく、ｎは０、１及び２を表すが、０及び１が好ましい。 In the general formula (II), Z 2 is OH, Cl or OC c H 2c + 1 (c represents a natural number of 1 to 12, the carbon chain may be linear or branched, Represents a methylene group that may be replaced by an oxygen atom as a group that is not directly bonded, but OH, Cl, OC c H 2c + 1 (c represents a natural number from 1 to 8, and the carbon chain is linear. Or may be branched, and the methylene group may be replaced by an oxygen atom as an oxygen atom is not directly bonded to each other.), Ot-C 4 H 9 and Os—C 3 H 7 Preferably, OH, OC c H 2c + 1 (c represents a natural number of 1 to 6, and the carbon chain is linear), Ot—C 4 H 9 and Os—C 3 H 7 are more preferable. . S 2 represents a single bond or C d H 2d (d represents a natural number of 1 to 6, the carbon chain may be linear or branched, and methylene as a group in which oxygen atoms are not directly bonded to each other. The group may be replaced by an oxygen atom.), L 3 is —O—, —COO—, a single bond or OC e H 2e (e represents a natural number from 1 to 12, and the carbon chain is linear. Or a branched methylene group, and a methylene group may be replaced with an oxygen atom as a group in which oxygen atoms are not directly bonded to each other.), L 4 represents —CH═CH—CO— or —CH It represents 2 CH 2 —CO—, and —CH═CH—CO— is preferred when excellent polymerizability is required, and —CH 2 CH 2 —CO— is preferred for improving compatibility. M 4 and M 5 are each independently 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, and tetrahydronaphthalene-2. , 6-diyl group, M 1 and M 2 are each independently unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogeno group, a cyano group, or a nitro group. However, a 1,4-phenylene group, a pyrimidine-2,5-diyl group, and a naphthalene-2,6-diyl group, which are independent of each other or may be substituted with a halogeno group, are preferable. More preferred are 1,4-phenylene group and naphthalene-2,6-diyl group which may be unsubstituted or substituted by a halogeno group, and n represents 0, 1 and 2, with 0 and 1 being preferred. That's right.
一般式（Ｉ）で表される重合性化合物は、具体的には、下記の一般式（Ｉ−１）〜一般式（Ｉ−２３）で表される化合物が好ましい。 Specifically, the polymerizable compound represented by the general formula (I) is preferably a compound represented by the following general formula (I-1) to general formula (I-23).
（式中、ｐは、０〜１２の整数を表すが、ｐが０であっても酸素原子同士が直接結合してしまうことはなく、この場合一方の酸素原子を除去する。）
一般式（ＩＩ）で表される化合物は、より具体的には、下記の一般式（ＩＩ−１）〜一般式（ＩＩ−２７）で表される化合物が好ましい。
(In the formula, p represents an integer of 0 to 12, but even if p is 0, oxygen atoms are not directly bonded to each other, and in this case, one oxygen atom is removed.)
More specifically, the compound represented by the general formula (II) is preferably a compound represented by the following general formula (II-1) to general formula (II-27).
（式中、ｐは、０〜１２の整数を表す。）
本発明の化合物は以下に記載する合成方法で合成することができる。
（製法１） 一般式（Ｉ−１）及び（ＩＩ−１）で表される化合物の製造
4-ブロモ-4’-ヒドロキシビフェニルとアクリル酸ターシャリーブチルとのパラジウム触媒による溝呂木−ヘック反応により、本発明の水酸基を有するビフェニル誘導体（Ｉ−１）を得ることができる。更に塩化メタアクリロイルとのエステル化反応により、本発明の重合性化合物（ＩＩ−１）を得ることができる。
(In the formula, p represents an integer of 0 to 12.)
The compound of the present invention can be synthesized by the synthesis method described below.
(Production method 1) Production of compounds represented by general formulas (I-1) and (II-1)
The biphenyl derivative (I-1) having a hydroxyl group of the present invention can be obtained by the Mizorogi-Heck reaction of 4-bromo-4'-hydroxybiphenyl and tertiary butyl acrylate with a palladium catalyst. Furthermore, the polymerizable compound (II-1) of the present invention can be obtained by an esterification reaction with methacryloyl chloride.
（製法２） 一般式（Ｉ−６）及び（ＩＩ−５）で表される化合物の製造
２−ブロモ−６−ヒドロキシナフタレンとアクリル酸ターシャリーブチルとのパラジウム触媒による溝呂木−ヘック反応により、本発明の水酸基を有するビフェニル誘導体（ＩＩ−５）を得ることができる。更に得られたビフェニル誘導体（ＩＩ−５）と６−クロロヘキシルアクリレートを炭酸カリウム等の塩基存在下でエーテル化反応させて、本発明の重合性化合物（Ｉ−６）を得ることができる。
(Production Method 2) Production of Compounds Represented by General Formulas (I-6) and (II-5) By the Mizorogi-Heck reaction of 2-bromo-6-hydroxynaphthalene and tertiary butyl acrylate with a palladium catalyst, The biphenyl derivative (II-5) having a hydroxyl group of the invention can be obtained. Furthermore, the polymerizable compound (I-6) of the present invention can be obtained by subjecting the obtained biphenyl derivative (II-5) and 6-chlorohexyl acrylate to an etherification reaction in the presence of a base such as potassium carbonate.
（製法３） 一般式（ＩＩ−７）で表される化合物の製造
６−メトキシ−２−ブロモナフタレンから調製したグリニア試薬とブロモヨウドベンゼンをパラジウム触媒存在下に反応させてフェニルナフタレン誘導体を得た後、酸により加水分解して、ナフトール誘導体を得ることができる。得られた化合物を製法２の２−ブロモ−６−ヒドロキシナフタレンに代えて使用することにより、一般式（ＩＩ−７）で表される化合物を得ることができる。
(Production Method 3) Production of Compound Represented by General Formula (II-7) A phenylnaphthalene derivative was obtained by reacting a grilinear reagent prepared from 6-methoxy-2-bromonaphthalene and bromoiodobenzene in the presence of a palladium catalyst. Thereafter, it can be hydrolyzed with an acid to obtain a naphthol derivative. By using the obtained compound in place of 2-bromo-6-hydroxynaphthalene in Production Method 2, a compound represented by the general formula (II-7) can be obtained.
