JPH0776195B2 - Fluorine-substituted biphenyl derivative and liquid crystal composition - Google Patents
Fluorine-substituted biphenyl derivative and liquid crystal compositionInfo
- Publication number
- JPH0776195B2 JPH0776195B2 JP63327755A JP32775588A JPH0776195B2 JP H0776195 B2 JPH0776195 B2 JP H0776195B2 JP 63327755 A JP63327755 A JP 63327755A JP 32775588 A JP32775588 A JP 32775588A JP H0776195 B2 JPH0776195 B2 JP H0776195B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoro
- methylhexyl
- product
- oxy
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 Fluorine-substituted biphenyl Chemical class 0.000 title claims description 116
- 239000000203 mixture Substances 0.000 title claims description 45
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims 3
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 239000000047 product Substances 0.000 description 104
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 83
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 239000002994 raw material Substances 0.000 description 54
- 238000004128 high performance liquid chromatography Methods 0.000 description 52
- 239000000126 substance Substances 0.000 description 52
- 238000004458 analytical method Methods 0.000 description 51
- 150000001793 charged compounds Chemical class 0.000 description 51
- 239000013076 target substance Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 46
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 29
- 238000000034 method Methods 0.000 description 28
- 229910052938 sodium sulfate Inorganic materials 0.000 description 28
- 235000011152 sodium sulphate Nutrition 0.000 description 28
- 239000002904 solvent Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- HFRUPPHPJRZOCM-UHFFFAOYSA-N 4-octoxyphenol Chemical compound CCCCCCCCOC1=CC=C(O)C=C1 HFRUPPHPJRZOCM-UHFFFAOYSA-N 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000003480 eluent Substances 0.000 description 15
- IALWCYFULVHLEC-UHFFFAOYSA-N 4-(octyloxy)benzoic acid Chemical compound CCCCCCCCOC1=CC=C(C(O)=O)C=C1 IALWCYFULVHLEC-UHFFFAOYSA-N 0.000 description 14
- 238000010898 silica gel chromatography Methods 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- GCQBIYCSSJYFJX-VIFPVBQESA-N 4-[(2s)-2-methylbutoxy]phenol Chemical compound CC[C@H](C)COC1=CC=C(O)C=C1 GCQBIYCSSJYFJX-VIFPVBQESA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000004990 Smectic liquid crystal Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- QGXAKXCLPXKZQY-AWEZNQCLSA-N 4-bromo-2-fluoro-1-[4-[(4s)-4-methylhexoxy]phenyl]benzene Chemical group C1=CC(OCCC[C@@H](C)CC)=CC=C1C1=CC=C(Br)C=C1F QGXAKXCLPXKZQY-AWEZNQCLSA-N 0.000 description 7
- 239000007818 Grignard reagent Substances 0.000 description 7
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 7
- 150000004795 grignard reagents Chemical class 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- QIXNVYCYRYRCAK-ZETCQYMHSA-N (4s)-1-bromo-4-methylhexane Chemical compound CC[C@H](C)CCCBr QIXNVYCYRYRCAK-ZETCQYMHSA-N 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- IOHLFWGBBXATQA-UHFFFAOYSA-N 4-bromo-2-fluoro-1-octoxybenzene Chemical compound CCCCCCCCOC1=CC=C(Br)C=C1F IOHLFWGBBXATQA-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001347 alkyl bromides Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- XVICHYQFMAVOKG-UHFFFAOYSA-N 4-decoxy-3-fluorobenzoic acid Chemical compound CCCCCCCCCCOC1=CC=C(C(O)=O)C=C1F XVICHYQFMAVOKG-UHFFFAOYSA-N 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 3
- CMAFZMCNXATNCV-UHFFFAOYSA-N 3-fluoro-4-octoxyphenol Chemical compound CCCCCCCCOC1=CC=C(O)C=C1F CMAFZMCNXATNCV-UHFFFAOYSA-N 0.000 description 3
- JZTPKAROPNTQQV-UHFFFAOYSA-N 3-fluorobenzonitrile Chemical compound FC1=CC=CC(C#N)=C1 JZTPKAROPNTQQV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- NSEVTLJIOWRDEU-UHFFFAOYSA-N 4-bromo-1-decoxy-2-fluorobenzene Chemical compound CCCCCCCCCCOC1=CC=C(Br)C=C1F NSEVTLJIOWRDEU-UHFFFAOYSA-N 0.000 description 3
- QTMHHQFADWIZCP-UHFFFAOYSA-N 4-decanoyloxybenzoic acid Chemical compound CCCCCCCCCC(=O)OC1=CC=C(C(O)=O)C=C1 QTMHHQFADWIZCP-UHFFFAOYSA-N 0.000 description 3
- NWHKQJPPILAVDT-UHFFFAOYSA-N 4-decoxyphenol Chemical compound CCCCCCCCCCOC1=CC=C(O)C=C1 NWHKQJPPILAVDT-UHFFFAOYSA-N 0.000 description 3
- RTRTWCIWPQFYDU-UHFFFAOYSA-N 4-decylbenzoic acid Chemical compound CCCCCCCCCCC1=CC=C(C(O)=O)C=C1 RTRTWCIWPQFYDU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229930195143 oxyphenol Natural products 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LSQXKKKWXIJEPM-UHFFFAOYSA-N 1-(2-fluoro-4-hydroxyphenyl)pentan-1-one Chemical compound CCCCC(=O)c1ccc(O)cc1F LSQXKKKWXIJEPM-UHFFFAOYSA-N 0.000 description 2
- LQASUDVYVOFKNK-UHFFFAOYSA-N 1-(3-fluoro-4-methoxyphenyl)ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1F LQASUDVYVOFKNK-UHFFFAOYSA-N 0.000 description 2
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 2
- NXWTWYULZRDBSA-UHFFFAOYSA-N 2-fluoro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1F NXWTWYULZRDBSA-UHFFFAOYSA-N 0.000 description 2
- KSUDMDCPWIYYNA-UHFFFAOYSA-N 2-fluoro-4-pentylphenol Chemical group CCCCCC1=CC=C(O)C(F)=C1 KSUDMDCPWIYYNA-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- XTZUFTFMACDIKN-LBPRGKRZSA-N 4-[(2s)-octan-2-yl]oxyphenol Chemical compound CCCCCC[C@H](C)OC1=CC=C(O)C=C1 XTZUFTFMACDIKN-LBPRGKRZSA-N 0.000 description 2
- SRXCVQYPECLZSS-UHFFFAOYSA-N 4-bromo-2-fluoro-1-(4-methylhexoxy)benzene Chemical compound CCC(C)CCCOC1=CC=C(Br)C=C1F SRXCVQYPECLZSS-UHFFFAOYSA-N 0.000 description 2
- IKXWLRNTFXFKMR-UHFFFAOYSA-N 4-decoxy-3-fluorophenol Chemical compound FC=1C=C(C=CC1OCCCCCCCCCC)O IKXWLRNTFXFKMR-UHFFFAOYSA-N 0.000 description 2
- CGTLMVREWQIWEC-UHFFFAOYSA-N 4-decylphenol Chemical compound CCCCCCCCCCC1=CC=C(O)C=C1 CGTLMVREWQIWEC-UHFFFAOYSA-N 0.000 description 2
- FHXJDKPJCDJBEM-UHFFFAOYSA-N 4-dodecoxyphenol Chemical compound CCCCCCCCCCCCOC1=CC=C(O)C=C1 FHXJDKPJCDJBEM-UHFFFAOYSA-N 0.000 description 2
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 2
- ZQLDNJKHLQOJGE-UHFFFAOYSA-M 4-octylbenzoate Chemical compound CCCCCCCCC1=CC=C(C([O-])=O)C=C1 ZQLDNJKHLQOJGE-UHFFFAOYSA-M 0.000 description 2
- ZQLDNJKHLQOJGE-UHFFFAOYSA-N 4-octylbenzoic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C=C1 ZQLDNJKHLQOJGE-UHFFFAOYSA-N 0.000 description 2
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 2
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005661 deetherification reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 150000005419 hydroxybenzoic acid derivatives Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QPRQEDXDYOZYLA-YFKPBYRVSA-N (S)-2-methylbutan-1-ol Chemical compound CC[C@H](C)CO QPRQEDXDYOZYLA-YFKPBYRVSA-N 0.000 description 1
- GSWTXZXGONEVJC-UHFFFAOYSA-N 1-(3-fluoro-4-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC=C(O)C(F)=C1 GSWTXZXGONEVJC-UHFFFAOYSA-N 0.000 description 1
- IAUANGRAOJIIBJ-UHFFFAOYSA-N 1-bromo-4-(2-fluorophenyl)benzene Chemical group FC1=CC=CC=C1C1=CC=C(Br)C=C1 IAUANGRAOJIIBJ-UHFFFAOYSA-N 0.000 description 1
- VIGAGZWJPRGWLQ-UHFFFAOYSA-N 1-phenyl-2-phenylmethoxybenzene Chemical group C=1C=CC=CC=1COC1=CC=CC=C1C1=CC=CC=C1 VIGAGZWJPRGWLQ-UHFFFAOYSA-N 0.000 description 1
- RIPIEQMRLBWTBL-UHFFFAOYSA-N 2-(4-methylhexoxy)benzoic acid Chemical compound CCC(C)CCCOC1=CC=CC=C1C(O)=O RIPIEQMRLBWTBL-UHFFFAOYSA-N 0.000 description 1
- REIVHYDACHXPNH-UHFFFAOYSA-N 2-fluoro-4-hydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C(F)=C1 REIVHYDACHXPNH-UHFFFAOYSA-N 0.000 description 1
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 description 1
- GDHXJNRAJRCGMX-UHFFFAOYSA-N 2-fluorobenzonitrile Chemical compound FC1=CC=CC=C1C#N GDHXJNRAJRCGMX-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- TURLXGVYWLLOPE-UHFFFAOYSA-N 3-fluoro-4-(4-octoxyphenyl)benzoic acid Chemical compound C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1F TURLXGVYWLLOPE-UHFFFAOYSA-N 0.000 description 1
- SQVFTDZEUGEJTQ-UHFFFAOYSA-N 3-fluoro-4-octoxybenzoic acid Chemical compound CCCCCCCCOC1=CC=C(C(O)=O)C=C1F SQVFTDZEUGEJTQ-UHFFFAOYSA-N 0.000 description 1
- QDWUZICREGZAKA-UHFFFAOYSA-N 3-fluoro-4-octylbenzoic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C=C1F QDWUZICREGZAKA-UHFFFAOYSA-N 0.000 description 1
- FEZWWSBZGCLPMD-UHFFFAOYSA-N 3-fluoro-4-pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1F FEZWWSBZGCLPMD-UHFFFAOYSA-N 0.000 description 1
- PFKITESTTSWHMP-UHFFFAOYSA-N 3-fluoro-4-phenylbenzoic acid Chemical compound FC1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 PFKITESTTSWHMP-UHFFFAOYSA-N 0.000 description 1
- IBMLGDKPIPQNME-UHFFFAOYSA-N 3-fluoro-4-phenylbenzonitrile Chemical group FC1=CC(C#N)=CC=C1C1=CC=CC=C1 IBMLGDKPIPQNME-UHFFFAOYSA-N 0.000 description 1
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- GTQZUSKKYDNKNK-UHFFFAOYSA-N 3-hexoxy-6-hydroxybenzene-1,2-dicarbonitrile Chemical compound CCCCCCOC1=CC=C(O)C(C#N)=C1C#N GTQZUSKKYDNKNK-UHFFFAOYSA-N 0.000 description 1
- SLKZDWAZOKIEEU-UHFFFAOYSA-N 4-(2-fluorophenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1F SLKZDWAZOKIEEU-UHFFFAOYSA-N 0.000 description 1
- WOIQLQNFGBYUQN-UHFFFAOYSA-N 4-(4-bromo-2-fluorophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1F WOIQLQNFGBYUQN-UHFFFAOYSA-N 0.000 description 1
- XXKSCUHKAVDSLW-UHFFFAOYSA-N 4-(4-bromophenyl)-3-fluorophenol Chemical group FC1=CC(O)=CC=C1C1=CC=C(Br)C=C1 XXKSCUHKAVDSLW-UHFFFAOYSA-N 0.000 description 1
- LXTQQCAUJMFTGK-UHFFFAOYSA-N 4-(4-decoxyphenyl)-3-fluorobenzoic acid Chemical compound C1=CC(OCCCCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1F LXTQQCAUJMFTGK-UHFFFAOYSA-N 0.000 description 1
- KPIPGSRBWWHXFH-NSHDSACASA-N 4-[(4s)-4-methylhexoxy]phenol Chemical compound CC[C@H](C)CCCOC1=CC=C(O)C=C1 KPIPGSRBWWHXFH-NSHDSACASA-N 0.000 description 1
- ZFYJFIXRMANMPW-UHFFFAOYSA-N 4-bromo-1-(4-decoxyphenyl)-2-fluorobenzene Chemical group C1=CC(OCCCCCCCCCC)=CC=C1C1=CC=C(Br)C=C1F ZFYJFIXRMANMPW-UHFFFAOYSA-N 0.000 description 1
- SRXCVQYPECLZSS-JTQLQIEISA-N 4-bromo-2-fluoro-1-[(4s)-4-methylhexoxy]benzene Chemical compound CC[C@H](C)CCCOC1=CC=C(Br)C=C1F SRXCVQYPECLZSS-JTQLQIEISA-N 0.000 description 1
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 1
- NEJZHJHZOUISSH-UHFFFAOYSA-N 4-undecoxybenzoic acid Chemical compound CCCCCCCCCCCOC1=CC=C(C(O)=O)C=C1 NEJZHJHZOUISSH-UHFFFAOYSA-N 0.000 description 1
- WHFLFRUGRPYTAF-UHFFFAOYSA-N 4-undecylbenzoic acid Chemical compound CCCCCCCCCCCC1=CC=C(C(O)=O)C=C1 WHFLFRUGRPYTAF-UHFFFAOYSA-N 0.000 description 1
- FEJJTZXKVURRKH-AWEZNQCLSA-N CC[C@H](C)CCCOC1=CC=C(C=C1)C2=C(C=C(C=C2)O)F Chemical group CC[C@H](C)CCCOC1=CC=C(C=C1)C2=C(C=C(C=C2)O)F FEJJTZXKVURRKH-AWEZNQCLSA-N 0.000 description 1
- BGCIDGIZZUQTDR-HNNXBMFYSA-N C[C@@H](CCCCC)OC1=CC=C(C=C1)C1=C(C=C(C=C1)C#N)F Chemical group C[C@@H](CCCCC)OC1=CC=C(C=C1)C1=C(C=C(C=C1)C#N)F BGCIDGIZZUQTDR-HNNXBMFYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YNJWKWKTYUQIEO-CYBMUJFWSA-N [(2r)-heptan-2-yl] 4-methylbenzenesulfonate Chemical compound CCCCC[C@@H](C)OS(=O)(=O)C1=CC=C(C)C=C1 YNJWKWKTYUQIEO-CYBMUJFWSA-N 0.000 description 1
- YCVMFKRVGOAHAA-VIFPVBQESA-N [(2s)-2-methylbutyl] 4-hydroxybenzoate Chemical compound CC[C@H](C)COC(=O)C1=CC=C(O)C=C1 YCVMFKRVGOAHAA-VIFPVBQESA-N 0.000 description 1
- YNJWKWKTYUQIEO-ZDUSSCGKSA-N [(2s)-heptan-2-yl] 4-methylbenzenesulfonate Chemical compound CCCCC[C@H](C)OS(=O)(=O)C1=CC=C(C)C=C1 YNJWKWKTYUQIEO-ZDUSSCGKSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- NKCLRAOPRANQDM-UHFFFAOYSA-N decan-4-yl benzoate Chemical compound CCCCCCC(CCC)OC(=O)C1=CC=CC=C1 NKCLRAOPRANQDM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- OSTIHFXUTPZJQL-UHFFFAOYSA-N fluoro benzoate Chemical compound FOC(=O)C1=CC=CC=C1 OSTIHFXUTPZJQL-UHFFFAOYSA-N 0.000 description 1
- 238000005911 haloform reaction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- SVAAESRYLKTFRE-UHFFFAOYSA-N undecan-4-yl benzoate Chemical compound C(C1=CC=CC=C1)(=O)OC(CCC)CCCCCCC SVAAESRYLKTFRE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【発明の詳細な説明】 ［技術分野］ 本発明は新規な液晶性化合物並びにこれらの液晶性化合
物の少なくとも１種を含有することを特徴とする液晶組
成物に関する。更に詳しく言えば本発明は強誘電性液晶
に関し、実用的な強誘電性液晶組成物作製の際、その組
成成分として有用で且つ科学的安定性に優れた新規なフ
ツ素置換ビフエニル誘導体並びにこれらの新規なフツ素
置換ビフエニル誘導体の少なくとも１種を含有する液晶
組成物に関する。TECHNICAL FIELD The present invention relates to a novel liquid crystal compound and a liquid crystal composition containing at least one kind of these liquid crystal compounds. More specifically, the present invention relates to a ferroelectric liquid crystal, and a novel fluorine-substituted biphenyl derivative which is useful as a constituent component of a practical ferroelectric liquid crystal composition and is excellent in scientific stability, and these compounds. The present invention relates to a liquid crystal composition containing at least one novel fluorine-substituted biphenyl derivative.