（製法４） 一般式（ＩＩ−１０）で表される化合物の製造
製法３で得られた一般式（ＩＩ−７）で表される化合物をトリフルオロ酢酸により、ターシャリーブチル基を脱離させて一般式（ＩＩ−１０）で表される化合物を得ることができる。
（製法５） 一般式（ＩＩ−１５）で表される化合物の製造
上記の一般式（ＩＩ−１）で表される化合物をPd/C存在下に水素ガスと反応させることにより還元して一般式（ＩＩ−１５）で表される化合物を得ることができる。
（製法６） 一般式（ＩＩ−１７）で表される化合物の製造
製法５で得られた一般式（ＩＩ−１５）で表される化合物をトリフルオロ酢酸により、ターシャリーブチル基を脱離させて一般式（ＩＩ−１７）で表される化合物を得ることができる。
（製法７） 一般式（Ｉ−１５）で表される化合物の製造
製法１で得られた一般式（ＩＩ−１）で表される化合物を安息香酸誘導体と脱水縮合することにより一般式（Ｉ−１５）で表される化合物を得ることができる。
(Production Method 4) Production of Compound Represented by General Formula (II-10) The compound represented by General Formula (II-7) obtained by Production Method 3 was removed from the tertiary butyl group with trifluoroacetic acid. Thus, a compound represented by the general formula (II-10) can be obtained.
(Production Method 5) Production of Compound Represented by General Formula (II-15) The compound represented by General Formula (II-1) is generally reduced by reacting with hydrogen gas in the presence of Pd / C. A compound represented by the formula (II-15) can be obtained.
(Manufacturing method 6) Manufacture of the compound represented by general formula (II-17) The compound represented by general formula (II-15) obtained by manufacturing method 5 was made to detach | desorb a tertiary butyl group with trifluoroacetic acid. Thus, a compound represented by the general formula (II-17) can be obtained.
(Manufacturing method 7) Manufacture of the compound represented by general formula (I-15) The compound represented by general formula (II-1) obtained by manufacturing method 1 is dehydrated and condensed with a benzoic acid derivative. The compound represented by -15) can be obtained.
本発明の水酸基を有する芳香族化合物、及びこれらの芳香族化合物を中間体とした重合性化合物は、従来の重合性基を有する安息香酸から製造方法により、大幅に製造コストを低下させることが可能である。更に重合性基を最終工程で結合させるため副生成物を抑制でき、高純度で製造することが可能となった。また、本発明のヒドロキシ安息香酸誘導体は芳香環に別々の置換基を導入することが可能であるため、多種多様の重合性化合物を容易に製造することができるため、大変有用である。 The aromatic compound having a hydroxyl group of the present invention and the polymerizable compound having these aromatic compounds as intermediates can greatly reduce the production cost by a production method from benzoic acid having a conventional polymerizable group. It is. Furthermore, since the polymerizable group is bonded in the final step, the by-product can be suppressed, and it becomes possible to produce with high purity. In addition, the hydroxybenzoic acid derivative of the present invention is very useful because a variety of polymerizable compounds can be easily produced because different substituents can be introduced into the aromatic ring.
本願発明の化合物は、ネマチック液晶、スメクチック液晶、キラルネマチック、キラルスメクチック、及びコレステリック液晶組成物に使用できる重合性化合物及びその中間体である。本願発明の重合性化合物は、重合性官能基としてアクリロイルオキシ基、メタアクリロイルオキシ基を有するものが特に好ましい。また、本願発明の重合性化合物または中間体から合成した重合性化合物の液晶組成物がコレステリック液晶の場合は、キラル化合物の添加が好ましい。更に重合性基を有しない液晶組成物に添加しても構わなく、特に高分子安定化液晶デバイスに有用な材料である。 The compounds of the present invention are polymerizable compounds and intermediates that can be used in nematic liquid crystals, smectic liquid crystals, chiral nematics, chiral smectics, and cholesteric liquid crystal compositions. The polymerizable compound of the present invention preferably has an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group. Moreover, when the liquid crystal composition of the polymerizable compound synthesized from the polymerizable compound or intermediate of the present invention is a cholesteric liquid crystal, addition of a chiral compound is preferable. Further, it may be added to a liquid crystal composition having no polymerizable group, and is a material useful particularly for polymer-stabilized liquid crystal devices.
本発明の中間体または重合性化合物より合成できる重合性化合物の具体例を一般式（ＩＶ−１）〜一般式（ＩＶ−１０）に示す。 Specific examples of the polymerizable compound that can be synthesized from the intermediate or polymerizable compound of the present invention are shown in general formula (IV-1) to general formula (IV-10).
（式中、ｑ及びｒは、０〜１２の整数を表すが、０の場合、酸素原子が直結するものを表す場合には一つ除去する。）
本発明の重合性化合物に必要に応じた重合開始剤や安定剤を含有する液晶組成物を重合させることによって製造される光学異方体は種々の用途に利用できる。例えば、本発明及び誘導される化合物を含有する重合性液晶組成物を、配向させない状態で重合させた場合、光散乱板、偏光解消板、モアレ縞防止板として利用可能である。また、重合性液晶組成物を配向させた状態において、重合させることにより製造された光学異方体は、物理的性質に光学異方性を有しており、有用である。このような光学異方体は、例えば、重合性液晶組成物表面を、布等でラビング処理した基板、もしくは有機薄膜を形成した基板表面を布等でラビング処理した基板、あるいはＳｉＯ２を斜方蒸着した配向膜を有する基板上に担持させるか、基板間に挟持させた後、液晶組成物を重合させることによって製造することができる。
(In the formula, q and r represent integers of 0 to 12, but in the case of 0, one is removed if it represents an oxygen atom directly connected.)
The optically anisotropic body produced by polymerizing the polymerizable compound of the present invention with a liquid crystal composition containing a polymerization initiator and a stabilizer as required can be used for various applications. For example, when the polymerizable liquid crystal composition containing the present invention and the compound to be derived is polymerized in an unaligned state, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. In addition, an optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic body is, for example, a substrate in which the surface of the polymerizable liquid crystal composition is rubbed with a cloth, or a substrate surface on which an organic thin film is formed is rubbed with a cloth, or SiO 2 is oblique It can be produced by polymerizing a liquid crystal composition after it is supported on a substrate having a deposited alignment film or sandwiched between substrates.
また、上記重合性液晶組成物を非重合性の液晶素子物に添加してもよい。液晶デバイスに関しては液晶媒体に重合性化合物を添加して表示特性を向上させる例が報告されており、液晶セル内の液晶分子の配向を制御するために本願化合物を使用することもできる。具体的な組成物としては通常の液晶デバイス、例えばＳＴＮ（スーパー・ツイステッド・ネマチック）液晶や、ＴＮ（ツイステッド・ネマチック）液晶、ＴＦＴ（薄膜トランジスター）液晶等に使用されるネマチック液晶組成物、強誘電液晶組成物等が挙げられる。 The polymerizable liquid crystal composition may be added to a non-polymerizable liquid crystal element. Regarding liquid crystal devices, examples have been reported in which display characteristics are improved by adding a polymerizable compound to a liquid crystal medium, and the present compound can be used to control the alignment of liquid crystal molecules in a liquid crystal cell. Specific compositions include ordinary liquid crystal devices such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, TFT (thin film transistor) liquid crystal, etc. A liquid crystal composition etc. are mentioned.
また、重合性官能基を有する化合物であって、液晶性を示さない化合物を添加することもできる。このような化合物としては、通常、この技術分野で高分子形成性モノマーあるいは高分子形成性オリゴマーとして認識されるものであれば特に制限なく使用することができるが、その添加量は組成物として液晶性を呈するように調整する必要がある。 Moreover, it is a compound which has a polymerizable functional group, Comprising: The compound which does not show liquid crystallinity can also be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。
（実施例１）
撹拌装置、冷却器、及び温度計を備えた反応容器に４−ブロモ−４’−ヒドロキシビフェニル １０ｇ（４０．１ミリモル）、ターシャリーブチルアクリレート ６．２ｇ（４８．２ミリモル）、トリエチルアミン ４．８ｇ（４８ミリモル）、酢酸パラジウム ５３０ｍｇ、ジメチルホルムアミド ３００ｍｌを仕込み、窒素ガス雰囲気下で反応器を１００℃に加熱し反応させた。反応終了後、酢酸エチル、ＴＨＦを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（１）に示す化合物１１ｇを得た。
EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
Example 1
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 10 g (40.1 mmol) of 4-bromo-4′-hydroxybiphenyl, 6.2 g (48.2 mmol) of tertiary butyl acrylate, 4.8 g of triethylamine (48 mmol), 530 mg of palladium acetate, and 300 ml of dimethylformamide were charged, and the reaction was performed by heating the reactor to 100 ° C. in a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After the solvent was distilled off, purification was performed with a double amount (weight ratio) silica gel column to obtain 11 g of the compound represented by the formula (1).
次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（１）に示す化合物３ｇ（１０．１ミリモル）、アクリル酸クロリド １ｇ（１１ミリモル）、塩化メチレン５０ｍｌを仕込み、窒素ガス雰囲気下で反応器を５℃以下に冷却した。次いでトリエチルアミン １．２ｇ（１２ミリモル）をゆっくり滴下した。滴下終了後、２０℃以下で３時間反応させた。反応終了後、塩化メチレンを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（２）に示す化合物 ３．６ｇを得た。 Next, a reaction vessel equipped with a stirrer, a cooler and a thermometer was charged with 3 g (10.1 mmol) of the compound represented by the above formula (1), 1 g (11 mmol) of acrylic acid chloride and 50 ml of methylene chloride, and nitrogen was added. The reactor was cooled to 5 ° C. or lower under a gas atmosphere. Next, 1.2 g (12 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, methylene chloride was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 3.6 g of a compound represented by the formula (2).
更に撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（２）に示す化合物３．６ｇを塩化メチレン１０ｍｌに溶解させた後、トリフルオロ酢酸１０ｍｌを滴下し、室温で３０分攪拌した。その後、酢酸エチル２００ｍｌを加えて純水、飽和食塩水で有機層を洗浄した。溶媒を留去し式（３）に示す目的の化合物 ２．４ｇを得た。 Further, 3.6 g of the compound represented by the above formula (2) was dissolved in 10 ml of methylene chloride in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and then 10 ml of trifluoroacetic acid was added dropwise thereto at room temperature for 30 minutes. Stir. Thereafter, 200 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. The solvent was distilled off to obtain 2.4 g of the objective compound represented by formula (3).
（物性値）
１Ｈ−ＮＭＲ（溶媒：重ジメチルスルホキシド）：δ：６．１６（ｄｄ，１Ｈ）， ６．４０−６．４７（ｍ，１Ｈ），６．５４−６．６０（ｍ，２Ｈ），７．２８（ｄ，２Ｈ），７．６２（ｄ，１Ｈ），７．７１−７．８０（ｍ，６Ｈ），１２．４２（ｓ，１Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１１９．１，１２２．２，１２６．９，１２７．５，１２７．７，１２８．８，１３０．９，１３２．１，１４２．１，１５０．６，１６４．３，１６７．８
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９ｃｍ−１
融点：２４３℃
（実施例２）
撹拌装置、冷却器、及び温度計を備えた反応容器に塩化アルミニウム（III）を１２．８ｇ（９６ミリモル）、ジクロロメタン１００ｍｌを加え攪拌した。次いで塩化アセチル ８．４ｇ（１１０ミリモル）を９０分かけてゆっくり滴下し、更に４−ブロモ−２−フルオロビフェニル ２０ｇ（８０ミリモル）のジクロロメタン溶液８０ｍｌを２時間かけてゆっくり滴下した。滴下終了後、更に２時間攪拌した。反応液を５００ｍｌの氷水にゆっくり注ぎ反応を終了させた後、ジクロロメタンで抽出し、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、乾燥を行いアセチル基を導入した化合物を２３ｇ得た。次いで、撹拌装置、冷却器、及び温度計を備えた反応容器にアセチル基を導入した化合物２３ｇ、ギ酸３００ｍｌを仕込み、３４．５％の過酸化水素水２０ｍｌを加え、加熱還流を６時間行った。反応終了後、１０％の亜硫酸水素ナトリウム水溶液４５０ｍｌ行い、過酸化物を分解した。析出した固体をろ過し酢酸エチルで溶解させ水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（４）に示す化合物１８ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated dimethyl sulfoxide): δ: 6.16 (dd, 1H), 6.40-6.47 (m, 1H), 6.54-6.60 (m, 2H), 7 .28 (d, 2H), 7.62 (d, 1H), 7.71-7.80 (m, 6H), 12.42 (s, 1H)
13 C-NMR (solvent: deuterated chloroform): δ: 119.1, 122.2, 126.9, 127.5, 127.7, 128.8, 130.9, 132.1, 142.1, 150 .6, 164.3, 167.8
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm −1
Melting point: 243 ° C
(Example 2)
To a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 12.8 g (96 mmol) of aluminum (III) chloride and 100 ml of dichloromethane were added and stirred. Next, 8.4 g (110 mmol) of acetyl chloride was slowly added dropwise over 90 minutes, and further 80 ml of a dichloromethane solution of 20 g (80 mmol) of 4-bromo-2-fluorobiphenyl was slowly added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 2 hours. The reaction solution was slowly poured into 500 ml of ice water to terminate the reaction, followed by extraction with dichloromethane, and the organic layer was washed with pure water and saturated brine. After the solvent was distilled off, drying was performed to obtain 23 g of a compound having an acetyl group introduced. Next, 23 g of a compound having an acetyl group introduced therein and 300 ml of formic acid were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and 20 ml of 34.5% hydrogen peroxide solution was added, followed by heating and refluxing for 6 hours. . After completion of the reaction, 450 ml of 10% aqueous sodium bisulfite solution was used to decompose the peroxide. The precipitated solid was filtered, dissolved with ethyl acetate, and the organic layer was washed with water and saturated brine. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column to obtain 18 g of a compound represented by the formula (4).