［背景技術］ 時計、電卓、パーソナルワープロ、ポケツトテレビ用等
の表示素子として、液晶表示素子は広く用いられてい
る。これは受光型で目が疲れなく、消費電力が少ない、
薄型である等の優れた特徴を有しているためであるが、
一方においては応答速度が遅い、メモリー性がない等か
ら応用面において制限があった。応用面の拡大を図るた
め、従来用いられていたツイステツドネマチツク（TN）
型表示方式を改良したスーパーツイステツドネマチツク
（STN）型表示方式等も見いだされている。しかし、こ
れらは大画面表示或いはグラフイツク表示用としては充
分ではなく、これらに代わる液晶表示素子の研究も種々
行なわれている。BACKGROUND ART Liquid crystal display devices are widely used as display devices for watches, calculators, personal word processors, pocket televisions, and the like. This is a light receiving type, eyes do not get tired, power consumption is low,
It is because it has excellent features such as being thin,
On the other hand, there were limitations in application because of slow response speed and lack of memory. Conventionally used twisted nematic (TN) to expand its application
A super twisted nematic (STN) type display system, which is an improved type display system, has also been found. However, these are not sufficient for large-screen display or graphic display, and various researches have been made on liquid crystal display elements that replace them.
その１つに強誘電性液晶［R.B.Meyerら;Physique、36L
−69（1975）］を利用した表示方式［N.A.Clarkら;Appl
ied Phys.lett.,36,899（1980）］である。One of them is a ferroelectric liquid crystal [RB Meyer et al .; Physique, 36L
−69 (1975)] display method [NAClark et al .; Appl
ied Phys.lett., 36,899 (1980)].
この方式は従来方式に比べて100倍もの高速応答である
こと、及びメモリー性があること等の優れた特徴を有し
ているため、液晶表示素子の用途拡大が期待されてい
る。強誘電性液晶は液晶分子長軸が層法線方向とある角
度を有する一連のスメクテツク液晶を差すが、実用的に
はカイラルスメクチツクＣ（SmC＊）相が用いられる。
実際の表示素子用としては、種々の強誘電性液晶化合物
から成る液晶組成物として、又は種々のスメチツク（Sm
C）相を有する化合物と強誘電性液晶化合物とから成る
液晶組成物として用いられるが、それは現在汎用されて
いるネマチツク液晶表示素子作製の場合と同様であり、
実用面において要求される種々の特性（動作温度範囲、
応答速度、自発分極、ラセンピツチ、化学的安定性等）
を満足させる為には、多成分を混合することは必要とな
る。Since this method has excellent characteristics such as a 100 times faster response than the conventional method and a memory property, it is expected that the application of the liquid crystal display device will be expanded. Ferroelectric liquid crystal refers to a series of smectic liquid crystals in which the long axis of the liquid crystal molecule has an angle with the layer normal direction, but in practice a chiral smectic C (SmC * ) phase is used.
As an actual display device, a liquid crystal composition comprising various ferroelectric liquid crystal compounds or various smectic (Sm
It is used as a liquid crystal composition consisting of a compound having a phase C) and a ferroelectric liquid crystal compound, which is the same as in the case of producing a nematic liquid crystal display element which is currently widely used,
Various characteristics required for practical use (operating temperature range,
Response speed, spontaneous polarization, spiral pitch, chemical stability, etc.)
In order to satisfy, it is necessary to mix multiple components.
しかしながら、未だ実用に供し得るほどの化合物は提供
されておらず、強誘電性液晶組成物作製の際に、有用な
成分となりうる種々の新規化合物の開発が望まれている
現状にある。However, a compound that can be put to practical use has not been provided yet, and under the present circumstances, it is desired to develop various novel compounds that can be useful components when preparing a ferroelectric liquid crystal composition.
本発明者らは、特に強誘電性を示す温度範囲並びに応答
速度に視点を置き、種々の新規構造を有する化合物をデ
ザインし、合成評価し、鋭意研究を重ねた結果、化学的
に安定でSmC＊相或いはSmCの相温度範囲の広い新規化合
物或いは応答速度の速い新規化合物を提供することに成
功した。The present inventors have designed, synthesized and evaluated compounds having various novel structures with a particular focus on the temperature range and response speed that exhibit ferroelectricity, and as a result of intensive research, the results show that they are chemically stable and SmC. * We succeeded in providing a new compound with a wide phase temperature range of SmC or SmC or a new compound with a fast response speed.
［発明の開示］ 本発明は、一般式、 （R1及びR2は炭素原子数１〜18の直鎖状または分枝鎖状
アルキル基を表しＹはCOOまたはOCOを表し、Ｚは単結
合、Ｏ、COOまたはOCOを表し、X1及びX2はいずれか一方
がフツ素原子で他方が水素原子であることを表し、X3及
びX4はそれぞれ水素原子、フツ素原子、塩素原子または
シアノ基を表す）で表されるフツ素置換ビフエニル誘導
体化合物並びにそれらの少なくとも一種を含有すること
を特徴とする液晶組成物を提供するものである。DISCLOSURE OF THE INVENTION The present invention has the general formula, (R 1 and R 2 represent a linear or branched alkyl group having 1 to 18 carbon atoms, Y represents COO or OCO, Z represents a single bond, O, COO or OCO, X 1 and X 2 represents that one is a fluorine atom and the other is a hydrogen atom, and X 3 and X 4 are each a hydrogen atom, a fluorine atom, a chlorine atom or a cyano group) The present invention provides a liquid crystal composition containing a biphenyl derivative compound and at least one of them.
本発明に係わる新規な液晶化合物は、それ自身単独でSm
C＊相或いはSmC相を有する化合物である場合は、もちろ
ん、強誘電性液晶組成物の成分として有効に利用し得る
が、単独でこれらの相を有しない化合物であつても強誘
電性液晶組成物作製時の諸特性を調製するために有効に
利用できる化合物である。The novel liquid crystal compound according to the present invention is, by itself, Sm.
In the case of a compound having a C * phase or an SmC phase, of course, it can be effectively used as a component of a ferroelectric liquid crystal composition, but even a compound having no such phase by itself is a ferroelectric liquid crystal composition. It is a compound that can be effectively used to adjust various properties at the time of producing a product.
以下に合成経路実施例等により更に詳しく説明する。The details will be described below with reference to synthetic route examples and the like.
［合成経路図１の説明］ （１−ａ）から（１−ｅ）に示した化合物は、フエノー
ル誘導体（X3及びX4がそれぞれＨ、Ｆ、Clを表す）を出
発原料として合成できる。即ち、ｐ−アルコキシフエノ
ール誘導体（１−ａ）は、原料のフエノール体をアルキ
ルプロマイド（またはアルキルトシレート）でエーテル
化し、これをBr2で臭素化し、次いでマグネシウムと反
応させてグリニヤール試薬を作製した後、硼酸トリアル
キルエステルとの反応、酸加水分解及び過酸化水素を用
いた酸化分解を順次行うことにより得られる。ｐ−アル
キルフエノール誘導体（１−ｂ）は、原料のフエノール
体を脂肪酸クロライド、AlCl3を用いてアシル化し、次
いでトリエチルシラン、CF3COOHを用いて還元反応を行
うことにより得られる。 [Synthesis Route Description of FIG. 1] The compounds shown in (1-a) to (1-e) can be synthesized using a phenol derivative (X 3 and X 4 represent H, F, and Cl, respectively) as a starting material. That is, the p-alkoxyphenol derivative (1-a) was prepared by etherifying a phenol compound as a raw material with an alkyl bromide (or an alkyl tosylate), brominating it with Br 2 , and then reacting it with magnesium to prepare a Grignard reagent. After that, it is obtained by sequentially performing reaction with boric acid trialkyl ester, acid hydrolysis, and oxidative decomposition using hydrogen peroxide. The p-alkylphenol derivative (1-b) is obtained by acylating the starting phenol compound with fatty acid chloride and AlCl 3 , and then performing a reduction reaction with triethylsilane and CF 3 COOH.
ｐ−アルコキシ安息香酸誘導体（１−ｃ）は、（１−
ａ）の合成中間体であるｐ−アルコキシブロモベンゼン
誘導体をシアン化銅でシアノ化し、次いでシアノ基を加
水分解することにより得られる。The p-alkoxybenzoic acid derivative (1-c) has the formula (1-
It is obtained by cyanating a p-alkoxy bromobenzene derivative, which is a synthetic intermediate of a), with copper cyanide, and then hydrolyzing the cyano group.
ｐ−アシルオキシ安息香酸誘導体（１−ｄ）は、原料の
フエノール体をアルキルブロマイド（またはアルキルト
シレート）でエーテル化し、これをBr2で臭素化し、次
いでシアン化銅でシアノ化して得られるアルコキシベン
ゾニトリル誘導体をAlCl3またはHBrを用いてエーテル開
裂反応させた後、アルカリ加水分解することによりヒド
ロキシ安息香酸誘導体に変換し、これを脂肪族酸クロラ
イドでエステル化することにより得られる。The p-acyloxybenzoic acid derivative (1-d) is an alkoxybenzoyl derivative obtained by etherifying the starting phenol compound with alkyl bromide (or alkyl tosylate), brominating it with Br 2 , and then cyanating it with copper cyanide. It is obtained by subjecting a nitrile derivative to an ether cleavage reaction with AlCl 3 or HBr, then converting it to a hydroxybenzoic acid derivative by alkali hydrolysis, and esterifying this with a fatty acid chloride.
ｐ−アルコキシカルボニルフエノール誘導体（１−ｅ）
は、（１−ｄ）の合成中間体であるヒドロキシ安息香酸
誘導体を脂肪族アルコール及び酸触媒を用いてエステル
化することにより得られる。p-alkoxycarbonylphenol derivative (1-e)
Can be obtained by esterifying a hydroxybenzoic acid derivative which is a synthetic intermediate of (1-d) using an aliphatic alcohol and an acid catalyst.
（１−ｆ）及び（１−ｇ）はモノブロモ置換アニソール
を出発原料として合成できる。即ち、モノブロム置換ア
ニソールをAlCl3及びアセチルクロライドでアセチル化
した後、HBrを用いてエーテル開裂反応を行い、次いで
アルキルブロマイド（またはアルキルトシレート）で再
びエーテル化し、これをシアン化銅を用いてシアン化し
て得られるモノシアノ置換ｐ−アルコキシアセトフエノ
ンについてバイヤービリガー酸化、加水分解を順次行う
ことによりモノシアノ置換ｐ−アルコキシフエノール
（１−ｆ）が得られる。また前記モノシアノ置換ｐ−ア
ルコキシアセトフエノンのハロホルム反応によりモノシ
アノ置換ｐ−アルコキシ安息香酸が得られる。(1-f) and (1-g) can be synthesized using monobromo-substituted anisole as a starting material. That is, monobrom-substituted anisole is acetylated with AlCl 3 and acetyl chloride, then ether cleavage reaction is carried out with HBr, and then etherification is again carried out with alkyl bromide (or alkyl tosylate), which is then cyanated with copper cyanide. By subjecting the monocyano-substituted p-alkoxyacetophenone obtained by the conversion to Bayer-Villiger oxidation and hydrolysis in order, a monocyano-substituted p-alkoxyphenol (1-f) is obtained. Also, a monocyano-substituted p-alkoxybenzoic acid can be obtained by a haloform reaction of the monocyano-substituted p-alkoxyacetophenone.
［合成経路図２の説明］ （２−ａ）、（２−ｂ）、（２−ｃ）および（２−ｄ）
の各化合物は２−フルオロ−４−ブロムビフエニルを出
発原料として合成できる。[Synthesis Route: Description of FIG. 2] (2-a), (2-b), (2-c) and (2-d)
Each compound can be synthesized using 2-fluoro-4-bromobiphenyl as a starting material.
２′−フルオロ−４′−ヒドロキシ−４−アルコキシビ
フエニル（２−ａ）は、原料のビフエニル体をAlCl3及
びアセチルクロライドを用いてアセチル化し、これにつ
いてバイヤービリーガー酸化、加水分解を行い、２′−
フルオロ−４′−ブロム−４−ヒドロキシビフエニルと
した後、アルキルブロマイド（またはアルキルトシレー
ト）でエーテル化し、次いでこれをマグネシウムと反応
させてグリニヤール試薬を作製した後、硼酸トリブチル
アルキルエステルと反応させ、酸加水分解、酸化分解を
順次行うことにより得られる。2′-fluoro-4′-hydroxy-4-alkoxybiphenyl (2-a) is acetylated from a raw material biphenyl using AlCl 3 and acetyl chloride, and is subjected to Bayer-Villeger oxidation and hydrolysis. 2'-
After making fluoro-4'-bromo-4-hydroxybiphenyl, it is etherified with alkyl bromide (or alkyl tosylate) and then reacted with magnesium to prepare a Grignard reagent, and then reacted with boric acid tributyl alkyl ester. It is obtained by sequentially performing acid hydrolysis and oxidative decomposition.
４−アルコキシ−２′−フルオロビフエニル−４′−カ
ルボン酸（２−ｂ）は、（２−ａ）の合成における中間
体２′−フルオロ−４′−ブロム−４−アルコキシビフ
エニルをシアノ化し、次いでアルカリ加水分解すること
により得られる。また、２−フルオロ−４−アルコキシ
ビフエニル−４′−カルボン酸（２−ｃ）は、原料のビ
フエニル体をCl2CHOCH3及びAlCl3を用いてホルミル化
し、次いで（CH2OH)2、BF3を用いてアセタール保護した
後、これをマグネシウムと反応させて得られるグリニャ
ール試薬と硼酸トリブチルと反応させ、次いでアルキル
プロマイド（またはアルキルトシレート）でエーテル化
し、保護基の開裂、CrO3を用いた酸化反応を順次行うこ
とにより得ることができる。4-Alkoxy-2'-fluorobiphenyl-4'-carboxylic acid (2-b) is the intermediate 2'-fluoro-4'-bromo-4-alkoxybiphenyl in the synthesis of (2-a). And then hydrolyzed with an alkali. Also, 2-fluoro-4-alkoxy Biff enyl-4'-carboxylic acid (2-c) is biphenyl of raw materials by using Cl 2 CHOCH 3 and AlCl 3 formylating, followed by (CH 2 OH) 2, After protecting with acetal using BF 3 , it is reacted with magnesium to react with Grignard reagent and tributyl borate, and then etherified with alkyl bromide (or alkyl tosylate) to cleave the protecting group and use CrO 3 . It can be obtained by sequentially performing the oxidation reaction.
２−フルオロ−４−アルコキシ−４′−ヒドロキシビフ
エニル（２−ｄ）は、（２−ａ）の合成中間体２′−フ
ルオロ−４′−ブロム−４−ヒドロキシビフエニルをベ
ンジル保護し、前記した硼酸トリブチルエステルを用い
る反応により２′−フルオロ−４′−ヒドロキシ−４−
ベンジルオキシビフエニルとした後、エーテル化、ベン
ジル保護基の開裂により得ることができる。2-fluoro-4-alkoxy-4'-hydroxybiphenyl (2-d) is benzyl-protected on the synthetic intermediate 2'-fluoro-4'-bromo-4-hydroxybiphenyl of (2-a), 2'-Fluoro-4'-hydroxy-4-by reaction with boric acid tributyl ester as described above.
It can be obtained by converting to benzyloxybiphenyl, etherification, and cleavage of the benzyl protecting group.
本発明の種々の新規化合物は、前記方法にて得られる
（１−ａ）〜（１−ｇ）及び（２−ａ）〜（２−ｄ）、
あるいは市販のカルボン酸誘導体とフエノール誘導体を
各々組み合わせ、常法のエステル化により得ることがで
きる。The various novel compounds of the present invention are (1-a) to (1-g) and (2-a) to (2-d), which are obtained by the above method.
Alternatively, it can be obtained by combining a commercially available carboxylic acid derivative and a phenol derivative with each other and carrying out a conventional esterification.
以下に実施例により本発明を説明するが、使用されてい
る略記号は下記の意味を表わす。The present invention will be described below with reference to examples, and the abbreviations used have the following meanings.
GLC ガスクロマトグラフイー HPLC 高速液体クロマトグラフイー IR 赤外線吸収スペクトル Mass 質量分析 m.p 融点 Ｃ 結晶 SX 同定出来なかつたスメクチック相 SB スメクチツクＢ相 SmC,SC スメクチツクＣ相 SmC＊,SC＊ カイラルスメクチツクＣ相 SA スメクチツクＡ相 Ch コレステリツク相 Ｉ 等方性液体 ？ 温度不明 実施例１ 反応器に無水塩化アルミニウム113g及び塩化メチレン60
0mlを仕込み０℃以下で攪拌下にアセチルクロライド113
gを滴下し、次いで４−ブロム−２−フルオロビフエニ
ル100gの塩化メチレン400ml溶液を滴下後、徐々に室温
に戻しながら７時間攪拌反応した。反応液を氷と希塩酸
中に注加し、塩化メチレン層を水洗、炭酸水素ナトリウ
ム水溶液洗浄、水洗し、芒硝で脱水後溶媒を留去し、残
留分をアセトンで再結晶して４−アセチル−２′−フル
オロ−４′−ブロムビフエニル96g（82.2％）を得た。GLC Gas chromatograph HPLC High performance liquid chromatograph IR Infrared absorption spectrum Mass Mass spectrometry mp Melting point C Crystal S X Unidentifiable smectic phase S B smectic B phase SmC, SC smectic C phase SmC * , SC * chiral smectic C Phase S A Smectic A Phase Ch Cholesteric Phase I Isotropic liquid? Unknown temperature Example 1 113 g of anhydrous aluminum chloride and 60 methylene chloride in the reactor
Charge 0 ml and stir acetyl chloride 113 at 0 ° C or below with stirring.
g, and then a solution of 100 g of 4-bromo-2-fluorobiphenyl in 400 ml of methylene chloride was dropped, and the mixture was stirred for 7 hours while gradually returning to room temperature. The reaction solution was poured into ice and diluted hydrochloric acid, and the methylene chloride layer was washed with water, washed with an aqueous solution of sodium hydrogen carbonate and washed with water, dehydrated with sodium sulfate and the solvent was distilled off, and the residue was recrystallized with acetone to give 4-acetyl-. 96 g (82.2%) of 2'-fluoro-4'-bromobiphenyl were obtained.