撹拌装置、冷却器、及び温度計を備えた反応容器に４−ブロモ−３−フルオロビフェニル １０ｇ（３７．４ミリモル）、ターシャリーブチルアクリレート ５．７ｇ（４４．８ミリモル）、トリエチルアミン ５．６ｇ（５６ミリモル）、酢酸パラジウム ４１０ｍｇ、ジメチルホルムアミド ３００ｍｌを仕込み、窒素ガス雰囲気下で反応器を１００℃に加熱し反応させた。反応終了後、酢酸エチル、ＴＨＦを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（５）に示す目的の化合物１０．５ｇを得た。 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 10 g (37.4 mmol) of 4-bromo-3-fluorobiphenyl, 5.7 g (44.8 mmol) of tertiary butyl acrylate, 5.6 g of triethylamine ( 56 mmol), 410 mg of palladium acetate and 300 ml of dimethylformamide were charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 10.5 g of the desired compound represented by the formula (5).
次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（５）に示す化合物１０．５ｇ（３３．４ミリモル）、アクリル酸クロリド ３．６ｇ（４０ミリモル）、塩化メチレン１００ｍｌを仕込み、窒素ガス雰囲気下で反応器を５℃以下に冷却した。次いでトリエチルアミン ４ｇ（４０ミリモル）をゆっくり滴下した。滴下終了後、２０℃以下で３時間反応させた。反応終了後、塩化メチレンを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行いアクリル基を有する化合物 １０．５ｇを得た。 Next, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 10.5 g (33.4 mmol) of the compound represented by the above formula (5), 3.6 g (40 mmol) of acrylic acid chloride, 100 ml of methylene chloride. And the reactor was cooled to 5 ° C. or lower under a nitrogen gas atmosphere. Next, 4 g (40 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, methylene chloride was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 10.5 g of a compound having an acrylic group.
更に撹拌装置、冷却器及び温度計を備えた反応容器に、アクリル基を有する化合物 １０．５ｇを塩化メチレン２０ｍｌに溶解させた後、トリフルオロ酢酸３０ｍｌを滴下し、室温で３０分攪拌した。その後、酢酸エチル２００ｍｌを加えて純水、飽和食塩水で有機層を洗浄した。溶媒を留去し式（６）に示す化合物 ８．９ｇを得た。 Furthermore, 10.5 g of the compound having an acrylic group was dissolved in 20 ml of methylene chloride in a reaction vessel equipped with a stirrer, a cooler and a thermometer, and then 30 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. Thereafter, 200 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. The solvent was distilled off to obtain 8.9 g of a compound represented by the formula (6).
（物性値）
１Ｈ−ＮＭＲ（溶媒：重ジメチルスルホキシド）：δ：６．１７（ｄｄ，１Ｈ）， ６．４１−６．４５（ｍ，１Ｈ），６．５５−６．６９（ｍ，２Ｈ），７．３８（ｄ，２Ｈ），７．５８−７．６９（ｍ，５Ｈ），７．７４（ｄ，２Ｈ），１２．４２（ｓ，１Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１１５．１，１１５．４，１２０．８，１２２．０，１２４．９，１２７．５，１２９．９，１３０．９，１３２．１，１３３．７，１４２．１，１５０．６，１６４．３，１６７．８
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９ｃｍ−１
融点：２１８℃
（実施例３）
撹拌装置、冷却器及び温度計を備えた反応容器に、実施例１記載の式（１）に示す化合物 ２０ｇ（６７．４ミリモル）、２−ヒドロキシエチルメタクリレート １０．５ｇ（８１ミリモル）、トリフェニルホスフィン ２６．５ｇ（１００ミリモル）、ジクロロメタン ４００ｍｌを仕込み、窒素ガス雰囲気下で反応容器を１０℃以下に冷却し、ジイソプロピルアゾジカルボキシレート １６．３ｇ（８１ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し、３時間反応させた。反応終了後、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（７）に示す目的の化合物２０ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated dimethyl sulfoxide): δ: 6.17 (dd, 1H), 6.41-6.45 (m, 1H), 6.55-6.69 (m, 2H), 7 .38 (d, 2H), 7.58-7.69 (m, 5H), 7.74 (d, 2H), 12.42 (s, 1H)
13 C-NMR (solvent: deuterated chloroform): δ: 115.1, 115.4, 120.8, 122.0, 124.9, 127.5, 129.9, 130.9, 132.1, 133 .7, 142.1, 150.6, 164.3, 167.8
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm −1
Melting point: 218 ° C
(Example 3)
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 20 g (67.4 mmol) of the compound represented by the formula (1) described in Example 1, 10.5 g (81 mmol) of 2-hydroxyethyl methacrylate, triphenyl 26.5 g (100 mmol) of phosphine and 400 ml of dichloromethane were charged, the reaction vessel was cooled to 10 ° C. or lower under a nitrogen gas atmosphere, and 16.3 g (81 mmol) of diisopropyl azodicarboxylate was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 3 hours. After completion of the reaction, the organic layer was washed with pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 20 g of the desired compound represented by the formula (7).
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１．５４（ｓ，９Ｈ），１．９５（ｓ，２Ｈ）４．２５（ｔ，２Ｈ）， ４．５３（ｔ，２Ｈ），５．５９（ｄｄ，１Ｈ），６．１５（ｓ，１Ｈ），６．３７（ｄ，１Ｈ），６．９８−７．０２（ｍ，２Ｈ），７．５２−７．５９（ｍ，６Ｈ），７．６２−７．６３（ｍ，２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１８．２，２８．１，６３．０，６６．０，８０．４，１１５．０，１１９．７，１２６．０，１２６．９，１２８．１，１２８．４，１３３．０，１３３．１，１３５．９，１４２．１，１４３．０，１５８．５，１６６．３，１６７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９ ｃｍ−１
融点：１３３℃
（実施例４）
撹拌装置備えたオートクレーブ容器に、式（１）に示される実施例１で合成した中間体３．６ｇ（１２ミリモル）、５％パラジウムカーボン １８０ｍｇ、テトラヒドロフラン５０ｍｌ、エタノール５ｍｌを仕込み、０．３ＭＰａの水素にて還元反応（室温、８時間）を行った。反応液をろ過した後、溶媒を留去して水素添加された化合物３．６ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 1.54 (s, 9H), 1.95 (s, 2H) 4.25 (t, 2H), 4.53 (t, 2H), 5. 59 (dd, 1H), 6.15 (s, 1H), 6.37 (d, 1H), 6.98-7.02 (m, 2H), 7.52-759 (m, 6H) , 7.62-7.63 (m, 2H)
13 C-NMR (solvent: deuterated chloroform): δ: 18.2, 28.1, 63.0, 66.0, 80.4, 115.0, 119.7, 126.0, 126.9, 128 1,128.4, 133.0, 133.1, 135.9, 142.1, 143.0, 158.5, 166.3, 167.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm −1
Melting point: 133 ° C
(Example 4)
An autoclave vessel equipped with a stirrer was charged with 3.6 g (12 mmol) of the intermediate synthesized in Example 1 shown in formula (1), 180 mg of 5% palladium carbon, 50 ml of tetrahydrofuran, and 5 ml of ethanol, and 0.3 MPa of hydrogen The reduction reaction was carried out at room temperature (8 hours). After the reaction solution was filtered, the solvent was distilled off to obtain 3.6 g of a hydrogenated compound.