GLC 100％ 反応器に（ａ）で得た４−アセチル−２′−アルオロ−
４′−ブロムビフエニル65g及び塩化メチレン300mlを仕
込み、10℃で攪拌下に88％ギ酸500ml、無水酢酸480mlを
滴下し、さらに濃硫酸1.5mlを加えた後、35％過酸化水
素水150mlを３時間を要して滴下し、滴下後徐々に昇温
して45〜50℃で30時間攪拌反応した。反応液を氷水に注
加し、ベンゼンで抽出、炭酸水素ナトリウム水溶液で洗
浄、水洗、芒硝脱水を意い、溶媒を留去し、残留分を得
た。この残留分とエチルアルコール2lを別の反応器に仕
込み、これに25％苛性カリ水溶液を加え、８時間還流攪
拌した。反応液を氷と希塩酸中に注加しベンゼンで抽
出、食塩水で洗浄、芒硝で脱水後、溶媒を留去し、残留
分をシリカゲルカラムクロマトグラフイー（溶離液ベン
ゼン）にて精製し、４−ヒドロキシ−２′−フルオロ−
４′−ブロムフエニル28.1g（47.5％）を得た。GLC 100% 4-acetyl-2'-arolo-obtained in (a) was added to the reactor.
Charge 65 g of 4'-bromobiphenyl and 300 ml of methylene chloride, add 500 ml of 88% formic acid and 480 ml of acetic anhydride under stirring at 10 ° C, add 1.5 ml of concentrated sulfuric acid, and add 150 ml of 35% hydrogen peroxide for 3 hours. Was added dropwise, and the temperature was gradually raised after the dropwise addition to carry out a stirring reaction at 45 to 50 ° C. for 30 hours. The reaction solution was poured into ice water, extracted with benzene, washed with an aqueous solution of sodium hydrogen carbonate, washed with water, and dehydrated with sodium sulfate. The solvent was distilled off to obtain a residue. This residue and 2 liters of ethyl alcohol were charged into another reactor, 25% aqueous potassium hydroxide solution was added thereto, and the mixture was stirred under reflux for 8 hours. The reaction mixture was poured into ice and diluted hydrochloric acid, extracted with benzene, washed with brine, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent benzene). -Hydroxy-2'-fluoro-
28.1 g (47.5%) of 4'-bromophenyl was obtained.
反応器に（ｂ）で得た４−ヒドロキシ−２′−フルオロ
−４′−ブロムフエニル5g（Ｓ）−４−メチルヘキシル
ブロマイド8.0g、炭酸カリウム4g及び２−ブタノン（ME
K）50mlを仕込み、攪拌還流下に８時間反応後、反応液
を希塩酸に注加し、ベンゼンで抽出、水洗、芒硝で脱水
後、溶媒を留去し、残留分をガラスチューブオーブン
（GTO）にて蒸留して得られる留分（GTO設定温度 165
℃/0.25mmHg）をシリカゲルカラムクロマトグラフイー
（溶離液ヘキサン：ベンゼン＝4;1）で精製し、（Ｓ）
−４−（４−メチルヘキシル）オキシ−２′−フルオロ
−４′−ブロムビフエニル4.47g（65.4％）を得た。 In the reactor, 4-hydroxy-2'-fluoro-4'-bromophenyl obtained in (b) 5 g (S) -4-methylhexyl bromide 8.0 g, potassium carbonate 4 g and 2-butanone (ME
K) 50 ml was charged, and after reacting for 8 hours under stirring and refluxing, the reaction solution was poured into dilute hydrochloric acid, extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was removed in a glass tube oven (GTO). Fraction obtained by distillation at (GTO set temperature 165
℃ / 0.25mmHg) was purified by silica gel column chromatography (eluent hexane: benzene = 4; 1), (S)
There was obtained 4.47 g (65.4%) of 4- (4-methylhexyl) oxy-2'-fluoro-4'-bromobiphenyl.
モノスポツト 反応器に（ｃ）で得た（Ｓ）−４−（４−メチルヘキシ
ル）オキシ−２′−フルオロ−４′−ブロムビフエニル
11.7g、シアン化第一銅（CuCN）3g及びジメチルホルム
アミド（DMF）50mlを仕込み、150〜155℃で54時間加熱
攪拌した。反応液を塩化第２鉄６水和物（FeCl3・6H
2O）13g、濃塩酸2ml及び水100mlからなる水溶液にて処
理し、ベンゼンで抽出し、水洗し、芒硝で脱水後、溶媒
を留去し、残留分（粗（Ｓ）−４−（４−メチルヘキシ
ル）オキシ−２′−フルオロ−４′−シアノビフエニ
ル）9.8gを得た。Mono spot (S) -4- (4-Methylhexyl) oxy-2'-fluoro-4'-bromobiphenyl obtained in (c) in a reactor
11.7 g, cuprous cyanide (CuCN) 3 g and dimethylformamide (DMF) 50 ml were charged, and the mixture was heated with stirring at 150 to 155 ° C. for 54 hours. Ferric chloride hexahydrate and the reaction solution (FeCl 3 · 6H
2 O) treated with an aqueous solution consisting of 13 g, concentrated hydrochloric acid 2 ml and water 100 ml, extracted with benzene, washed with water, dehydrated with mirabilite and evaporated to remove the residue (crude (S) -4- (4 -Methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl) 9.8 g was obtained.
反応器に（ｃ）で得た残留分（粗（Ｓ）−４−（４−メ
チルヘキシル）オキシ−２′−フルオロ−４′−シアノ
ビフエニル）9.8g、15％苛性ソーダ水溶液100ml、テト
ラヒドロフラン（THF）100ml及びメタノール50mlを仕込
み、32時間攪拌還流した。反応液を氷冷水に注加し、濃
塩酸を加えて酸性とし、析出物を取し、これをメタノ
ール/2−ブタノンで再結晶して（Ｓ）−４−（４−メチ
ルヘキシル）オキシ−２′−フルオロビフエニル−４′
−カルボン酸6.6gを得た。 9.8 g of the residue (crude (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl) obtained in (c) in a reactor, 100 ml of 15% caustic soda aqueous solution, tetrahydrofuran (THF) 100 ml and 50 ml of methanol were charged, and the mixture was stirred and refluxed for 32 hours. The reaction mixture was poured into ice-cold water, acidified by adding concentrated hydrochloric acid, and the precipitate was collected and recrystallized from methanol / 2-butanone to give (S) -4- (4-methylhexyl) oxy-. 2'-fluorobiphenyl-4 '
-6.6 g of carboxylic acid are obtained.
反応器に（ｅ）で得た（Ｓ）−４−（４−メチルヘキシ
ル）オキシ−２′−フルオロビフエニル−４′−カルボ
ン酸0.3g、N,N−ジシクロヘキシルカルボジイミド（DC
C）0.22g、４−（ジメチルアミノ）ピリジン0.11g、４
−オクチルオキシフエノール0.21g及び塩化メチレン30m
lを仕込み、10時間室温で攪拌反応した。反応液を過
し、液を水洗し、芒硝で脱水後、溶媒を留去し、残留
分をシリカゲルカラムクロマトグラフイー（溶離液ヘキ
サン／ベンゼン＝1/1）で精製し、さらにメタノール／
アセトンで再結晶して、（Ｓ）−４−オクチルオキシフ
エニル４−（４−メチルヘキシル）オキシ−２′−フ
ルオロビフエニル−４′−カルボキシレート0.34g（70.
0％）を得た。 In the reactor, 0.3 g of (S) -4- (4-methylhexyl) oxy-2'-fluorobiphenyl-4'-carboxylic acid obtained in (e), N, N-dicyclohexylcarbodiimide (DC
C) 0.22 g, 4- (dimethylamino) pyridine 0.11 g, 4
-Octyloxyphenol 0.21g and methylene chloride 30m
Then, the reaction mixture was stirred for 10 hours at room temperature. The reaction solution was passed, the solution was washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent hexane / benzene = 1/1) and further methanol /
Recrystallization from acetone gave 0.34 g of (S) -4-octyloxyphenyl 4- (4-methylhexyl) oxy-2'-fluorobiphenyl-4'-carboxylate (70.
0%) was obtained.
この物の純度はHPLCで98％以上であつた。またIR及びMa
ss分析で534で分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was higher than 98% by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 534 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例２ 実施例１（ｆ）における４−オクチルオキシフエノール
0.21gに替えて４−デシルオキシフエノール0.25gを用
い、他は実施例１（ｆ）と同様に操作して（Ｓ）−４−
デシルオキシフエニル４−（４−メチルヘキシル）オ
キシ−２′−フルオロビフエニル−４′−カルボキシレ
ート0.39g（76.5％）を得た。Example 2 4-octyloxyphenol in Example 1 (f)
0.25 g of 4-decyloxyphenol was used in place of 0.21 g, and the same procedure as in Example 1 (f) was repeated except that (S) -4-
0.39 g (76.5%) of decyloxyphenyl 4- (4-methylhexyl) oxy-2'-fluorobiphenyl-4'-carboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で562に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 562 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例３ 実施例１（ｆ）における４−オクチルオキシフエノール
0.21gに替えて４−ドデシルオキシフエノール0.24gを用
い、他は実施例１（ｆ）と同様に操作して（Ｓ）−４−
ドデシルオキシフエニル４−（４−メチルヘキシル）
オキシ−２′−フルオロビフエニル−４′−カルボキシ
レート0.42g（77.7％）を得た。Example 3 4-octyloxyphenol in Example 1 (f)
0.24 g of 4-dodecyloxyphenol was used in place of 0.21 g, and the same procedure as in Example 1 (f) was repeated except that (S) -4-
Dodecyloxyphenyl 4- (4-methylhexyl)
There was obtained 0.42 g (77.7%) of oxy-2'-fluorobiphenyl-4'-carboxylate.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で590に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 590 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例４ 実施例１（ｆ）における４−オクチルオキシフエノール
0.21gに替えて４−オクチルフエノール0.21gを用い、他
は実施例１（ｆ）と同様に操作して（Ｓ）−４−オクチ
ルフエニル４−（４−メチルヘキシル）オキシ−２′
−フルオロビフエニル−４′−カルボキシレート0.38g
（80.9％）を得た。Example 4 4-octyloxyphenol in Example 1 (f)
4-Octylphenol 0.21 g was used in place of 0.21 g, and the same procedure as in Example 1 (f) was repeated except that (S) -4-octylphenyl 4- (4-methylhexyl) oxy-2 ′ was used.
-Fluorobiphenyl-4'-carboxylate 0.38 g
(80.9%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で518に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 518 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例１（ｆ）における４−オクチルオキシフエノール
0.21gに替えて４−デシルフエノール0.23gを用い、他は
実施例１（ｆ）と同様に操作して（Ｓ）−４−デシルフ
エニル４−（４−メチルヘキシル）オキシ−２′−フ
ルオロビフエニル−４′−カルボキシレート0.48g（96.
8％）を得た。 4-octyloxyphenol in Example 1 (f)
0.23 g of 4-decylphenol was used in place of 0.21 g, and the same procedure as in Example 1 (f) was repeated except that (S) -4-decylphenyl 4- (4-methylhexyl) oxy-2′-fluorobif was used. 0.48 g (96.
8%).
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で546に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was observed at 546 and the relation of the raw materials used, that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例６ 反応器に２−フルオロフエノール15g、オクチルブロマ
イド25.9g、水酸化カリウム46.2g並びにシクロヘキサノ
ン150mlを仕込み、120〜130℃で12時間攪拌した。反応
液を希塩酸に注加し、ベンゼン抽出、水洗、芒硝で脱水
後溶媒を留去した。残留分並びにクロロホルム100mlを
別の容器に仕込み、室温攪拌下臭素44gを滴下し、さら
に同温度で６時間攪拌後、希苛性ソーダ水溶液に注加し
攪拌した。クロロホルム層を水洗、芒硝で脱水し、溶媒
を留去した残留分を減圧蒸留して、４−オクチルオキシ
−３−フルオロブロムベンゼン32g（78.8％）を得た。Example 6 The reactor was charged with 15 g of 2-fluorophenol, 25.9 g of octyl bromide, 46.2 g of potassium hydroxide and 150 ml of cyclohexanone, and the mixture was stirred at 120 to 130 ° C for 12 hours. The reaction solution was poured into diluted hydrochloric acid, extracted with benzene, washed with water, dehydrated with sodium sulfate, and the solvent was distilled off. The residue and 100 ml of chloroform were placed in another container, 44 g of bromine was added dropwise with stirring at room temperature, and the mixture was further stirred at the same temperature for 6 hours and then poured into a dilute caustic soda aqueous solution and stirred. The chloroform layer was washed with water, dehydrated with sodium sulfate, and the residue obtained by distilling off the solvent was distilled under reduced pressure to obtain 32 g (78.8%) of 4-octyloxy-3-fluorobromobenzene.
b.p 122〜130℃/0.3mmHg 反応器にマグネシウム0.87g及びヨウ素の少量を仕込
み、（ａ）で得た４−オクチルオキシ−３−フルオロブ
ロムベンゼン9gのTHF30ml溶液の少量を加えて加熱し、
反応開始後残りのTHF溶液を滴下した。滴下終了後３時
間還流し、グリニヤール試薬を作成した。別の反応器に
硼酸トリブチルエステル10.2gを仕込み、これに先に作
成したグリニヤール試薬を攪拌下に40℃で滴下し、滴下
後１時間同温度で攪拌した。放冷後、攪拌下に10％硫酸
水溶液を滴下し、反応液にベンゼン100mlを加えて抽出
した。別の反応器にこのベンゼン抽出液を仕込み、40〜
50℃で攪拌下に35％過酸化水素水30mlを滴下し、さらに
２時間攪拌反応した。反応液を水に注加し、ベンゼン層
を亜硫酸水素ナトリウム水溶液で処理し、水洗し、芒硝
で脱水後、溶媒を留去し、残留分をガラスチューブオー
ブン（GTO）を用いて蒸留（b.p.125−140℃/0.15mmHg）
し、その留分をヘキサンで再結晶して４−オクチルオキ
シ−３−フルオロフエノール2.6g（36.5％）を得た。bp 122-130 ℃ / 0.3mmHg A reactor was charged with 0.87 g of magnesium and a small amount of iodine, and a small amount of a solution of 4-octyloxy-3-fluorobromobenzene 9 g obtained in (a) 9 g in THF 30 ml was added and heated.
After the reaction was started, the remaining THF solution was added dropwise. After completion of dropping, the mixture was refluxed for 3 hours to prepare a Grignard reagent. Into another reactor, 10.2 g of boric acid tributyl ester was charged, and the Grignard reagent prepared above was added dropwise thereto at 40 ° C. with stirring, and after the addition, the mixture was stirred at the same temperature for 1 hour. After allowing to cool, 10% aqueous sulfuric acid solution was added dropwise with stirring, and 100 ml of benzene was added to the reaction solution for extraction. Charge this benzene extract into another reactor, 40 ~
30 ml of 35% hydrogen peroxide solution was added dropwise with stirring at 50 ° C., and the mixture was reacted for 2 hours with stirring. The reaction solution was poured into water, the benzene layer was treated with an aqueous solution of sodium hydrogen sulfite, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was distilled using a glass tube oven (GTO) (bp125- 140 ℃ / 0.15mmHg)
Then, the fraction was recrystallized with hexane to obtain 2.6 g (36.5%) of 4-octyloxy-3-fluorophenol.
実施例１（ｆ）における４−オクチルオキシフエノール
0.21gに替えて（ｂ）で得られた４−オクチルオキシ−
３−フルオロフエノール0.24gを用い、他は実施例１
（ｆ）と同様に操作して（Ｓ）−４−オクチルオキシ−
３−フルオロフエニル４−（４−メチルヘキシル）オ
キシ−２′−フルオロビフエニル−４′−カルボキシレ
ート0.34g（68.0％）を得た。 4-octyloxyphenol in Example 1 (f)
4-octyloxy-obtained in (b) in place of 0.21 g
Using 0.24 g of 3-fluorophenol, other than Example 1
Operating in the same manner as in (f), (S) -4-octyloxy-
0.34 g (68.0%) of 3-fluorophenyl 4- (4-methylhexyl) oxy-2'-fluorobiphenyl-4'-carboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で552に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 552 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例７ 実施例６（ａ）におけるオクチルブロマイド25.9gに替
えてデシルブロマイド29.6gを用い、他は実施例６
（ａ）と同様に操作して４−デシルオキシ−３−フルオ
ロブロムベンゼン30.4g（68.5％）を得た。Example 7 29.6 g of decyl bromide was used instead of 25.9 g of octyl bromide in Example 6 (a), and other examples were used.