次いで撹拌装置、冷却器及び温度計を備えた反応容器に、上記の水素添加された化合物３．６ｇ（１２ミリモル）、４−（６−アクリロイルオキシヘキシルオキシ）安息香酸 ３．５ｇ（１２ミリモル）、ジメチルアミノピリジン １５０ｍｇ、ジイソプロピルカルボジイミド １．８ｇ（１４ミリモル） 塩化メチレン１５０ｍｌを仕込み、窒素ガス雰囲気下で６時間反応させた。反応終了後、塩化メチレン １００ｍｌを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（８）に示す目的の化合物４．８ｇを得た。この化合物は、９７℃〜１００℃の温度でネマチック液晶相を示した。 Next, 3.6 g (12 mmol) of the above hydrogenated compound and 3.5 g (12 mmol) of 4- (6-acryloyloxyhexyloxy) benzoic acid were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer. Dimethylaminopyridine 150 mg and diisopropylcarbodiimide 1.8 g (14 mmol) were charged with 150 ml of methylene chloride and reacted for 6 hours in a nitrogen gas atmosphere. After completion of the reaction, 100 ml of methylene chloride was added, and the organic layer was washed with 10% hydrochloric acid aqueous solution, pure water, and saturated brine. After the solvent was distilled off, the residue was purified with a double amount (weight ratio) silica gel column to obtain 4.8 g of the desired compound represented by the formula (8). This compound exhibited a nematic liquid crystal phase at a temperature of 97 ° C to 100 ° C.
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１．４３（ｓ，９Ｈ），１．４７−１．５１（ｍ，４Ｈ），１．７１−１．７５（ｍ，２Ｈ），１．８３−１．８５（ｍ，２Ｈ），２．５６（ｔ，２Ｈ），２．９３−２．９７（ｍ，２Ｈ），４．０５（ｔ，２Ｈ），４．１７（ｔ，２Ｈ），５．８１（ｄｄ，１Ｈ），６．０９−６．１６（ｍ，１Ｈ），６．３８（ｄｄ，１Ｈ），６．９５（ｄ，２Ｈ），７．２４−７．３５（ｍ，４Ｈ），７．５０（ｄ，２Ｈ），７．６０（ｄ，２Ｈ），８．１５（ｄ，２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：２５．６，２５．７，２８．０，２８．５，２８．９，３０．７，３６．９，６４．４，６８．０，８０．４，１１４．２，１２１．５，１２２．０，１２７．０，１２７．９，１２８．５，１２８．７，１３０．５，１３２．３，１３８．３，１３８．６，１３９．９，１５０．３，１６３．４，１６４．９，１７２．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９ ｃｍ−１
融点：９７℃
（実施例５）
撹拌装置、冷却器、及び温度計を備えた反応容器に４−ブロモ−４’−ヒドロキシビフェニル １０ｇ（４０．１ミリモル）、ｎ−ブチルアクリレート ７．７ｇ（６０ミリモル）、トリエチルアミン ６ｇ（６０ミリモル）、酢酸パラジウム ５３０ｍｇ、ジメチルホルムアミド ３００ｍｌを仕込み、窒素ガス雰囲気下で反応器を１００℃に加熱し反応させた。反応終了後、酢酸エチル、ＴＨＦを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（９）に示す化合物９ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 1.43 (s, 9H), 1.47-1.51 (m, 4H), 1.71-1.75 (m, 2H), 1. 83-1.85 (m, 2H), 2.56 (t, 2H), 2.93-2.97 (m, 2H), 4.05 (t, 2H), 4.17 (t, 2H) , 5.81 (dd, 1H), 6.09-6.16 (m, 1H), 6.38 (dd, 1H), 6.95 (d, 2H), 7.24-7.35 (m , 4H), 7.50 (d, 2H), 7.60 (d, 2H), 8.15 (d, 2H)
13 C-NMR (solvent: deuterated chloroform): δ: 25.6, 25.7, 28.0, 28.5, 28.9, 30.7, 36.9, 64.4, 68.0, 80 4, 114.2, 121.5, 122.0, 127.0, 127.9, 128.5, 128.7, 130.5, 132.3, 138.3, 138.6, 139.9 , 150.3, 163.4, 164.9, 172.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm −1
Melting point: 97 ° C
(Example 5)
In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 10 g (40.1 mmol) of 4-bromo-4′-hydroxybiphenyl, 7.7 g (60 mmol) of n-butyl acrylate, and 6 g (60 mmol) of triethylamine. Then, 530 mg of palladium acetate and 300 ml of dimethylformamide were charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 9 g of a compound represented by the formula (9).
撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（９）に示す化合物 ９ｇ（３０ミリモル）、４−（６−アクリロイルオキシヘキシルオキシ）安息香酸 ８．７ｇ（３０ミリモル）、ジメチルアミノピリジン ４５０ｍｇ、ジイソプロピルカルボジイミド ４．５ｇ（３６ミリモル） 塩化メチレン１５０ｍｌを仕込み、窒素ガス雰囲気下で６時間反応させた。反応終了後、応終了後、塩化メチレン １００ｍｌを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（１０）に示す目的の化合物１２ｇを得た。この化合物は、９０℃〜１９０℃まで幅広い温度でスメクチック液晶相を示した。 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 9 g (30 mmol) of the compound represented by the above formula (9), 8.7 g (30 mmol) of 4- (6-acryloyloxyhexyloxy) benzoic acid, Dimethylaminopyridine (450 mg) and diisopropylcarbodiimide (4.5 g, 36 mmol) were charged with 150 ml of methylene chloride and reacted in a nitrogen gas atmosphere for 6 hours. After completion of the reaction, after completion of the reaction, 100 ml of methylene chloride was added, and the organic layer was washed with 10% aqueous hydrochloric acid, pure water, and saturated saline. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column to obtain 12 g of the desired compound represented by the formula (10). This compound exhibited a smectic liquid crystal phase at a wide temperature range from 90 ° C to 190 ° C.