The same operation as in (a) was performed to obtain 30.4 g (68.5%) of 4-decyloxy-3-fluorobromobenzene.
b.p.125〜147℃/0.5〜1.0mmHg 実施例６（ｂ）における４−オクチルオキシ−３−フル
オロブロムベンゼン9gに替えて（ａ）で得られた４−デ
シルオキシ−３−フルオロブロムベンゼン9.8gを用い、
他は実施例６（ｂ）と同様に操作して４−デシルオキシ
−３−フルオロフエノール0.57g（7.1％）を得た。bp125-147 ℃ / 0.5-1.0mmHg Using 9 g of 4-octyloxy-3-fluorobromobenzene in Example 6 (b) and 9.8 g of 4-decyloxy-3-fluorobromobenzene obtained in (a),
Others were operated similarly to Example 6 (b), and 0.57 g (7.1%) of 4-decyloxy-3-fluorophenol was obtained.
b.p.130〜160℃/0.3mmHg（GTO設定温度） 実施例１（ｆ）における４−オクチルオキシフエノール
0.21gに替えて（ｂ）で得られた４−デシルオキシ−３
−フルオロフエノール0.26gを用い、他は実施例１
（ｆ）と同様に操作して（Ｓ）−４−デシルオキシ−３
−フルオロフエニル４−（４−メチルヘキシル）オキ
シ−２′−フルオロビフエニル−４′−カルボキシレー
ト0.39g（74.0％）を得た。bp130-160 ℃ / 0.3mmHg (GTO set temperature) 4-octyloxyphenol in Example 1 (f)
4-decyloxy-3 obtained in (b) in place of 0.21 g
-Using 0.26 g of fluorophenol, other than Example 1
Operating in the same manner as in (f), (S) -4-decyloxy-3
0.39 g (74.0%) of -fluorophenyl 4- (4-methylhexyl) oxy-2'-fluorobiphenyl-4'-carboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例８ 反応器に２−フルオロフエノール10g並びに塩化メチレ
ン50mlを仕込み、氷水冷攪拌下に、無水塩化アルミニウ
ム17.8gを徐々に加え、次いで、０℃以下でペンタノイ
ルクロライド11.8gを滴下し、１時間同温度で、２時間
室温で反応した。反応液を水に注加し、希塩酸を加え、
ベンゼンで抽出し、水洗し、芒硝で脱水後、溶媒を留去
し、残留分を減圧蒸溜して３−フルオロ−４−ペンタノ
イルフエノール14g（80.0％）を得た。Example 8 2-Fluorophenol (10 g) and methylene chloride (50 ml) were charged into the reactor, and anhydrous aluminum chloride (17.8 g) was gradually added to the mixture while stirring with ice-water cooling. Then, it reacted at room temperature for 2 hours. The reaction solution is poured into water, diluted hydrochloric acid is added,
It was extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain 14 g (80.0%) of 3-fluoro-4-pentanoylphenol.
b.p.113〜121℃/0.3mmHg 反応器に（ａ）で得られた３−フルオロ−４−ペンタノ
イルフエノール14g並びにトリフルオロ酢酸50mlを仕込
み、室温攪拌下にトリエチルシラン20.3gを滴下し、20
時間同温度で反応した。反応液を希苛性ソーダ水溶液に
注加し、塩酸酸性とした後、ベンゼンで抽出し、水洗
し、芒硝で脱水後、溶媒を留去し、残留分を減圧蒸留し
て３−フルオロ−４−ペンチルフエノール11.9g（91.5
％）を得た。b.p 67〜68℃/0.3mmHg 実施例１（ｆ）における４−オクチルオキシフエノール
0.21gに替えて（ｂ）で得られた３−フルオロ−４−ペ
ンチルフエノール0.32gを用い、他は実施例１（ｆ）と
同様に操作して（Ｓ）−４−ペンチル−２−フルオロフ
エニル４−（４−メチルヘキシル）オキシ−２′−フ
ルオロビフエニル−４′−カルボキシレート0.29g（64.
6％）を得た。bp113-121 ℃ / 0.3mmHg A reactor was charged with 14 g of 3-fluoro-4-pentanoylphenol obtained in (a) and 50 ml of trifluoroacetic acid, and 20.3 g of triethylsilane was added dropwise under stirring at room temperature.
Reacted at the same temperature for a time. The reaction solution was poured into a dilute aqueous solution of sodium hydroxide, acidified with hydrochloric acid, extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to give 3-fluoro-4-pentyl. 11.9 g of phenol (91.5
%) Was obtained. bp 67-68 ℃ / 0.3mmHg 4-octyloxyphenol in Example 1 (f)
0.32 g of 3-fluoro-4-pentylphenol obtained in (b) was used in place of 0.21 g, and (S) -4-pentyl-2-fluoro was used in the same manner as in Example 1 (f). Phenyl 4- (4-methylhexyl) oxy-2'-fluorobiphenyl-4'-carboxylate 0.29 g (64.
6%).
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で494に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質か目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was found at 494 and the relationship between the raw materials used and that the substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例９ 実施例１（ｃ）において、（Ｓ）−４−メチルヘキシル
ブロマイド8.0gに替えて（Ｒ）−１−メチルヘキシルト
シレート2.1gを用い、他は実施例１（ｃ）と同様に操作
して（Ｓ）−４−（１−メチルヘキシル）オキシ−２′
−フルオロ−４′−ブロムビフエニル4.9g（71.7％）を
得た。Example 9 In Example 1 (c), 2.1 g of (R) -1-methylhexyltosylate was used in place of 8.0 g of (S) -4-methylhexyl bromide, and the same procedure as in Example 1 (c) was followed. Te (S) -4- (1-methylhexyl) oxy-2 '
4.9 g (71.7%) of -fluoro-4'-bromobiphenyl were obtained.
実施例１（ｄ）において、（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロ−４′−ブロムビフエ
ニル11.7gに替えて、（ａ）で得られた（Ｓ）−４−
（１−メチルヘキシル）オキシ−２′−フルオロ−４′
−ブロムビフエニル11.7gを用い、他は実施例１（ｄ）
と同様に操作して粗（Ｓ）−４−（１−メチルヘキシ
ル）オキシ−２′−フルオロ−４′−シアノビフエニル
9.5gを得た。 In Example 1 (d), (S) -4- (4-methylhexyl) oxy-2′-fluoro-4′-bromobiphenyl 11.7 g was used instead of (S) -4-obtained.
(1-Methylhexyl) oxy-2'-fluoro-4 '
-Using 11.7 g of brombiphenyl, otherwise Example 1 (d)
The same procedure as in the above was carried out to obtain crude (S) -4- (1-methylhexyl) oxy-2′-fluoro-4′-cyanobiphenyl
9.5 g was obtained.
実施例１（ｅ）において、（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロ−４′−シアノビフエ
ニル9.8gに替えて、（ｂ）で得られた（Ｓ）−４−（１
−メチルヘキシル）オキシ−２′−フルオロ−４′−シ
アノビフエニル9.5gを用い、他は実施例１（ｅ）と同様
に操作して（Ｓ）−４−（１−メチルヘキシル）オキシ
−２′−フルオロ−４′−ビフエニルカルボン酸6.2gを
得た。 In Example 1 (e), (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl was replaced by 9.8 g, and the (S) -4-obtained in (b) was used. (1
-Methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl was used, but otherwise the same procedure as in Example 1 (e) was followed and (S) -4- (1-methylhexyl) oxy-2 '. 6.2 g of -fluoro-4'-biphenylcarboxylic acid was obtained.
反応器に（Ｓ）−４−（１−メチルヘキシル）オキシ−
２′−フルオロ−４′−ビフエニルカルボン酸0.3g、４
−オクチルオキシフエノール0.22g、DCC 0.22g、４−
ピロリジノピリジン0.15g及び塩化メチレン30mlを仕込
み、７時間室温攪拌した。反応液を過し、液を水洗
し、芒硝で脱水後、溶媒を留去し、残留分をヘキサン／
ベンゼン＝1/1を溶離液としたシリカゲルカラムクロマ
トグラフイーにて精製し、さらにアセトン／メタノール
混合溶媒で再結晶して（Ｓ）−４−オクチルオキシフエ
ニル４−（１−メチルヘキシル）オキシ−２′−フル
オロ−４′−ビフエニルカルボキシレート0.28g（57.7
％）を得た。 (S) -4- (1-methylhexyl) oxy-
2'-fluoro-4'-biphenylcarboxylic acid 0.3 g, 4
-Octyloxyphenol 0.22g, DCC 0.22g, 4-
Pyrrolidinopyridine (0.15 g) and methylene chloride (30 ml) were charged, and the mixture was stirred at room temperature for 7 hours. The reaction solution was passed, the solution was washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was mixed with hexane /
Purify by silica gel column chromatography using benzene = 1/1 as eluent, and recrystallize with acetone / methanol mixed solvent to obtain (S) -4-octyloxyphenyl 4- (1-methylhexyl) oxy. -2'-fluoro-4'-biphenylcarboxylate 0.28 g (57.7
%) Was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で534に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 534 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例10 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて４−デシルオキシフエノール0.25gを用
い、他は実施例９（ｄ）と同様に操作して（Ｓ）−４−
デシルオキシフエニル４−（１−メチルヘキシル）オ
キシ−２′−フルオロ−４′−ビフエニルカルボキシレ
ート0.35g（68.6％）を得た。Example 10 In Example 9 (d), 4-octyloxyphenol was replaced with 0.22 g and 4-decyloxyphenol was used in the same amount as in Example 9 (d) except that 0.25 g of 4-decyloxyphenol was used.
0.35 g (68.6%) of decyloxyphenyl 4- (1-methylhexyl) oxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で562に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 562 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例11 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて４−ドデシルオキシフエノール0.28gを
用い、他は実施例９（ｄ）と同様に操作して（Ｓ）−４
−ドデシルオキシフエニル４−（１−メチルヘキシ
ル）オキシ−２′−フルオロ−４′−ビフエニルカルボ
キシレート0.44g（82.1％）を得た。Example 11 In Example 9 (d), 0.28 g of 4-octyloxyphenol was used in place of 0.22 g of 4-octyloxyphenol, and 0.28 g of 4-dodecyloxyphenol was used. Otherwise, the same operation as in Example 9 (d) was followed (S) -4.
0.44 g (82.1%) of -dodecyloxyphenyl 4- (1-methylhexyl) oxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で590に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 590 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例12 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて４−オクチルフエノール0.21gを用い、
他は実施例９（ｄ）と同様に操作して（Ｓ）−４−オク
チルフエニル４−（１−メチルヘキシル）オキシ−
２′−フルオロ−４′−ビフエニルカルボキシレート0.
36g（76.4％）を得た。Example 12 In Example 9 (d), 4-octyloxyphenol 0.21 g was used in place of 4-octyloxyphenol 0.22 g,
Otherwise by operating as in Example 9 (d), (S) -4-octylphenyl 4- (1-methylhexyl) oxy-
2'-fluoro-4'-biphenylcarboxylate 0.
36 g (76.4%) were obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で518に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 518 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例13 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて４−デシルフエノール0.23gを用い、他
は実施例９（ｄ）と同様に操作して（Ｓ）−４−デシル
フエニル４−（１−メチルヘキシル）オキシ−２′−
フルオロ−４′−ビフエニルカルボキシレート0.33g（6
6.5％）を得た。Example 13 In Example 9 (d), 0.23 g of 4-octyloxyphenol was used in place of 0.22 g of 4-octyloxyphenol, and 0.23 g of 4-decylphenol was used. Otherwise, the same operation as in Example 9 (d) was carried out, and (S) -4-decylphenyl 4- (1-Methylhexyl) oxy-2'-
Fluoro-4'-biphenylcarboxylate 0.33 g (6
6.5%).
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で546に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was observed at 546 and the relation of the raw materials used, that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例14 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて４−オクチルオキシ−３−フルオロフ
エノール0.24gを用い、他は実施例９（ｄ）と同様に操
作して（Ｓ）−４−オクチルオキシ−３−フルオロフエ
ニル４−（１−メチルヘキシル）オキシ−２′−フル
オロ−４′−ビフエニルカルボキシレート0.35g（70.0
％）を得た。Example 14 In Example 9 (d), 0.24 g of 4-octyloxyphenol was used in place of 0.22 g of 4-octyloxyphenol, and 0.24 g of 4-octyloxy-3-fluorophenol was used. Otherwise, the same operation as in Example 9 (d) was carried out (S)- 4-octyloxy-3-fluorophenyl 4- (1-methylhexyl) oxy-2'-fluoro-4'-biphenylcarboxylate 0.35 g (70.0
%) Was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で552に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 552 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例15 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて実施例７（ｃ）で得られる４−デシル
オキシ−３−フルオロフエノール0.26gを用い、他は実
施例９（ｄ）と同様に操作して（Ｓ）−４−デシルオキ
シ−３−フルオロフエニル４−（１−メチルヘキシ
ル）オキシ−２′−フルオロ−４′−ビフエニルカルボ
キシレート0.41g（77.8％）を得た。Example 15 In Example 9 (d), 4-octyloxyphenol 0.22 g was used in place of 4-decyloxy-3-fluorophenol 0.26 g obtained in Example 7 (c), and the same as in Example 9 (d). After that, 0.41 g (77.8%) of (S) -4-decyloxy-3-fluorophenyl-4- (1-methylhexyl) oxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例16 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて実施例８（ｂ）で得られる２−フルオ
ロ−４−ペンチルフエノール0.26gを用い、他は実施例
９（ｄ）と同様に操作して（Ｓ）−２−フルオロ−４−
ペンチルフエニル４−（１−メチルヘキシル）オキシ
−２′−フルオロ−４′−ビフエニルカルボキシレート
0.33g（73.5％）を得た。Example 16 In Example 9 (d), 4-octyloxyphenol 0.22 g was replaced with 2-fluoro-4-pentylphenol 0.26 g obtained in Example 8 (b), and the same as in Example 9 (d). To (S) -2-fluoro-4-
Pentylphenyl 4- (1-methylhexyl) oxy-2'-fluoro-4'-biphenylcarboxylate
0.33 g (73.5%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で494に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 494 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例17 実施例９（ｄ）において、４−オクチルオキシフエノー
ル0.22gに替えて2,3−ジシアノ−４−ヘキシルオキシフ
エノール0.24gを用い、他は実施例９（ｄ）と同様に操
作して（Ｓ）−2,3−ジシアノ−４−ヘキシルオキシフ
エニル４−（１−メチルヘキシル）オキシ−２′−フ
ルオロ−４′−ビフエニルカルボキシレート0.16g（31.
7％）を得た。Example 17 In Example 9 (d), 0.23 g of 2,3-dicyano-4-hexyloxyphenol was used in place of 0.22 g of 4-octyloxyphenol, and other operations were performed in the same manner as in Example 9 (d) (S ) -2,3-Dicyano-4-hexyloxyphenyl 4- (1-methylhexyl) oxy-2'-fluoro-4'-biphenylcarboxylate 0.16 g (31.
7%).
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で556に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was found at 556 and the relation of the raw materials used, that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例18 実施例１（ｃ）における、（Ｓ）−４−メチルヘキシル
ブロマイド8.0gに替えてデシルブロマイド10.1gを用
い、他は実施例１（ｃ）と同様に操作して４−デシルオ
キシ−２′−フルオロ−４′−ブロムビフエニル6.2g
（81.4％）を得た。Example 18 In the same manner as in Example 1 (c), except that 10.1 g of decyl bromide was used instead of 8.0 g of (S) -4-methylhexyl bromide in Example 1 (c), 4-decyloxy-2'- was used. Fluoro-4'-bromobiphenyl 6.2g
(81.4%) was obtained.
実施例１（ｄ）における、（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロ−４′−ブロムビフエ
ニル11.7gに替えて、（ａ）で得られた４−デシルオキ
シ−２′−フルオロ−４′−ブロムビフエニル7.0gを用
い、他は実施例１（ｄ）と同様に操作して粗４−デシル
オキシ−２′−フルオロ−４′−シアノビフエニルを
得、これをメタノールで再結晶して粗４−デシルオキシ
−２′−フルオロ−４′−シアノビフエニル5.4gを得
た。 In place of 11.7 g of (S) -4- (4-methylhexyl) oxy-2′-fluoro-4′-bromobiphenyl in Example 1 (d), 4-decyloxy-2 ′ obtained in (a) was replaced. Using 7.0 g of -fluoro-4'-bromobiphenyl, the same procedure as in Example 1 (d) was carried out otherwise to obtain crude 4-decyloxy-2'-fluoro-4'-cyanobiphenyl, which was recrystallized from methanol. Thus, 5.4 g of crude 4-decyloxy-2'-fluoro-4'-cyanobiphenyl was obtained.
実施例１（ｅ）における、粗（Ｓ）−４−（４−メチル
ヘキシル）オキシ−２′−フルオロ−４′−シアノビフ
エニル9.8gに替えて、（ｂ）で得られた粗４−デシルオ
キシ−２′−フルオロ−４′−シアノビフエニル5.4gを
用い、他は実施例１（ｅ）と同様に操作し、再結晶をア
セトンで行うことにより４−デシルオキシ−２′−フル
オロ−４′−ビフエニルカルボン酸5.5gを得た。 In place of 9.8 g of crude (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl in Example 1 (e), the crude 4-decyloxy-obtained in (b) was replaced. 4-decyloxy-2'-fluoro-4'-biphenyl was obtained by using 5.4 g of 2'-fluoro-4'-cyanobiphenyl and otherwise operating in the same manner as in Example 1 (e), and performing recrystallization with acetone. 5.5 g of carboxylic acid was obtained.
反応器に（ｃ）で得られた４−デシルオキシ−２′−フ
ルオロ−４′−ビフエニルカルボン酸0.3g、DCC 0.19
g、４−（ジメチルアミノ）ピリジン0.10g、（Ｓ）−４
−（２−メチルブチル）オキシフエノール0.16g及び塩
化メチレン30mlを仕込み、18時間室温で攪拌反応した。
反応液を過し、液を水洗し、芒硝で脱水後、溶媒を
留去し、残留分をシリカゲルカラムクロマトグラフイー
（溶離液ヘキサン／ベンゼン＝1/1）にて精製し、次い
でメタノール／アセトン混合溶媒で再結晶して（Ｓ）−
４−（２−メチルブチル）オキシフエニル４−デシル
オキシ−２′−フルオロ−４′−カルボキシレート0.31
g（72.1％）を得た。 In the reactor, 0.3 g of 4-decyloxy-2'-fluoro-4'-biphenylcarboxylic acid obtained in (c), DCC 0.19
g, 4- (dimethylamino) pyridine 0.10 g, (S) -4
0.16 g of-(2-methylbutyl) oxyphenol and 30 ml of methylene chloride were charged, and the reaction was carried out with stirring at room temperature for 18 hours.
Pass the reaction solution, wash the solution with water, dehydrate with sodium sulfate, evaporate the solvent, and purify the residue by silica gel column chromatography (eluent hexane / benzene = 1/1), then methanol / acetone. Recrystallize with mixed solvent (S)-
4- (2-methylbutyl) oxyphenyl 4-decyloxy-2'-fluoro-4'-carboxylate 0.31
g (72.1%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で534に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 534 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例19 実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、（Ｓ）−４−
（４−メチルヘキシル）オキシフエニル0.18gを用い、
他は実施例18（ｄ）と同様に操作して（Ｓ）−４−（４
−メチルヘキシル）オキシフエニル４−デシルオキシ
−２′−フルオロ−４′−ビフエニルカルボキシレート
0.33g（73.3％）を得た。Example 19 In place of (S) -4- (2-methylbutyl) oxyphenol 0.16 g in Example 18 (d), (S) -4-
(4-methylhexyl) oxyphenyl 0.18 g was used,
Otherwise by performing the same operation as in Example 18 (d), (S) -4- (4
-Methylhexyl) oxyphenyl 4-decyloxy-2'-fluoro-4'-biphenylcarboxylate
0.33 g (73.3%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で562に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 562 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例20 実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、（Ｓ）−４−
（１−メチルヘプチル）オキシフエニル0.20gを用い、
他は実施例18（ｄ）と同様に操作して（Ｓ）−４−（１
−メチルヘプチル）オキシフエニル４−デシルオキシ
−２′−フルオロ−４′−ビフエニルカルボキシレート
0.29g（63.0％）を得た。Example 20 In place of (S) -4- (2-methylbutyl) oxyphenol 0.16 g in Example 18 (d), (S) -4-
Using 0.20 g of (1-methylheptyl) oxyphenyl,
Others are operated similarly to Example 18 (d), and (S) -4- (1
-Methylheptyl) oxyphenyl 4-decyloxy-2'-fluoro-4'-biphenylcarboxylate
0.29 g (63.0%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で576に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 576 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例21 反応器に２−フルオロフエノール37g及び二硫化炭素100
mlを仕込み、氷水冷攪拌下に無水塩化アルミニウム59g
を加え、０℃以下で無水酢酸33gを滴下し、１時間同温
度で反応した。反応液を希塩酸に注加し、塩化メチレン
で抽出し、水洗し、芒硝で脱水後、溶媒を留去し、残留
分をメタノールで再結晶して３−フルオロ−４−メトキ
シアセトフエノン33g（66.9g）を得た。Example 21 37 g of 2-fluorophenol and 100 carbon disulfide in the reactor
ml, and while stirring under ice-water cooling, 59 g of anhydrous aluminum chloride
Was added, and 33 g of acetic anhydride was added dropwise at 0 ° C or lower, and the mixture was reacted at the same temperature for 1 hour. The reaction solution was poured into diluted hydrochloric acid, extracted with methylene chloride, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was recrystallized from methanol to give 3-fluoro-4-methoxyacetophenone 33 g ( 66.9 g) was obtained.
反応器に（ａ）で得られた３−フルオロ−４−メトキシ
アセトフエノン25g、48％臭化水素酸300ml並びに酢酸15
0mlを仕込み、17時間攪拌還流した。反応液を水に注加
し、塩化メチレンで抽出し、水洗し、芒硝で脱水後、溶
媒を留去し、残留分をシリカゲルカラムクロマトグラフ
イー（溶離液塩化メチレン）にて精製し３−フルオロ−
４−ヒドロキシアセトフエノン8.8g（38.4％）を得た。 In a reactor, 25 g of 3-fluoro-4-methoxyacetophenone obtained in (a), 300 ml of 48% hydrobromic acid and 15% of acetic acid were added.
0 ml was charged and the mixture was stirred and refluxed for 17 hours. The reaction solution was poured into water, extracted with methylene chloride, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent methylene chloride) to give 3-fluoro. −
8.8 g (38.4%) of 4-hydroxyacetophenone was obtained.
反応器に（Ｓ）−１−メチルヘキシルトシレート6.4g、
（ｂ）で得られた３−フルオロ−４−ヒドロキシアセト
フエノン2.9g、炭酸カリウム4.1g及び２−ブタノン（ME
K）30mlを仕込み、５時間還流攪拌した。反応液を水に
注加し、ベンゼンで抽出し、水洗し、芒硝で脱水後、溶
媒を留去し、残留分をシリカゲルカラムクロマトグラフ
イー（溶離液ヘキサン／酢酸エチル＝10/1）にて精製
し、（Ｒ）−３−フルオロ−４−（１−メチルヘキサ
ン）オキシアセトフエノン3.0g（63.2％）を得た。 6.4 g of (S) -1-methylhexyltosylate in the reactor,
2.9 g of 3-fluoro-4-hydroxyacetophenone obtained in (b), 4.1 g of potassium carbonate and 2-butanone (ME
(K) 30 ml was charged and the mixture was stirred under reflux for 5 hours. The reaction solution was poured into water, extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (eluent hexane / ethyl acetate = 10/1). Purification yielded 3.0 g (63.2%) of (R) -3-fluoro-4- (1-methylhexane) oxyacetophenone.
反応器に（ｃ）で得た（Ｒ）−３−フルオロ−４−（１
−メチルヘキシル）オキシアセトフエノン1.9g及び塩化
メチレン30mlを仕込み、10℃で攪拌下に88％ギ酸20ml、
無水酢酸10mlを滴下し、さらに濃硫酸1mlを加えた後、3
5％過酸化水素水20mlを滴下し、滴下後徐々に昇温して4
5〜50℃で９時間攪拌反応した。反応液を氷水に注加
し、ベンゼンで抽出、炭酸水素ナトリウム水溶液で洗
浄、水洗、芒硝脱水を行い、溶媒を留去し、残留分を得
た。この残留分とメチルアルコール30mlを別の反応器に
仕込み、これに25％苛性カリ水溶液を加え、４時間還流
攪拌した。反応液を氷と希塩酸中に注加し、ベンゼンで
抽出、食塩水で洗浄、芒硝で脱水後、溶媒を留去し、残
留分をシリカゲルカラムクロマトグラフイー（溶離液塩
化メチレン）にて精製し、（Ｒ）−３−フルオロ−４−
（１−メチルヘキシル）オキシフエノール1.33g（78.2
％）を得た。 (R) -3-fluoro-4- (1) obtained in (c) in the reactor
-Methylhexyl) oxyacetophenone (1.9 g) and methylene chloride (30 ml) were charged, and 88% formic acid (20 ml) was stirred at 10 ° C.
After adding 10 ml of acetic anhydride dropwise and adding 1 ml of concentrated sulfuric acid,
Add 20 ml of 5% hydrogen peroxide solution and gradually raise the temperature after dropping.
The reaction was carried out with stirring at 5 to 50 ° C for 9 hours. The reaction solution was poured into ice water, extracted with benzene, washed with an aqueous sodium hydrogen carbonate solution, washed with water and dehydrated with sodium sulfate, and the solvent was distilled off to obtain a residue. This residue and 30 ml of methyl alcohol were charged into another reactor, to which 25% aqueous potassium hydroxide solution was added, and the mixture was stirred under reflux for 4 hours. The reaction solution was poured into ice and dilute hydrochloric acid, extracted with benzene, washed with brine, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent methylene chloride). , (R) -3-fluoro-4-
(1-Methylhexyl) oxyphenol 1.33 g (78.2
%) Was obtained.
実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、（ｄ）で得られ
た（Ｒ）−３−フルオロ−４−（１−メチルヘキシル）
オキシフエノール0.18gを用い、他は実施例18（ｄ）と
同様に操作して（Ｒ）−３−フルオロ−４−（１−メチ
ルヘキシル）オキシフエニル４−デシルオキシ−２′
−フルオロ−４′−ビフエニルカルボキシレート0.23g
（50.0％）を得た。 (R) -3-fluoro-4- (1-methylhexyl) obtained in (d) was replaced with 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d).
The same procedure as in Example 18 (d) was carried out except that 0.18 g of oxyphenol was used, and (R) -3-fluoro-4- (1-methylhexyl) oxyphenyl 4-decyloxy-2 '.
-Fluoro-4'-biphenylcarboxylate 0.23 g
(50.0%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例22 実施例６（ａ）におけるオクチルブロマイド25.9gに替
えて、（Ｓ）−４−メチルヘキシルブロマイド25.0gを
用い、他は実施例６（ａ）と同様に操作して、（Ｓ）−
４−（４−メチルヘキシル）オキシ−３−フルオロブロ
ムベンゼン25.9g（66.9％）を得た。Example 22 In place of 25.9 g of octyl bromide in Example 6 (a), 25.0 g of (S) -4-methylhexyl bromide was used, and otherwise the same operation as in Example 6 (a) was carried out, and (S)-
25.9 g (66.9%) of 4- (4-methylhexyl) oxy-3-fluorobromobenzene was obtained.
実施例６（ｂ）における４−オクチルオキシ−３−フル
オロブロムベンゼン9gに替えて、（ａ）で得られた
（Ｓ）−４−（４−メチルヘキシル）オキシ−３−フル
オロブロムベンゼン8.6gを用い、他は実施例６（ｂ）と
同様に操作して、シリカゲルカラムクロマトグラフイー
（溶離液ヘキサン／酢酸エチル＝10/1）にて精製し
（Ｓ）−４−（４−メチルヘキシル）オキシ−３−フル
オロフエノール3.2g（47.4％）を得た。 In place of 9 g of 4-octyloxy-3-fluorobromobenzene in Example 6 (b), 8.6 g of (S) -4- (4-methylhexyl) oxy-3-fluorobromobenzene obtained in (a). The same procedure as in Example 6 (b) was carried out, and the product was purified by silica gel column chromatography (eluent hexane / ethyl acetate = 10/1) and purified by (S) -4- (4-methylhexyl). ) Oxy-3-fluorophenol (3.2 g, 47.4%) was obtained.
実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、（ｂ）で得られ
た（Ｓ）−４−（４−メチルヘキシル）オキシフエノー
ル0.18gを用い、他は実施例18（ｄ）と同様に操作して
（Ｓ）−４−（４−メチルヘキシル）オキシ−３−フル
オロフエニル４−デシルオキシ−２′−フルオロ−
４′−ビフエニルカルボキシレート0.25g（53.5％）を
得た。 In place of 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d), 0.18 g of (S) -4- (4-methylhexyl) oxyphenol obtained in (b) was used. Used in the same manner as in Example 18 (d), except that (S) -4- (4-methylhexyl) oxy-3-fluorophenyl-4-decyloxy-2'-fluoro-
0.25 g (53.5%) of 4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例23 反応器に（Ｓ）−１−メチルヘプチルトシレート22.8
g、３−ブロム−４−ヒドロキシアセトフエノン11.5g、
炭酸カリウム14.8g並びに２−ブタノン100mlを仕込み、
16時間還流攪拌した。反応液を水に注加し、ベンゼンで
抽出し、10％苛性ソーダ水溶液で洗浄し、次いで水洗
し、芒硝で脱水後、溶媒を留去し、粗（Ｒ）−３−ブロ
ム−４−（１−メチルヘプチル）オキシアセトフエノン
12.6gを得た。Example 23 (S) -1-Methylheptylsilate 22.8 in reactor
g, 3-bromo-4-hydroxyacetophenone 11.5 g,
Charge 14.8 g of potassium carbonate and 100 ml of 2-butanone,
The mixture was stirred under reflux for 16 hours. The reaction solution was poured into water, extracted with benzene, washed with a 10% aqueous sodium hydroxide solution, then washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and crude (R) -3-bromo-4- (1 -Methylheptyl) oxyacetophenone
12.6 g was obtained.
反応器に（ａ）で得た粗（Ｒ）−３−ブロム−４−（１
−メチルヘプチル）オキシアセトフエノン5g、87％ギ酸
40ml、無水酢酸20ml並びに塩化メチレン30mlを仕込み、
氷冷攪拌下に、濃硫酸1ml、次いで35％過酸化水素水100
mlを滴下し、24時間攪拌反応した。反応液を水に注加
し、塩化メチレンで抽出後、水洗し、芒硝で脱水し、溶
媒を留去して、粗（Ｒ）−３−ブロム−４−（１−メチ
ルヘプチル）オキシ−１−アセチルオキシベンゼン5.0g
を得た。別の反応器にこの残留分5.0g、シアン化第一銅
1.57g並びにＮ−メチル−２−ピロリジン30mlを仕込
み、140〜160℃で26時間攪拌した。反応液を塩化第二鉄
5g、濃塩酸2ml並びに水30mlからなる水溶液にて処理
し、クロロホルムで抽出し、水洗し、芒硝で脱水し、溶
媒を留去後、GTO（ガラスチューブオーブン）にて減圧
蒸溜して（Ｒ）−３−シアノ−４−（１−メチルヘプチ
ル）オキシフエノール1.0gを得た。 The crude (R) -3-bromo-4- (1) obtained in (a) was added to the reactor.
-Methylheptyl) oxyacetophenone 5g, 87% formic acid
Charge 40 ml, acetic anhydride 20 ml and methylene chloride 30 ml,
1 ml of concentrated sulfuric acid, then 100% of 35% hydrogen peroxide under ice cooling
ml was added dropwise and the reaction was carried out with stirring for 24 hours. The reaction solution was poured into water, extracted with methylene chloride, washed with water, dehydrated with sodium sulfate, and the solvent was distilled off to give crude (R) -3-bromo-4- (1-methylheptyl) oxy-1. -Acetyloxybenzene 5.0 g
Got In a separate reactor 5.0 g of this residue, cuprous cyanide
1.57 g and N-methyl-2-pyrrolidine (30 ml) were charged, and the mixture was stirred at 140 to 160 ° C. for 26 hours. The reaction solution is ferric chloride
Treated with an aqueous solution consisting of 5 g, concentrated hydrochloric acid 2 ml and water 30 ml, extracted with chloroform, washed with water, dehydrated with Glauber's salt, distilled off the solvent, and then distilled under reduced pressure in a GTO (glass tube oven) (R). 1.0 g of -3-cyano-4- (1-methylheptyl) oxyphenol was obtained.
実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、（ｂ）で得られ
た（Ｒ）−３−シアノ−４−（１−メチルヘプチル）オ
キシフエノール0.20gを用い、他は実施例18（ｄ）と同
様に操作して（Ｒ）−３−シアノ−４−（１−メチルヘ
プチル）オキシフエニル４−デシルオキシ−２′−フ
ルオロ−４′−ビフエニルカルボキシレート0.24g（49.
5％）を得た。 The (R) -3-cyano-4- (1-methylheptyl) oxy obtained in (b) was replaced with 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d). (R) -3-Cyano-4- (1-methylheptyl) oxyphenyl 4-decyloxy-2'-fluoro-4'-bif was prepared by the same procedure as in Example 18 (d) except that 0.20 g of phenol was used. 0.24 g of ethyl carboxylate (49.
5%).
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で601に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 601 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例24 反応器に３−フルオロ−４−シアノフエノール1g、15％
苛性ソーダ水溶液20ml並びにメタノール30mlを仕込み、
10時間攪拌還流した。反応液を氷冷水に注加し、濃塩酸
を加えて酸性とし、析出物を取し、水洗後、ヘキサン
で再結晶して２−フルオロ−４−ヒドロキシ安息香酸0.
97g（85.1％）を得た。Example 24 3-fluoro-4-cyanophenol 1g in reactor, 15%
Charge 20 ml of caustic soda solution and 30 ml of methanol,
The mixture was stirred and refluxed for 10 hours. The reaction solution was poured into ice-cold water, acidified by adding concentrated hydrochloric acid, the precipitate was taken, washed with water and recrystallized with hexane to give 2-fluoro-4-hydroxybenzoic acid.
97 g (85.1%) were obtained.