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：０．９５−０．９９（ｍ，３Ｈ），１．４４−１．４８（ｍ，６Ｈ），１．６３−１．７３（ｍ，４Ｈ），１．８３−１．９０（ｍ，２Ｈ），４．０５（ｔ，２Ｈ），４．１７−４．２４（ｍ，４Ｈ），５．８１（ｄｄ，１Ｈ），６．０９−６．１６（ｍ，１Ｈ），６．３８−６．５０（ｍ，２Ｈ），６．９６（ｄ，２Ｈ），７．２６−７．３１（ｍ，２Ｈ），７．６１（ｓ，４Ｈ），７．６２−７．６８（ｍ，２Ｈ），７．７０−７．７４（ｄ，１Ｈ），８．１４−８．１８（ｄ，２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１３．７，１９．１，２５．６，２８．５，２８．９，３０．７，６４．４，６８．０，１１４．２，１１８．１，１２１．４，１２２．２，１２７．４，１２７．４，１２８．０，１２８．５，１３０．５，１３２．４，１３７．７，１４２．１，１４３．９，１５０．９，１６３．４，１６４．８，１６６．２，１６７．０
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９ ｃｍ−１
融点：９０℃
（実施例６）
撹拌装置、冷却器、及び温度計を備えた反応容器に６−ブロモ−２−ナフトール ２０ｇ（９０ミリモル）、ターシャリーブチルアクリレート １７．２ｇ（１３４ミリモル）、トリエチルアミン １４ｇ（１３４ミリモル）、酢酸パラジウム １ｇ、ジメチルホルムアミド ３００ｍｌを仕込み、窒素ガス雰囲気下で反応器を１００℃に加熱し反応させた。反応終了後、酢酸エチル、ＴＨＦを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（１１）に示す化合物１３ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 0.95-0.99 (m, 3H), 1.44-1.48 (m, 6H), 1.63-1.73 (m, 4H) ), 1.83-1.90 (m, 2H), 4.05 (t, 2H), 4.17-4.24 (m, 4H), 5.81 (dd, 1H), 6.09- 6.16 (m, 1H), 6.38-6.50 (m, 2H), 6.96 (d, 2H), 7.26-7.31 (m, 2H), 7.61 (s, 4H), 7.62-7.68 (m, 2H), 7.70-7.74 (d, 1H), 8.14-8.18 (d, 2H)
13 C-NMR (solvent: deuterated chloroform): δ: 13.7, 19.1, 25.6, 28.5, 28.9, 30.7, 64.4, 68.0, 114.2, 118 1, 121.4, 122.2, 127.4, 127.4, 128.0, 128.5, 130.5, 132.4, 137.7, 142.1, 143.9, 150.9 , 163.4, 164.8, 166.2, 167.0
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm −1
Melting point: 90 ° C
(Example 6)
In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 20 g (90 mmol) of 6-bromo-2-naphthol, 17.2 g (134 mmol) of tertiary butyl acrylate, 14 g (134 mmol) of triethylamine, 1 g of palladium acetate Then, 300 ml of dimethylformamide was charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After the solvent was distilled off, purification was performed with a double amount (weight ratio) silica gel column to obtain 13 g of a compound represented by the formula (11).
撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（１１）に示す化合物 ７ｇ（２６ミリモル）、３−クロロプロピルアクリレート ４．６ｇ（３１ミリモル）、炭酸カリウム ４．３ｇ（３１ミリモル）、ジメチルホルムアミド １００ｍｌを仕込み、窒素ガス雰囲気下で反応器を９０℃に加熱し、６時間反応させた。反応終了後、応終了後、酢酸エチルを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行いアクリル基を有する化合物 ８ｇを得た。 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 7 g (26 mmol) of the compound represented by the above formula (11), 4.6 g (31 mmol) of 3-chloropropyl acrylate, 4.3 g of potassium carbonate (31 Mmol) and 100 ml of dimethylformamide were charged, and the reactor was heated to 90 ° C. in a nitrogen gas atmosphere and reacted for 6 hours. After completion of the reaction, after completion of the reaction, ethyl acetate was added, and the organic layer was washed with 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 8 g of a compound having an acrylic group.
更に撹拌装置、冷却器及び温度計を備えた反応容器に、アクリル基を有する化合物 １０．５ｇを塩化メチレン２０ｍｌに溶解させた後、トリフルオロ酢酸２０ｍｌを滴下し、室温で３０分攪拌した。その後、酢酸エチル３００ｍｌを加えて純水、飽和食塩水で有機層を洗浄した。その後溶媒を留去して式（１２）に示す目的の化合物 ６ｇを得た。この化合物は、１５３℃〜１８０℃まで幅広い温度でネマチック液晶相を示した。 Furthermore, 10.5 g of the compound having an acrylic group was dissolved in 20 ml of methylene chloride in a reaction vessel equipped with a stirrer, a cooler and a thermometer, and then 20 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. Thereafter, 300 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. Thereafter, the solvent was distilled off to obtain 6 g of the desired compound represented by the formula (12). This compound exhibited a nematic liquid crystal phase at a wide temperature range from 153 ° C. to 180 ° C.