反応器に（ａ）で得られた２−フルオロ−４−ヒドロキ
シ安息香酸0.97g、（Ｓ）−２−メチルブタノール10ml
並びに触媒量の濃硫酸を仕込み、５時間攪拌還流した。
反応液を水に注加し、ベンゼンで抽出し、水洗し、芒硝
で脱水後、溶媒を留去し、残留分をヘキサンで再結晶し
て（Ｓ）−３−フルオロ−４−（２−メチルブチル）オ
キシカルボニルフエノール1.1g（78％）を得た。 In the reactor, 0.97 g of 2-fluoro-4-hydroxybenzoic acid obtained in (a) and 10 ml of (S) -2-methylbutanol.
Further, a catalytic amount of concentrated sulfuric acid was charged, and the mixture was stirred and refluxed for 5 hours.
The reaction solution was poured into water, extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was recrystallized from hexane to obtain (S) -3-fluoro-4- (2- 1.1 g (78%) of methylbutyl) oxycarbonylphenol was obtained.
実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、（ｂ）で得られ
た（Ｓ）−３−フルオロ−４−（２−メチルブチル）オ
キシカルボニルフエノール0.20gを用い、他は実施例18
（ｄ）と同様に操作して（Ｓ）−３−フルオロ−４−
（２−メチルブチル）オキシカルボニルフエニル４−
デシルオキシ−２′−フルオロ−４′−ビフエニルカル
ボキシレート0.18g（38.3％）を得た。 The (S) -4-fluoro-4- (2-methylbutyl) oxycarbonyl obtained in (b) was replaced with 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d). Using 0.20 g of phenol, other than Example 18
Operating in the same manner as (d), (S) -3-fluoro-4-
(2-Methylbutyl) oxycarbonylphenyl 4-
0.18 g (38.3%) of decyloxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例25 実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、（Ｓ）−４−
（２−メチルブチル）オキシカルボニルフエノール0.18
gを用い、他は実施例18（ｄ）と同様に操作して（Ｓ）
−４−（２−メチルブチル）オキシカルボニルフエニル
４−デシルオキシ−２′−フルオロ−４′−ビフエニ
ルカルボキシレート0.29g（64.0％）を得た。Example 25 In place of (S) -4- (2-methylbutyl) oxyphenol 0.16 g in Example 18 (d), (S) -4-
(2-Methylbutyl) oxycarbonylphenol 0.18
g and using the same procedure as in Example 18 (d) except for (S)
0.29 g (64.0%) of 4- (2-methylbutyl) oxycarbonylphenyl 4-decyloxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で562に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 562 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例26 実施例１（ｃ）における、（Ｓ）−４−メチルヘキシル
ブロマイド8.0gに替えてオクチルブロマイド8.8gを用
い、他は実施例１（ｃ）と同様に操作して４−オクチル
オキシ−２′−フルオロ−４′−ブロムビフエニル6.0g
（84.5％）を得た。Example 26 In the same manner as in Example 1 (c), except that 8.8 g of octyl bromide was used instead of 8.0 g of (S) -4-methylhexyl bromide in Example 1 (c), 4-octyloxy-2 ′ was used. -Fluoro-4'-bromobiphenyl 6.0 g
(84.5%) was obtained.
実施例１（ｄ）における、（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロ−４′−ブロムビフエ
ニル11.7gに替えて、（ａ）で得られた４−オクチルオ
キシ−２′−フルオロ−４′−ブロムビフエニル12.1g
を用い他は実施例１（ｄ）と同様に操作して粗４−オク
チルオキシ−２′−フルオロ−４′−シアノビフエニル
10.1gを得た。 In place of 11.7 g of (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-bromobiphenyl in Example 1 (d), 4-octyloxy-2 obtained in (a) was replaced. ′ -Fluoro-4′-bromobiphenyl 12.1 g
Was used in the same manner as in Example 1 (d) except that crude 4-octyloxy-2'-fluoro-4'-cyanobiphenyl was used.
I got 10.1g.
実施例１（ｅ）における、粗（Ｓ）−４−（４−メチル
ヘキシル）オキシ−２′−フルオロ−４′−シアノビフ
エニル9.8gに替えて、（ｂ）で得られた粗４−オクチル
オキシ−２′−フルオロ−４′−シアノビフエニル10.1
g用い他は実施例１（ｅ）と同様に操作し、再結晶をア
セトンで行うことにより４−オクチルオキシ−２′−フ
ルオロ−４′−ビフエニルカルボン酸6.4g（60.3％）を
得た。 In place of 9.8 g of crude (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl in Example 1 (e), the crude 4-octyloxy obtained in (b) was used. -2'-fluoro-4'-cyanobiphenyl 10.1
The procedure of Example 1 (e) was repeated except that g was used, and recrystallization was carried out with acetone to obtain 6.4 g (60.3%) of 4-octyloxy-2'-fluoro-4'-biphenylcarboxylic acid. .
反応器に（ｃ）で得られた４−オクチルオキシ−２′−
フルオロ−４′−ビフエニルカルボン酸0.4g、DCC0.25
g、４−（ジメチルアミノ）ピリジン0.15g、（Ｓ）−４
−（１−メチルヘプチル）オキシフエノール0.28g及び
塩化メチレン30mlを仕込み、18時間室温で攪拌反応し
た。反応液を過し、液を水洗し、芒硝で脱水後、溶
媒を留去し、残留分をシリカゲルカラムクロマトグラフ
イー（溶離液ヘキサン／ベンゼン＝1/1）にて精製し、
次いでメタノール／アセトン混合溶媒で再結晶して
（Ｓ）−４−（１−メチルヘプチル）オキシフエニル
４−オクチルオキシ−２′−フルオロ−４′−ビフエニ
ルカルボキシレート0.43g（67.5％）を得た。 In the reactor, the 4-octyloxy-2'- obtained in (c)
Fluoro-4'-biphenylcarboxylic acid 0.4 g, DCC0.25
g, 4- (dimethylamino) pyridine 0.15 g, (S) -4
0.28 g of-(1-methylheptyl) oxyphenol and 30 ml of methylene chloride were charged and the reaction was carried out with stirring at room temperature for 18 hours. Pass the reaction solution, wash the solution with water, dehydrate with sodium sulfate, distill off the solvent, and purify the residue by silica gel column chromatography (eluent hexane / benzene = 1/1).
Then, it was recrystallized from a mixed solvent of methanol / acetone to obtain 0.43 g (67.5%) of (S) -4- (1-methylheptyl) oxyphenyl 4-octyloxy-2'-fluoro-4'-biphenylcarboxylate. .
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で548に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 548 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例27 実施例26（ｄ）における（Ｓ）−４−（１−メチルヘプ
チル）オキシフエノール0.28gに替えて、実施例23
（ｂ）で得られる（Ｓ）−３−シアノ−４−（１−メチ
ルヘプチル）オキシフエノール0.28gを用い、他は実施
例26（ｄ）と同様に操作して（Ｓ）−３−シアノ−４−
（１−メチルヘプチル）オキシフエニル４−オクチル
オキシ−２′−フルオロ−４′−ビフエニルカルボキシ
レート0.42g（63.6％）を得た。Example 27 Example 23 was replaced with 0.28 g of (S) -4- (1-methylheptyl) oxyphenol in Example 26 (d).
Using 0.28 g of (S) -3-cyano-4- (1-methylheptyl) oxyphenol obtained in (b), the same procedure as in Example 26 (d) is repeated except that (S) -3-cyano is used. -4-
0.42 g (63.6%) of (1-methylheptyl) oxyphenyl 4-octyloxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で574に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was observed at 574 and the relation of the raw materials used, that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例28 実施例26（ｄ）における、（Ｓ）−４−（１−メチルヘ
プチル）オキシフエノール0.28gに替えて、実施例21
（ｃ）で得られる（Ｒ）−３−フルオロ−４−（１−メ
チルヘキシル）オキシフエノール0.28gを用い、他は実
施例26（ｄ）と同様に操作して（Ｓ）−３−フルオロ−
４−（１−メチルヘキシル）オキシフエニル４−オク
チルオキシ−２′−フルオロ−４′−ビフエニルカルボ
キシレート0.41g（64.1％）を得た。Example 28 Example 21 was replaced with 0.28 g of (S) -4- (1-methylheptyl) oxyphenol in Example 26 (d).
Using 0.28 g of (R) -3-fluoro-4- (1-methylhexyl) oxyphenol obtained in (c), the same procedure as in Example 26 (d) is repeated except that (S) -3-fluoro is used. −
0.41 g (64.1%) of 4- (1-methylhexyl) oxyphenyl 4-octyloxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で552に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 552 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−１に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-1.
実施例29 実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、４−オクチルオ
キシフエノール0.19gを用い、他は実施例18（ｄ）と同
様に操作して、４−オクチルオキシフエニル４−デシ
ルオキシ−２′−フルオロ−４′−ビフエニルカルボキ
シレート0.36g（77.4％）を得た。Example 29 Using 0.19 g of 4-octyloxyphenol in place of 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d), the same operation as in Example 18 (d) was followed. Thus, 0.36 g (77.4%) of 4-octyloxyphenyl 4-decyloxy-2'-fluoro-4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で576に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 576 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−２に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-2.
実施例30 実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、４−オクチルフ
エノール0.18gを用い、他は実施例18（ｄ）と同様に操
作して、４−オクチルフエニル４−デシルオキシ−
２′−フルオロ−４′−ビフエニルカルボキシレート0.
30g（66.7％）を得た。Example 30 Using 0.18 g of 4-octylphenol in place of 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d), the same operation as in Example 18 (d) was repeated, 4-octylphenyl 4-decyloxy-
2'-fluoro-4'-biphenylcarboxylate 0.
Obtained 30 g (66.7%).
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で560に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 560 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−２に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-2.
実施例31 実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、実施例８（ｂ）
で得られる２−フルオロ−４−ペンチルフエノール0.23
gを用い、他は実施例18（ｄ）と同様に操作して２−フ
ルオロ−４−ペンチルフエニル４−デシルオキシ−
２′−フルオロ−４′−ビフエニルカルボキシレート0.
21g（48.8％）を得た。Example 31 Example 8 (b) was used instead of 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d).
2-fluoro-4-pentylphenol 0.23 obtained in
2-fluoro-4-pentylphenyl-4-decyloxy- was prepared by the same procedure as in Example 18 (d) except that g was used.
2'-fluoro-4'-biphenylcarboxylate 0.
21 g (48.8%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で536に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 536 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−２に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-2.
実施例32 実施例18（ｄ）における（Ｓ）−４−（２−メチルブチ
ル）オキシフエノール0.16gに替えて、実施例６（ｂ）
で得られる３−フルオロ−４−オクチルオキシフエノー
ル0.19gを用い、他は実施例18（ｄ）と同様に操作して
３−フルオロ−４−オクチルオキシフエニル４−デシ
ルオキシ−２′−フルオロ−４′−ビフエニルカルボキ
シレート0.22g（45.8％）を得た。Example 32 Example 6 (b) was used instead of 0.16 g of (S) -4- (2-methylbutyl) oxyphenol in Example 18 (d).
Using 0.19 g of 3-fluoro-4-octyloxyphenol obtained in 1. above, the same procedure as in Example 18 (d) was followed except that 3-fluoro-4-octyloxyphenyl 4-decyloxy-2'-fluoro- 0.22 g (45.8%) of 4'-biphenylcarboxylate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で594に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 594 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−２に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-2.
実施例33 反応器にマグネシウム片1.03g並びに少量のヨウ素を仕
込み、これに実施例１（ｃ）で得られた（Ｓ）−４−
（４−メチルヘキシ）オキシ−２′−フルオロ−４′−
ブロムビフエニル14gのTHF20ml溶液の少量を加え、加温
して反応を開始させた後 残りのTHF溶液を攪拌下に滴
下し、更に２時間攪拌還流し、グリニヤール試薬を作成
した。Example 33 A reactor was charged with 1.03 g of magnesium pieces and a small amount of iodine, which was obtained in Example 1 (c) (S) -4-.
(4-Methylhex) oxy-2'-fluoro-4'-
A small amount of brombiphenyl (14 g) in THF (20 ml) was added, and the mixture was heated to start the reaction. The remaining THF solution was added dropwise with stirring, and the mixture was further refluxed with stirring for 2 hours to prepare a Grignard reagent.
別の容器に硼酸トリブチルエステル13.2gを仕込み、40
〜48℃で先に作成したグリニヤール試薬を攪拌下に滴下
し、さらに２時間同温度で攪拌した。次いで、30℃以下
で10％硫酸40mlを滴下後、ベンゼン100mlを加えて抽出
した。有機層を分取して別の反応器に仕込み、これに35
％過酸化水素水30mlを40℃で攪拌下に滴下し、同温度で
２時間反応した。反応液を水に注加し、有機層を亜硫酸
水素ナトリウムで処理し、水洗し、芒硝で脱水後、残留
分をシリカゲルカラムクロマトグラフイー（溶離液ヘキ
サン／酢酸エチル＝10/1）にて精製し（Ｓ）−４−（４
−メチルヘキシル）オキシ−２′−フルオロ−４′−ヒ
ドロキシビフエニル6.08g（52.4％）を得た。Charge 13.2 g of boric acid tributyl ester into another container and
The Grignard reagent prepared above was added dropwise at ˜48 ° C. with stirring, and the mixture was further stirred at the same temperature for 2 hours. Then, 40 ml of 10% sulfuric acid was added dropwise at 30 ° C or lower, and 100 ml of benzene was added for extraction. Separate the organic layer and charge it in another reactor.
30% aqueous hydrogen peroxide was added dropwise at 40 ° C. with stirring, and the mixture was reacted at the same temperature for 2 hours. The reaction solution was poured into water, the organic layer was treated with sodium hydrogen sulfite, washed with water, dehydrated with sodium sulfate, and the residue was purified by silica gel column chromatography (eluent hexane / ethyl acetate = 10/1). (S) -4- (4
6.08 g (52.4%) of -methylhexyl) oxy-2'-fluoro-4'-hydroxybiphenyl were obtained.
反応器に（ａ）で得た（Ｓ）−４−（４−メチルヘキシ
ル）オキシ−２′−フルオロ−４′−ヒドロキシビフエ
ニル0.25g、４−オクチルオキシ安息香酸0.21g、DCC0.2
0g、４−（ジメチルアミノ）ピリジン0.09g及び塩化メ
チレン30mlを仕込み、11時間室温で攪拌反応した。 In the reactor, (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-hydroxybiphenyl obtained in (a) 0.25 g, 4-octyloxybenzoic acid 0.21 g, DCC0.2
0 g, 4- (dimethylamino) pyridine 0.09 g and methylene chloride 30 ml were charged, and the reaction was carried out with stirring at room temperature for 11 hours.
反応液を過し、液を水洗し、芒硝で脱水後、溶媒を
留去し、残留分をシリカゲルカラムクロマトグラフイー
（溶離液ヘキサン／ベンゼン＝2/1）にて精製し、次い
でメタノール（アセトン混合溶媒で再結晶して（Ｓ）−
４−（４−メチルヘキシル）オキシ−２′−フルオロビ
フエニル−４′−イル４−オクチルオキシベンゾエー
ト0.27g（61.5％）を得た。Pass the reaction solution, wash the solution with water, dehydrate with sodium sulfate, evaporate the solvent, and purify the residue by silica gel column chromatography (eluent hexane / benzene = 2/1), then methanol (acetone). Recrystallize with mixed solvent (S)-
0.27 g (61.5%) of 4- (4-methylhexyl) oxy-2'-fluorobiphenyl-4'-yl 4-octyloxybenzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で534に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 534 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例34 実施例33（ｂ）における４−オクチルオキシ安息香酸0.
21gに替えて４−ウンデシル安息香酸0.24gを用い、他は
実施例33（ｂ）と同様に操作して（Ｓ）−４−（４−メ
チルヘキシル）オキシ−２′−フルオロビフエニル−
４′−イル４−ウンデシルベンゾエート0.45g（94.3
％）を得た。Example 34 4-octyloxybenzoic acid in Example 33 (b)
21 g was replaced with 0.24 g of 4-undecylbenzoic acid, and the same procedure as in Example 33 (b) was repeated except that (S) -4- (4-methylhexyl) oxy-2′-fluorobiphenyl-
0.45 g of 4'-yl 4-undecyl benzoate (94.3
%) Was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で576に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 576 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例35 実施例33（ｂ）における４−オクチルオキシ安息香酸0.
21gに替えて４−オクチル安息香酸0.19を用い、他は実
施例33（ｂ）と同様に操作して（Ｓ）−４−（４−メチ
ルヘキシル）オキシ−２′−フルオロビフエニル−４′
−イル４−オクチルベンゾエート0.19g（44.2％）を
得た。Example 35 4-octyloxybenzoic acid in Example 33 (b)
4-octylbenzoic acid 0.19 was used in place of 21 g, and the same procedure as in Example 33 (b) was repeated except that (S) -4- (4-methylhexyl) oxy-2′-fluorobiphenyl-4 ′ was used.
0.19 g (44.2%) of -yl 4-octyl benzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で518に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 518 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例36 実施例33（ｂ）における４−オクチルオキシ安息香酸0.
21gに替えて４−デシル安息香酸0.22gを用い、他は実施
例33（ｂ）と同様に操作して（Ｓ）−４−（４−メチル
ヘキシル）オキシ−２′−フルオロビフエニル−４′−
イル４−デシルベンゾエート0.26g（57.8％）を得
た。Example 36 4-octyloxybenzoic acid in Example 33 (b)
21 g was replaced with 0.22 g of 4-decylbenzoic acid, and the same operation as in Example 33 (b) was repeated except that (S) -4- (4-methylhexyl) oxy-2′-fluorobiphenyl-4 was used. ′-
0.26 g (57.8%) of yl 4-decyl benzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で546に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was observed at 546 and the relation of the raw materials used, that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例37 実施例１（ｄ）における（Ｓ）−４−（４−メチルヘキ
シル）オキシ−２−フルオロ−４′−ブロムビフエニル
11.7gに替えて、実施例６（ａ）で得られた４−オクチ
ルオキシ−３−フルオロブロムベンゼン8.8gを用い、他
は実施例１（ｄ）と同様に操作して、粗４−オクチルオ
キシ−３−フルオロベンゾニトリル4.7gを得た。Example 37 (S) -4- (4-Methylhexyl) oxy-2-fluoro-4′-bromobiphenyl in Example 1 (d)
Instead of 11.7 g, 8.8 g of 4-octyloxy-3-fluorobromobenzene obtained in Example 6 (a) was used, and otherwise the same as in Example 1 (d), the crude 4-octyl was used. 4.7 g of oxy-3-fluorobenzonitrile was obtained.
実施例１（ｅ）における粗（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロ−４′−シアノビフエ
ニル9.8gに替えて、（ａ）で得られた粗４−オクチルオ
キシ−３−フルオロベンゾニトリル4.7gを用い、他は同
様に操作して、４−オクチルオキシ−３−フルオロ安息
香酸3.5g（69.2％）を得た。 In place of 9.8 g of crude (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl in Example 1 (e), the crude 4-octyloxy-obtained in (a) was replaced. Using the same procedure as above, except that 4.7 g of 3-fluorobenzonitrile was used, 3.5 g (69.2%) of 4-octyloxy-3-fluorobenzoic acid was obtained.
実施例33（ｂ）における４−オクチルオキシ安息香酸0.
21gに替えて、（ｂ）で得た４−オクチルオキシ−３−
フルオロ安息香酸0.31gを用い、他は実施例33（ｂ）と
同様に操作することにより（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロビフエニル−４′−イ
ル４−オクチルオキシ−３−フルオロベンゾエート0.
3g（54.5％）を得た。 4-octyloxybenzoic acid in Example 33 (b)
4-octyloxy-3-obtained in (b) in place of 21 g
By using 0.31 g of fluorobenzoic acid and otherwise operating in the same manner as in Example 33 (b), (S) -4- (4-methylhexyl) oxy-2′-fluorobiphenyl-4′-yl-4- Octyloxy-3-fluorobenzoate 0.
3 g (54.5%) were obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で552に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 552 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例38 実施例１（ｄ）における（Ｓ）−４−（４−メチルヘキ
シル）オキシ−２−フルオロ−４′−ブロムビフエニル
11.7gに替えて、実施例７（ａ）で得られた４−デシル
オキシ−３−フルオロブロムベンゼン9.7gを用い、他は
実施例１（ｄ）と同様に操作して、粗４−デシルオキシ
−３−フルオロベンゾニトリル7.8gを得た。Example 38 (S) -4- (4-Methylhexyl) oxy-2-fluoro-4′-bromobiphenyl in Example 1 (d)
Instead of 11.7 g, 9.7 g of 4-decyloxy-3-fluorobromobenzene obtained in Example 7 (a) was used, and otherwise the same as in Example 1 (d), the crude 4-decyloxy- 7.8 g of 3-fluorobenzonitrile was obtained.
実施例１（ｅ）における粗（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロ−４′−シアノビフエ
ニル9.8gに替えて、（ａ）で得られた粗４−デシルオキ
シ−３−フルオロベンゾニトリル7.8gを用い、他は同様
に操作して、４−デシルオキシ−３−フルオロ安息香酸
5.0g（60.2％）を得た。 The crude 4-decyloxy-3 obtained in (a) was replaced by 9.8 g of crude (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-cyanobiphenyl in Example 1 (e). 4-decyloxy-3-fluorobenzoic acid was used in the same manner except that 7.8 g of fluorobenzonitrile was used.
5.0 g (60.2%) was obtained.
実施例33（ｂ）における４−オクチルオキシ安息香酸0.
21gに替えて、（ｂ）で得た４−デシルオキシ−３−フ
ルオロ安息香酸0.30gを用い、他は実施例33（ｂ）と同
様に操作することにより（Ｓ）−４−（４−メチルヘキ
シル）オキシ−２′−フルオロビフエニル−４′−イル
４−デシルオキシ−３−フルオロベンゾエート0.3g
（62.5％）を得た。 4-octyloxybenzoic acid in Example 33 (b)
Instead of 21 g, 0.30 g of 4-decyloxy-3-fluorobenzoic acid obtained in (b) was used, and otherwise the same operation as in Example 33 (b) was conducted to obtain (S) -4- (4-methyl). Hexyl) oxy-2'-fluorobiphenyl-4'-yl 4-decyloxy-3-fluorobenzoate 0.3 g
(62.5%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例39 実施例33（ｂ）における４−オクチルオキシ安息香酸0.
21gに替えて、４−デカノイルオキシ安息香酸0.24gを用
い、他は実施例33（ｂ）と同様に操作することにより
（Ｓ）−４−（４−メチルヘキシル）オキシ−２′−フ
ルオロビフエニル−４′−イル４−デカノイルオキシ
ベンゾエート0.29g（60.4％）を得た。Example 39 4-octyloxybenzoic acid in Example 33 (b)
By replacing 0.2 g of 4-decanoyloxybenzoic acid in place of 21 g and by operating in the same manner as in Example 33 (b) except that (S) -4- (4-methylhexyl) oxy-2′-fluoro, 0.29 g (60.4%) of biphenyl-4'-yl 4-decanoyloxybenzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で576に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 576 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例40 実施例33（ａ）における（Ｓ）−４−（４−メチルヘキ
シル）オキシ−２′−フルオロ−４′−ブロムビフエニ
ル14gに替えて、実施例９（ａ）で得られる（Ｒ）−４
−（１−メチルヘキシル）オキシ−２′−フルオロ−
４′−ブロムビフエニル14gを用い、他は実施例33
（ａ）と同様に操作して、（Ｒ）−４−（１−メチルヘ
キシル）オキシ−２′−フルオロ−４′−ヒドロキシビ
フエニル2.7g（23.3％）を得た。Example 40 (R) -4 obtained in Example 9 (a) in place of (S) -4- (4-methylhexyl) oxy-2′-fluoro-4′-bromobiphenyl 14 g in Example 33 (a).
-(1-Methylhexyl) oxy-2'-fluoro-
14 'of 4'-bromobiphenyl was used, except for Example 33.
The same procedure as in (a) was performed to obtain 2.7 g (23.3%) of (R) -4- (1-methylhexyl) oxy-2'-fluoro-4'-hydroxybiphenyl.
反応器に（ａ）で得た（Ｒ）−４−（１−メチルヘキシ
ル）オキシ−２′−フルオロ−４′−ヒドロキシビフエ
ニル0.30g、４−オクチルオキシ安息香酸0.25g、DCC0.2
0g、４−（ジメチルアミノ）ピリジン0.12g及び塩化メ
チレン30mlを仕込み、11時間室温で攪拌反応した。 In the reactor, (R) -4- (1-methylhexyl) oxy-2'-fluoro-4'-hydroxybiphenyl obtained in (a) 0.30 g, 4-octyloxybenzoic acid 0.25 g, DCC0.2
0 g, 4- (dimethylamino) pyridine 0.12 g and methylene chloride 30 ml were charged, and the reaction was carried out with stirring at room temperature for 11 hours.
反応液を過し、液を水洗し、芒硝で脱水後、溶媒を
留去し、残留分をシリカゲルカラムクロマトグラフイー
（溶離液ヘキサン／ベンゼン＝2/1）にて精製し、次い
でメタノール／アセトン混合溶媒で再結晶して（Ｒ）−
４−（１−メチルヘキシル）オキシ−２′−フルオロビ
フエニル−４′−イル４−オクチルオキシベンゾエー
ト0.40g（75.5％）を得た。Pass the reaction solution, wash the solution with water, dehydrate with sodium sulfate, evaporate the solvent, and purify the residue by silica gel column chromatography (eluent hexane / benzene = 2/1), then methanol / acetone. Recrystallize with mixed solvent (R)-
0.40 g (75.5%) of 4- (1-methylhexyl) oxy-2'-fluorobiphenyl-4'-yl 4-octyloxybenzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で534に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 534 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例41 実施例40（ｂ）における４−オクチルオキシ安息香酸0.
25gに替えて、４−ウンデシルオキシ安息香酸0.29gを用
い、他は実施例40（ｂ）と同様に操作して（Ｒ）−４−
（１−メチルヘキシル）オキシ−２′−フルオロビフエ
ニル−４′−イル４−ウンデシルオキシベンゾエート
0.35g（61.4％）を得た。Example 41 4-octyloxybenzoic acid in Example 40 (b)
In place of 25 g, 0.29 g of 4-undecyloxybenzoic acid was used, and otherwise the same as in Example 40 (b), the operation (R) -4-
(1-Methylhexyl) oxy-2'-fluorobiphenyl-4'-yl 4-undecyloxybenzoate
0.35 g (61.4%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で576に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 576 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例42 実施例40（ｂ）における４−オクチルオキシ安息香酸0.
25gに替えて、４−オクチル安息香酸0.23gを用い、他は
実施例40（ｂ）と同様に操作して（Ｒ）−４−（１−メ
チルヘキシル）オキシ−２′−フルオロビフエニル−
４′−イル４−オクチルベンゾエート0.23g（45.1
％）を得た。Example 42 4-octyloxybenzoic acid in Example 40 (b)
In place of 25 g, 0.23 g of 4-octylbenzoic acid was used, and the same operation as in Example 40 (b) was followed except that (R) -4- (1-methylhexyl) oxy-2′-fluorobiphenyl-
0.23 g of 4'-yl 4-octyl benzoate (45.1
%) Was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で518に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 518 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例43 実施例40（ｂ）における４−オクチルオキシ安息香酸0.
25gに替えて、４−デシル安息香酸0.29gを用い、他は実
施例40（ｂ）と同様に操作して、（Ｒ）−４−（１−メ
チルヘキシル）オキシ−２′−フルオロビフエニル−
４′−イル４−デシルベンゾエート0.39g（72.2％）
を得た。Example 43 4-octyloxybenzoic acid in Example 40 (b)
In place of 25 g, 0.29 g of 4-decylbenzoic acid was used, and otherwise the same operation as in Example 40 (b) was conducted to obtain (R) -4- (1-methylhexyl) oxy-2′-fluorobiphenyl. −
0.39 g of 4'-yl 4-decylbenzoate (72.2%)
Got
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で546に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was observed at 546 and the relation of the raw materials used, that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例44 実施例40（ｂ）における４−オクチルオキシ安息香酸0.
25gに替えて、実施例37（ｂ）で得られる３−フルオロ
−４−オクチル安息香酸0.31gを用い、他は実施例40
（ｂ）と同様に操作して、（Ｒ）−４−（１−メチルヘ
キシル）オキシ−２′−フルオロビフエニル−４′−イ
ル３−フルオロ−４−オクチルオキシベンゾエート0.
33g（60.0％）を得た。Example 44 4-octyloxybenzoic acid in Example 40 (b)
In place of 25 g, 0.31 g of 3-fluoro-4-octylbenzoic acid obtained in Example 37 (b) was used, and the other was used in Example 40.
Operating as in (b), (R) -4- (1-methylhexyl) oxy-2'-fluorobiphenyl-4'-yl 3-fluoro-4-octyloxybenzoate.
33 g (60.0%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で552に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 552 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例45 実施例40（ｂ）における４−オクチルオキシ安息香酸0.
25gに替えて、実施例38（ｂ）で得られる３−フルオロ
−４−デシルオキシ安息香酸0.3gを用い、他は実施例40
（ｂ）と同様に操作して、（Ｒ）−４−（１−メチルヘ
キシル）オキシ−２′−フルオロビフエニル−４′−イ
ル３−フルオロ−４−デシルオキシベンゾエート0.39
g（67.2％）を得た。Example 45 4-octyloxybenzoic acid in Example 40 (b)
In place of 25 g, 0.3 g of 3-fluoro-4-decyloxybenzoic acid obtained in Example 38 (b) was used, and in others, Example 40 was used.
Operating in the same manner as in (b), (R) -4- (1-methylhexyl) oxy-2'-fluorobiphenyl-4'-yl 3-fluoro-4-decyloxybenzoate 0.39
g (67.2%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例46 実施例40（ｂ）における４−オクチルオキシ安息香酸0.
25gに替えて、４−デカノイルオキシ安息香酸0.29gを用
い、他の実施例40（ｂ）と同様に操作して、（Ｒ）−４
−（１−メチルヘキシル）オキシ−２′−フルオロビフ
エニル−４′−イル４−デカノイルオキシベンゾエー
ト0.29g（50.9％）を得た。Example 46 4-octyloxybenzoic acid in Example 40 (b)
In place of 25 g, 0.29 g of 4-decanoyloxybenzoic acid was used and operated in the same manner as in Example 40 (b) to give (R) -4.
0.29 g (50.9%) of-(1-methylhexyl) oxy-2'-fluorobiphenyl-4'-yl 4-decanoyloxybenzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で576に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 576 in the ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例47 実施例１（ｃ）における（Ｓ）−４−メチルヘキシルブ
ロマイド8.0gに替え、デシルブロマイド4.7gを用い、他
は実施例１（ｃ）と同様に操作して、４−デシルオキシ
−２′−フルオロ−４′−ブロムビフエニル6.2g（81.4
％）を得た。Example 47 In place of 8.0 g of (S) -4-methylhexyl bromide in Example 1 (c), 4.7 g of decyl bromide was used, and otherwise the same operation as in Example 1 (c) was carried out, and 4-decyloxy-2'- Fluoro-4'-bromobiphenyl 6.2 g (81.4
%) Was obtained.
実施例33（ａ）における（Ｓ）−４−（４−メチルヘキ
シル）オキシ−２′−フルオロ−４′−ブロムビフエニ
ル14gに替えて（ａ）で得られた４−デシルオキシ−
２′−フルオロ−４′−ブロムビフエニル15.6gを用
い、他は実施例33（ａ）と同様に操作して４−デシルオ
キシ−２′−フルオロ−４′−ヒドロキシフエニル29.7
g（22.5％）を得た。 4-decyloxy-obtained in (a) in place of (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-bromobiphenyl 14 g in Example 33 (a).
2-decyloxy-2'-fluoro-4'-hydroxyphenyl 29.7 was prepared by the same procedure as in Example 33 (a) except that 15.6 g of 2'-fluoro-4'-bromobiphenyl was used.
g (22.5%) was obtained.
反応器に（ｂ）で得た４−デシルオキシ−２′−フルオ
ロ−４′−ヒドロキシビフエニル0.30g、（Ｒ）−４−
（１−メチルヘキシル）オキシ安息香酸0.22g、DCC0.21
g、４−（ジメチルアミノ）ピリジン0.10g及び塩化メチ
レン30mlを仕込み、11時間室温で攪拌反応した。 In the reactor, 0.30 g of 4-decyloxy-2'-fluoro-4'-hydroxybiphenyl obtained in (b), (R) -4-
(1-Methylhexyl) oxybenzoic acid 0.22 g, DCC0.21
Then, g, 4- (dimethylamino) pyridine (0.10 g) and methylene chloride (30 ml) were charged, and the mixture was reacted with stirring at room temperature for 11 hours.
反応液を過し、液を水洗し、芒硝で脱水後、溶媒を
留去し、残留分をシリカゲルカラムクロマトグラフイー
（溶離液ヘキサン／ベンゼン＝2/1）にて精製し、次い
でメタノール／アセトン混合溶媒で再結晶して（Ｒ）−
４−デシルオキシ−２′−フルオロビフエニル−４′−
イル４−（１−メチルヘキシル）オキシベンゾエート
0.39g（79.6％）を得た。Pass the reaction solution, wash the solution with water, dehydrate with sodium sulfate, evaporate the solvent, and purify the residue by silica gel column chromatography (eluent hexane / benzene = 2/1), then methanol / acetone. Recrystallize with mixed solvent (R)-
4-decyloxy-2'-fluorobiphenyl-4'-
Ile 4- (1-methylhexyl) oxybenzoate
0.39 g (79.6%) was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で562に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 562 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例48 実施例47（ｃ）における（Ｒ）−４−（１−メチルヘキ
シル）オキシ安息香酸0.22gに替えて、（Ｓ）−４−
（４−メチルヘキシル）オキシ安息香酸0.21gを用い、
他の実施例47（ｃ）と同様に操作して（Ｓ）−４−デシ
ルオキシ−２′−フルオロビフエニル−４′−イル４
−（４−メチルヘキシル）オキシベンゾエート0.29g（5
9.2％）を得た。Example 48 In place of 0.22 g of (R) -4- (1-methylhexyl) oxybenzoic acid in Example 47 (c), (S) -4-
Using (4-methylhexyl) oxybenzoic acid 0.21 g,
By operating in the same manner as in other Example 47 (c), (S) -4-decyloxy-2'-fluorobiphenyl-4'-yl 4
-(4-Methylhexyl) oxybenzoate 0.29 g (5
9.2%).