（物性値）
Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：２．１７−２．２８（ｍ，２Ｈ），４．１９（ｔ，２Ｈ），４．４０−４．４３（ｍ，２Ｈ），５．８３（ｄｄ，１Ｈ），６．１１−６．１９（ｍ，１Ｈ），６．３８−６．４６（ｍ，１Ｈ），７．１３−７．２２（ｍ，２Ｈ），７．６４−７．８１（ｍ，３Ｈ），７．８９−７．９４（ｍ，２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：２８．５，６１．３，６３．２，１０６．７，１１５．９，１１９．７，１２４．２，１２７．５，１２８．３，１３０．３，１３０．９，１３１．０，１３７．７，１４７．９，１５７．０，１６３．４，１６５．０
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９ ｃｍ−１
融点：１５３℃
（参考例）重合性化合物の合成方法
撹拌装置、冷却器及び温度計を備えた反応容器に実施例３で合成した式（７）の化合物
１０ｇ（２４．４ミリモル）、トリフルオロ酢酸 ２０ｍｌ、ジクロロメタン ２０ｍｌを加え、室温で１時間攪拌した後、酢酸エチル１００ｍｌ、テトラヒドロフラン １５０ｍｍｌを加えて純水、飽和食塩水で有機層を洗浄した。溶媒を留去し淡黄色の固体を８ｇ得る。次いで、撹拌装置、冷却器及び温度計を備えた反応容器に上記の化合物 ８．５ｇ、アクリル酸＝２−（４−ヒドロキシフェニル）エチル ４．６ｇ（２４ミリモル）、ジメチルアミノピリジン ３００ｍｇ、塩化メチレン １００ｍｌを仕込み、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド ３．５ｇ（２８ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い、塩化メチレン／メタノールによる再結晶により式（１３）に示す目的の化合物１０．３ｇを得た。この化合物は、１２３℃から１８０℃以上まで幅広い温度で液晶相を示した。
(Physical property value)
H-NMR (solvent: deuterated chloroform): δ: 2.17-2.28 (m, 2H), 4.19 (t, 2H), 4.40-4.43 (m, 2H), 5.83 (Dd, 1H), 6.11-6.19 (m, 1H), 6.38-6.46 (m, 1H), 7.13-7.22 (m, 2H), 7.64-7 .81 (m, 3H), 7.89-7.94 (m, 2H)
13 C-NMR (solvent: deuterated chloroform): δ: 28.5, 61.3, 63.2, 106.7, 115.9, 119.7, 124.2, 127.5, 128.3, 130 .3, 130.9, 131.0, 137.7, 147.9, 157.0, 163.4, 165.0
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm −1
Melting point: 153 ° C
(Reference Example) Synthesis Method of Polymerizable Compound 10 g (24.4 mmol) of the compound of formula (7) synthesized in Example 3 in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 20 ml of trifluoroacetic acid, dichloromethane After adding 20 ml and stirring at room temperature for 1 hour, 100 ml of ethyl acetate and 150 ml of tetrahydrofuran were added, and the organic layer was washed with pure water and saturated brine. The solvent is distilled off to obtain 8 g of a pale yellow solid. Then, 8.5 g of the above compound, 4.6 g (24 mmol) of acrylic acid = 2- (4-hydroxyphenyl) ethyl, 300 mg of dimethylaminopyridine, methylene chloride in a reaction vessel equipped with a stirrer, a condenser and a thermometer. Charge 100 ml and keep the reaction vessel at 5 ° C or below with an ice-cooled bath. Under an atmosphere of nitrogen gas, 3.5 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified with a double amount (weight ratio) silica gel column, and 10.3 g of the desired compound represented by the formula (13) was obtained by recrystallization with methylene chloride / methanol. This compound exhibited a liquid crystal phase at a wide temperature from 123 ° C. to 180 ° C. or higher.
実施例３の中間体を用いることにより、出発原料の４−ブロモ−４’−ヒドロキシビフェニルから４工程で合成することが可能であり、総収率は５８％であった。 By using the intermediate of Example 3, it was possible to synthesize from the starting material 4-bromo-4'-hydroxybiphenyl in 4 steps, and the total yield was 58%.
（比較例）重合性化合物の合成方法
撹拌装置、冷却器、ディーンスターク及び温度計を備えた反応容器にｐ−ヒドロキシ桂皮酸 １６ｇ（１００ミリモル）、硫酸 ５ｍｌ、メタノール １００ｍｌを加え、６時間還流し、ｐ−ヒドロキシ桂皮酸メチルエステル １７ｇを得る。次いで、撹拌装置、冷却器及び温度計を備えた反応容器に上記で合成したｐ−ヒドロキシ桂皮酸メチルエステル１７ｇ、トリエチルアミン １５ｇ（１５０ミリモル）、塩化メチレン １５０ｍｌを仕込み、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でトリフルオロメタンスルホン酸無水物 ３０ｇ （１０６ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去し、式（１４）に示す化合物 ２８ｇを得た。
(Comparative example) Synthesis method of polymerizable compound To a reaction vessel equipped with a stirrer, a cooler, a Dean Stark, and a thermometer, 16 g (100 mmol) of p-hydroxycinnamic acid, 5 ml of sulfuric acid, and 100 ml of methanol were added and refluxed for 6 hours. 17 g of p-hydroxycinnamic acid methyl ester are obtained. Next, 17 g of p-hydroxycinnamic acid methyl ester synthesized above, 15 g (150 mmol) of triethylamine, and 150 ml of methylene chloride were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and the temperature was kept at 5 ° C. or less in an ice-cooled bath. Keep the reaction vessel in place. Under an atmosphere of nitrogen gas, 30 g (106 mmol) of trifluoromethanesulfonic anhydride was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 28 g of a compound represented by the formula (14).
撹拌装置、及び温度計を備えた反応容器に式（１４）の化合物２８ｇ（９０ミリモル）、水酸化ナトリウム ３．６ｇ（９０ミリモル）、メタノール ２００ｍｌ、純水 ２０ｍｌを仕込み、室温で４時間反応させた。反応終了後、反応容器に純水を加え固体を析出させた。析出物にジクロロメタン２００ｍｌ、１０％塩酸 １００ｍｌ加え、有機層を更に純水、飽和食塩水で洗浄した。有機層を留去し、式（１５）に示す化合物 １９ｇを得た。 A reaction vessel equipped with a stirrer and a thermometer was charged with 28 g (90 mmol) of the compound of formula (14), 3.6 g (90 mmol) of sodium hydroxide, 200 ml of methanol, and 20 ml of pure water, and reacted at room temperature for 4 hours. It was. After completion of the reaction, pure water was added to the reaction vessel to precipitate a solid. To the precipitate, 200 ml of dichloromethane and 100 ml of 10% hydrochloric acid were added, and the organic layer was further washed with pure water and saturated brine. The organic layer was distilled off to obtain 19 g of a compound represented by the formula (15).
撹拌装置、冷却器、ディーンスターク及び温度計を備えた反応容器にｐ−ヒドロキシフェニルエタノール １３．８ｇ（１００ミリモル）、ｐ−トルエンスルホン酸−水和物 １．９ｇ、３−クロロプロピオン酸 １４ｇ（１３０ミリモル）、トルエン１５０ｍｌを加え、６時間還流する。反応終了後、飽和炭酸水素ナトリウム、純水で洗浄後、溶媒を留去して式（１６）に示す化合物 ２１ｇを得た。 In a reaction vessel equipped with a stirrer, a condenser, a Dean Stark and a thermometer, 13.8 g (100 mmol) of p-hydroxyphenylethanol, 1.9 g of p-toluenesulfonic acid-hydrate, 14 g of 3-chloropropionic acid ( 130 mmol) and 150 ml of toluene are added and refluxed for 6 hours. After completion of the reaction, the mixture was washed with saturated sodium bicarbonate and pure water, and the solvent was distilled off to obtain 21 g of a compound represented by the formula (16).