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で562に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質が目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 562 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例49 実施例１（ｄ）における（Ｓ）−４−（４−メチルヘキ
シル）オキシ−２′−フルオロ−４′−ブロムビフエニ
ル11.7gに替えて、実施例22（ａ）で得られる（Ｓ）−
４−（４−メチルヘキシル）オキシ−３−フルオロブロ
ムベンゼン8.50gを用い、他は実施例１（ｄ）と同様に
操作して、粗（Ｓ）−４−（４−メチルヘキシル）オキ
シ−３−フルオロベンゾニトリル5.2gを得た。Example 49 (S) -4- (4-methylhexyl) oxy-2'-fluoro-4'-bromobiphenyl 11.7 g in Example 1 (d) was replaced with (S) -obtained in Example 22 (a).
Crude (S) -4- (4-methylhexyl) oxy- was used by the same procedure as in Example 1 (d) except that 8.50 g of 4- (4-methylhexyl) oxy-3-fluorobromobenzene was used. 5.2 g of 3-fluorobenzonitrile was obtained.
実施例１（ｅ）における粗（Ｓ）−４−（４−メチルヘ
キシル）オキシ−２′−フルオロ−４′−シアノビフエ
ニル9.8gに替えて、（ａ）で得られた粗（Ｓ）−４−
（４−メチルヘキシル）オキシ−３−フルオロベンゾニ
トリル5.2gを用い、他は実施例１（ｅ）と同様に操作し
て（Ｓ）−４−（４−メチルヘキシル）オキシ−３−フ
ルオロ安息香酸4.9gを得た。 The crude (S) -4 obtained in (a) was replaced with 9.8 g of crude (S) -4- (4-methylhexyl) oxy-2′-fluoro-4′-cyanobiphenyl in Example 1 (e). −
5.2 g of (4-methylhexyl) oxy-3-fluorobenzonitrile was used, and the same procedure as in Example 1 (e) was repeated except that (S) -4- (4-methylhexyl) oxy-3-fluorobenzoic acid was used. 4.9 g of acid was obtained.
実施例47（ｃ）における（Ｒ）−４−（１−メチルヘキ
シル）オキシ安息香酸0.22gに替えて、（ｂ）で得られ
た（Ｓ）−４−（４−メチルヘキシル）オキシ−３−フ
ルオロ安息香酸0.28gを用い、他は実施例47（ｃ）と同
様に操作して（Ｓ）−４−デシルオキシ−２′−フルオ
ロビフエニル−４′−イル４−メチルヘキシル）オキ
シ−３−フルオロベンゾエート0.37g（73.3％）を得
た。 (R) -4- (1-Methylhexyl) oxybenzoic acid in Example 47 (c) was replaced with 0.22 g of (S) -4- (4-methylhexyl) oxy-3 obtained in (b). Using 0.28 g of -fluorobenzoic acid and otherwise operating the same as in Example 47 (c), (S) -4-decyloxy-2'-fluorobiphenyl-4'-yl 4-methylhexyl) oxy-3. -0.37 g (73.3%) of fluorobenzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質か目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例50 反応器に苛性ソーダ3.9g並びに水30mlを仕込み、氷冷攪
拌下に０℃にて臭素8gを滴下し、次亜臭素酸ソーダ水溶
液を調製した。別の容器に実施例21（ｂ）で得られる
（Ｒ）−３−フルオロ−４−（１−メチルヘキシル）オ
キシアセトフエノン1.19g並びに1,4−ジオキサン30mlを
仕込み、先に調製した次亜臭素酸ソーダ水溶液を室温に
て滴下し、50℃にて１時間加熱攪拌した。反応液を希塩
酸に注加し、次いで重亜硫酸ソーダにて処理後、ベンゼ
ンで抽出し、水洗し、芒硝で脱水後、溶媒を留去し、
（Ｒ）−３−フルオロ−４−（１−メチルヘキシル）オ
キシ安息香酸1.0gを得た。Example 50 The reactor was charged with 3.9 g of caustic soda and 30 ml of water, and 8 g of bromine was added dropwise at 0 ° C. under ice-cooling stirring to prepare an aqueous solution of sodium hypobromite. In a separate container, charged with (R) -3-fluoro-4- (1-methylhexyl) oxyacetophenone (1.19 g) obtained in Example 21 (b) and 1,4-dioxane (30 ml) were prepared as follows. An aqueous sodium bromate solution was added dropwise at room temperature, and the mixture was heated with stirring at 50 ° C. for 1 hour. The reaction solution was poured into dilute hydrochloric acid, then treated with sodium bisulfite, extracted with benzene, washed with water, dehydrated with sodium sulfate, and the solvent was distilled off.
1.0 g of (R) -3-fluoro-4- (1-methylhexyl) oxybenzoic acid was obtained.
実施例47（ｃ）における（Ｒ）−４−（１−メチルヘキ
シル）オキシ安息香酸0.22gに替えて、（ａ）で得られ
た（Ｒ）−４−（１−メチルヘキシル）オキシ−３−フ
ルオロ安息香酸0.39gを用い、他は実施例47（ｃ）と同
様に操作して（Ｒ）−４−デシルオキシ−２′−フルオ
ロビフエニル−４′−イル４−（１−メチルヘキシ
ル）オキシ−３−フルオロベンゾエート0.33g（66.0
％）を得た。 In place of 0.22 g of (R) -4- (1-methylhexyl) oxybenzoic acid in Example 47 (c), (R) -4- (1-methylhexyl) oxy-3 obtained in (a) was used. Using 0.39 g of -fluorobenzoic acid and otherwise operating as in Example 47 (c), (R) -4-decyloxy-2'-fluorobiphenyl-4'-yl 4- (1-methylhexyl). Oxy-3-fluorobenzoate 0.33 g (66.0
%) Was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で580に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質か目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
From the fact that a molecular ion peak was observed at 580 by ss analysis and the relation of the raw materials used, it was confirmed that the obtained substance was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例51 反応器に実施例23（ａ）で得られる（Ｒ）−３−ブロム
−４−（１−メチルヘプチル）オキシアセトフエノン6.
0g、シアン化第一銅2.46g並びにＮ−メチル−２−ピロ
リジノン30mlを仕込み、140〜150℃で28時間加熱攪拌し
た。反応液を塩化第二鉄8g、濃塩酸2ml及び水20mlから
なる水溶液にて処理し、クロロホルムで抽出し、水洗
し、芒硝で脱水後、溶媒を留去し、残留分をシリカゲル
クロマトグラフイー（溶離液ヘキサン／ベンゼン＝3/
1）で精製し、（Ｒ）−３−シアノ−４−（１−メチル
ヘプチル）オキシアセトフエノン1.28g（25.7％）を得
た。Example 51 (R) -3-Brom-4- (1-methylheptyl) oxyacetophenone obtained in Example 23 (a) in a reactor 6.
0 g, cuprous cyanide 2.46 g and N-methyl-2-pyrrolidinone 30 ml were charged, and the mixture was heated and stirred at 140 to 150 ° C. for 28 hours. The reaction solution was treated with an aqueous solution containing 8 g of ferric chloride, 2 ml of concentrated hydrochloric acid and 20 ml of water, extracted with chloroform, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was chromatographed on silica gel ( Eluent hexane / benzene = 3 /
Purification in 1) gave 1.28 g (25.7%) of (R) -3-cyano-4- (1-methylheptyl) oxyacetophenone.
反応器に苛性ソーダ4.4g並びに水30mlを仕込み、氷冷攪
拌下に０℃にて臭素5gを滴下し、次亜臭素酸ソーダ水溶
液を調製した。別の容器に（ａ）で得られた（Ｒ）−３
−シアノ−４−（１−メチルヘプチル）オキシアセトフ
エノン1.28g並びに1,4−ジオキサン20mlを仕込み、先に
調製した次亜臭素酸ソーダ水溶液を室温にて滴下し、40
℃にて１時間加熱攪拌した。 4.4 g of caustic soda and 30 ml of water were charged into the reactor, and 5 g of bromine was added dropwise at 0 ° C. under ice-cooling stirring to prepare an aqueous solution of sodium hypobromite. (R) -3 obtained in (a) in a separate container
-Cyano-4- (1-methylheptyl) oxyacetophenone (1.28 g) and 1,4-dioxane (20 ml) were charged, and the previously prepared aqueous solution of sodium hypobromite was added dropwise at room temperature.
The mixture was heated and stirred at 0 ° C for 1 hour.
反応液を希塩酸に注加し、次いで重亜硫酸ソーダにて処
理後、ベンゼンで抽出し、水洗し、芒硝で脱水後、溶媒
を留去し、残留分をヘキサンで再結晶して（Ｒ）−３−
シアノ−４−（１−メチルヘプチル）オキシ安息香酸0.
81g（62.8％）を得た。The reaction solution was poured into diluted hydrochloric acid, then treated with sodium bisulfite, extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was recrystallized with hexane (R)- 3-
Cyano-4- (1-methylheptyl) oxybenzoic acid 0.
81 g (62.8%) were obtained.
実施例47（ｃ）における（Ｒ）−４−（１−メチルヘキ
シル）オキシ安息香酸0.22gに替えて、（ｂ）で得られ
た（Ｒ）−３−シアノ−４−（１−メチルヘプチル）オ
キシ安息香酸0.24gを用い、他は実施例47（ｃ）と同様
に操作して（Ｒ）−４−デシルオキシ−２′−フルオロ
ビフエニル−４′−イル３−シアノ−４−（１−メチ
ルヘプチル）オキシベンゾエート0.21g（40.4％）を得
た。 In place of 0.22 g of (R) -4- (1-methylhexyl) oxybenzoic acid in Example 47 (c), (R) -3-cyano-4- (1-methylheptyl) obtained in (b) was used. ) Using 0.24 g of oxybenzoic acid and otherwise operating as in Example 47 (c), (R) -4-decyloxy-2'-fluorobiphenyl-4'-yl-3-cyano-4- (1 -0.21 g (40.4%) of methyl heptyl) oxybenzoate was obtained.
この物の純度はHPLCで99％以上であつた。またIR及びMa
ss分析で601に分子イオンピークが認められたこと、並
びに用いた原料の関係から、得られた物質か目的物であ
ることを確認した。The purity of this product was 99% or more by HPLC. Also IR and Ma
It was confirmed by ss analysis that a molecular ion peak was found at 601 and the relationship between the raw materials used and that the substance obtained was the target substance.
この物をメトラーホツトステージFP−82にはさみ、偏光
顕微鏡下で相変化を観察した。その結果を表−３に示
す。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results are shown in Table-3.
実施例52 表面にポリビニルアルコール（PVA）を塗布し、その表
面をラビングして平行配向処理を施した透明電極を備え
たセル厚３μｍの液晶セルを作製し、この液晶セルに実
施例14、41、45の化合物をそれぞれ封入し、等方性液体
から SmC＊相まで徐冷して液晶素子を作製した。この
液晶素子を２枚の偏光板に挾み、±25V、200Hzの矩形波
を印加し、透過光強度の変化から応答時間をそれぞれ求
めた。その結果を下に示す。Example 52 Polyvinyl alcohol (PVA) was applied to the surface, and the surface was rubbed to prepare a liquid crystal cell having a cell thickness of 3 μm, which was provided with a transparent electrode subjected to parallel alignment treatment. , 45 compounds were each encapsulated and slowly cooled from the isotropic liquid to the SmC * phase to prepare a liquid crystal device. This liquid crystal element was sandwiched between two polarizing plates, a rectangular wave of ± 25 V and 200 Hz was applied, and the response time was determined from the change in transmitted light intensity. The results are shown below.
実施例番号 応答時間（μsec） 測定温度
（℃） 14 260 35 41 240 75.6 45 225 60.2 実施例53 実施例13並びに実施例23で得られた化合物をそれぞれ下
記に示すピリミジン液晶組成物と重量比10:90の割合で
混合し、新たに液晶組成物を調製した。これら液晶組成
物の応答時間（τ）を実施例52に示した手順に従つて測
定した。その結果を下に示す。Example No. Response time (μsec) Measurement temperature (° C.) 14 260 35 41 240 75.6 45 225 60.2 Example 53 The compounds obtained in Example 13 and Example 23 were prepared in the following pyrimidine liquid crystal composition and weight ratio 10 respectively. The liquid crystal composition was newly prepared by mixing in a ratio of 90. The response time (τ) of these liquid crystal compositions was measured according to the procedure shown in Example 52. The results are shown below.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 255/57 Ｃ０９Ｋ 19/20 9279−4Ｈ 19/46 // Ｃ０７Ｃ 39/367 43/225 Ｃ 7419−4Ｈ 43/23 Ｅ 7419−4Ｈ 49/813 49/84 Ｄ 9049−4Ｈ 65/03 Ａ 9356−4Ｈ 65/24 69/88 255/54 255/56 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C07C 255/57 C09K 19/20 9279-4H 19/46 // C07C 39/367 43/225 C 7419 -4H 43/23 E 7419-4H 49/813 49/84 D 9049-4H 65/03 A 9356-4H 65/24 69/88 255/54 255/56
Claims (10)
アルキル基を表しＹはCOOまたはOCOを表し、Ｚは単結
合、Ｏ、COOまたはOCOを表し、X1及びX2はいずれか一方
がフツ素原子で他方が水素原子であることを表し、X3及
びX4はそれぞれ水素原子、フツ素原子、塩素原子または
シアノ基を表す）で表されるフツ素置換ビフエニル誘導
体化合物。1. A general formula, (R 1 and R 2 represent a linear or branched alkyl group having 1 to 18 carbon atoms, Y represents COO or OCO, Z represents a single bond, O, COO or OCO, X 1 and X 2 represents that one is a fluorine atom and the other is a hydrogen atom, and X 3 and X 4 are each a hydrogen atom, a fluorine atom, a chlorine atom or a cyano group) Biphenyl derivative compounds.
R2が不斉炭素原子を有するアルキル基である請求項１記
載の化合物。2. R 1 and / or R in the general formula (I)
The compound according to claim 1, wherein R 2 is an alkyl group having an asymmetric carbon atom.
X2がフツ素原子である請求項１又は２に記載の化合物。3. X 1 in the general formula (I) is a hydrogen atom.
The compound according to claim 1 or 2, wherein X 2 is a fluorine atom.
ある請求項２記載の化合物。4. The compound according to claim 2, wherein the compound is an optically active compound.
である請求項１記載の化合物。5. The compound according to claim 1, which is a compound having no optical activity.
アルキル基を表し、ＹはCOOまたはOCOを表し、Ｚは単結
合、Ｏ、COOまたはOCOを表し、X1及びX2はいずれか一方
がフツ素原子で他方が水素原子であることを表し、X3及
びX4はそれぞれ水素原子、フツ素原子、塩素原子または
シアノ基を表す）で表されるフツ素置換ビフエニル誘導
体化合物の少なくとも一種を含有することを特徴とする
液晶組成物。6. A general formula (R 1 and R 2 represent a linear or branched alkyl group having 1 to 18 carbon atoms, Y represents COO or OCO, Z represents a single bond, O, COO or OCO, X 1 And X 2 represents that one of them is a fluorine atom and the other is a hydrogen atom, and X 3 and X 4 are each a hydrogen atom, a fluorine atom, a chlorine atom or a cyano group) A liquid crystal composition comprising at least one kind of substituted biphenyl derivative compound.
けるR1及び（又は）R2が不斉炭素原子を有するアルキル
基である化合物を含有する請求項６記載の液晶組成物。7. The liquid crystal composition according to claim 6, wherein the compound includes a compound in which R 1 and / or R 2 in the general formula (I) is an alkyl group having an asymmetric carbon atom.
けるX1が水素原子でX2がフツ素原子である化合物を含有
する請求項６又は７に記載の液晶組成物。8. The liquid crystal composition according to claim 6, wherein the compound contains a compound in which X 1 in the general formula (I) is a hydrogen atom and X 2 is a fluorine atom.
する化合物である請求項７記載の液晶組成物。9. The liquid crystal composition according to claim 7, wherein the compound of the general formula (I) is a compound having optical activity.
有しない化合物である請求項６記載の液晶組成物。10. The liquid crystal composition according to claim 6, wherein the compound of the general formula (I) is a compound having no optical activity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63327755A JPH0776195B2 (en) | 1988-12-27 | 1988-12-27 | Fluorine-substituted biphenyl derivative and liquid crystal composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63327755A JPH0776195B2 (en) | 1988-12-27 | 1988-12-27 | Fluorine-substituted biphenyl derivative and liquid crystal composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02174747A JPH02174747A (en) | 1990-07-06 |
| JPH0776195B2 true JPH0776195B2 (en) | 1995-08-16 |
Family
ID=18202625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63327755A Expired - Lifetime JPH0776195B2 (en) | 1988-12-27 | 1988-12-27 | Fluorine-substituted biphenyl derivative and liquid crystal composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776195B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5545747A (en) * | 1990-08-16 | 1996-08-13 | Kanto Kagaku Kabushiki Kaisha | Cyclobutanecarboxylic acid derivatives and liquid crystalline compositions containing them |
| JP4963863B2 (en) * | 2006-04-27 | 2012-06-27 | 株式会社Ａｄｅｋａ | Novel compound and liquid crystal composition containing the compound |
| JP5687920B2 (en) * | 2010-03-03 | 2015-03-25 | 日本エイアンドエル株式会社 | Thermoplastic resin composition |
-
1988
- 1988-12-27 JP JP63327755A patent/JPH0776195B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02174747A (en) | 1990-07-06 |
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