撹拌装置、冷却器及び温度計を備えた反応容器に上記の式（１５）の化合物 １９ｇ（６４ミリモル）、式（１６）に示す３−クロロプロピオン酸＝２−（４−ヒドロキシフェニル）エチル １７．５ｇ（７６ミリモル）、ジメチルアミノピリジン １ｇ、塩化メチレン ２００ｍｌを仕込み、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド ９．５ｇ（７６ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い、式（１７）に示す目的の化合物２２．７ｇを得た。 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 19 g (64 mmol) of the compound of the above formula (15), 3-chloropropionic acid = 2- (4-hydroxyphenyl) ethyl 17 .5 g (76 mmol), 1 g of dimethylaminopyridine, and 200 ml of methylene chloride were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath. In an atmosphere of nitrogen gas, 9.5 g (76 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed with a double amount (weight ratio) silica gel column to obtain 22.7 g of the desired compound represented by the formula (17).
次いで撹拌装置、冷却器、及び温度計を備えた反応容器に式（１７）の化合物２２．７ｇ（４５ミリモル）、ｐ−ヒドロキシフェニルほう酸 ８ｇ（５７ミリモル）、炭酸カリウム １０ｇ（７０ミリモル）、トリフェニルホスフィン ２３．５ｇ（９０ミリモル）、酢酸パラジウム５００ｍｇ、テトラヒドロフラン２００ｍｌ、純水４０ｍｌを仕込み、６時間還流させた。反応終了後、反応液をろ過し、ろ液に酢酸エチル３００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、２倍量（重量比）のシリカゲルカラム、再結晶により精製を行い、式（１８）に示す化合物 ２０．３ｇを得た。 Then, 22.7 g (45 mmol) of the compound of the formula (17), 8 g (57 mmol) of p-hydroxyphenylboric acid, 10 g (70 mmol) of potassium carbonate, 23.5 g (90 mmol) of phenylphosphine, 500 mg of palladium acetate, 200 ml of tetrahydrofuran and 40 ml of pure water were charged and refluxed for 6 hours. After completion of the reaction, the reaction solution was filtered, 300 ml of ethyl acetate was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed by recrystallization using a double amount (weight ratio) silica gel column to obtain 20.3 g of a compound represented by the formula (18).
撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（１８）に示す化合物２０．３ｇ（４５ミリモル）、３−クロロプロピルアクリレート ８．７ｇ（５４ミリモル）、炭酸カリウム ９．３ｇ（６７ミリモル）、ジメチルホルムアミド １５０ｍｌを仕込み、ガス雰囲気下で反応器を９０℃に加熱し、６時間反応させた。反応終了後、応終了後、酢酸エチルを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行いメタアクリル基を有する式（１９）に示す化合物 １７ｇを得た。
更に撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（１９）に示す化合物１７ｇ（３０ミリモル）、トリエチルアミン ６ｇ（６０ミリモル）、ジクロロメタン１００ｍｌを加え、還流で５時間反応させた。反応終了後、溶媒を留去し２倍量（重量比）のシリカゲルカラムにより精製を行い式（１３）に示す目的の化合物１３．５ｇを得た。 Furthermore, 17 g (30 mmol) of the compound represented by the above formula (19), 6 g (60 mmol) of triethylamine and 100 ml of dichloromethane were added to a reaction vessel equipped with a stirrer, a cooler and a thermometer, and reacted at reflux for 5 hours. . After completion of the reaction, the solvent was distilled off and the residue was purified with a double amount (weight ratio) silica gel column to obtain 13.5 g of the desired compound represented by the formula (13).
比較例１に示した合成方法では、目的物である重合性化合物を得るために８工程必要であり、且つ収率（総収率２５％）も悪かった。
（実施例７）
以下に示す組成の重合性液晶組成物（組成物１）を調製した。
In the synthesis method shown in Comparative Example 1, 8 steps were required to obtain the target polymerizable compound, and the yield (total yield 25%) was also poor.
(Example 7)
A polymerizable liquid crystal composition (Composition 1) having the following composition was prepared.
重合性液晶組成物は、良好な相溶安定性を有し、ネマチック液晶相を示した。この組成物に光重合開始剤 イルガキュアー９０７（チバスペシャリティーケミカル社製）を３％添加して重合性液晶組成物（組成物２）を調製した。この組成物２のシクロヘキサノン溶液を、ポリイミド付きガラスにスピンコートし、これに高圧水銀ランプを用いて４ｍＷ／ｃｍ２の紫外線を１２０秒間照射した後、１８０℃で３０分加熱した。得られた光学異方体は、均一な配向状態を保っていた。この光学異方体の表面硬度（ＪＩＳ−Ｓ−Ｋ−５４００による）はＨであった。得られた光学異方体の加熱前の位相差を１００％としたとき、２４０℃、１時間加熱後の位相差は８９％であり、位相差減少率は１１％だった。本発明のターシャリーブチル基を有する化合物は、高温で加熱することによりタシャリーブチル基が脱離し、カルボン酸を生成することができる。その結果、生成したカルボン酸による水素結合により位相差の減少を抑制することができた。
（比較例２）
以下に示す組成の重合性液晶組成物（組成物３）を調製した。
(Comparative Example 2)
A polymerizable liquid crystal composition (Composition 3) having the following composition was prepared.
重合性液晶組成物は、良好な相溶安定性を有し、ネマチック液晶相を示した。この組成物に光重合開始剤 イルガキュアー９０７（チバスペシャリティーケミカル社製）を３％添加して重合性液晶組成物（組成物４）を調製した。この組成物４のシクロヘキサノン溶液を、ポリイミド付きガラスにスピンコートし、これに高圧水銀ランプを用いて４ｍＷ／ｃｍ２の紫外線を１２０秒間照射した後、１８０℃で３０分加熱した。得られた光学異方体は、均一な配向状態を保っていた。この光学異方体の表面硬度（ＪＩＳ−Ｓ−Ｋ−５４００による）はＢであった。得られた光学異方体の加熱前の位相差を１００％としたとき、２４０℃、１時間加熱後の位相差は７１％であり、位相差減少率は２９％だった。水素結合による配向規制力がないため、位相差の減少が大きかった。 The polymerizable liquid crystal composition had good compatibility stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 3% to prepare a polymerizable liquid crystal composition (Composition 4). The cyclohexanone solution of this composition 4 was spin-coated on a glass with polyimide, irradiated with 4 mW / cm 2 of ultraviolet rays for 120 seconds using a high-pressure mercury lamp, and then heated at 180 ° C. for 30 minutes. The obtained optical anisotropic body maintained a uniform alignment state. The surface hardness (according to JIS-S-K-5400) of this optical anisotropic body was B. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 71%, and the phase difference reduction rate was 29%. Since there was no orientation regulating force due to hydrogen bonding, the phase difference was greatly reduced.
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