JPH04234837A - Lactic acid derivative - Google Patents
Lactic acid derivativeInfo
- Publication number
- JPH04234837A JPH04234837A JP13169291A JP13169291A JPH04234837A JP H04234837 A JPH04234837 A JP H04234837A JP 13169291 A JP13169291 A JP 13169291A JP 13169291 A JP13169291 A JP 13169291A JP H04234837 A JPH04234837 A JP H04234837A
- Authority
- JP
- Japan
- Prior art keywords
- derivative
- liquid crystal
- added
- compound
- 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.)
- Granted
Links
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims description 14
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 8
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- -1 chalcone derivative, a bicyclohexane derivative Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 4
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical class C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 3
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical class C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 claims description 2
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical class C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003216 pyrazines Chemical class 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 150000003230 pyrimidines Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 43
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 abstract 2
- HWRPMRBDVWWCCF-UHFFFAOYSA-N (5-hexyl-2-phenyldiazenylphenyl) 2-butoxypropanoate Chemical compound C(CCCCC)C1=CC(=C(C=C1)N=NC1=CC=CC=C1)OC(C(C)OCCCC)=O HWRPMRBDVWWCCF-UHFFFAOYSA-N 0.000 abstract 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 abstract 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 abstract 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 235000021286 stilbenes Nutrition 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 58
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 229910001868 water Inorganic materials 0.000 description 34
- 239000000243 solution Substances 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 239000007832 Na2SO4 Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 150000004694 iodide salts Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 6
- LXSVWFRZICUOLU-UHFFFAOYSA-N 2-butoxypropanoic acid Chemical compound CCCCOC(C)C(O)=O LXSVWFRZICUOLU-UHFFFAOYSA-N 0.000 description 5
- PADLHDBOFPQDHI-UHFFFAOYSA-N 2-butoxypropanoyl chloride Chemical compound CCCCOC(C)C(Cl)=O PADLHDBOFPQDHI-UHFFFAOYSA-N 0.000 description 5
- RBADEBYNLRPXLQ-UHFFFAOYSA-N 4-[(4-hexoxyphenyl)diazenyl]phenol Chemical compound OC1=CC=C(C=C1)N=NC1=CC=C(C=C1)OCCCCCC RBADEBYNLRPXLQ-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229940116333 ethyl lactate Drugs 0.000 description 5
- IWZNLKUVIIFUOG-UHFFFAOYSA-N 2-chloro-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(Cl)=CC1=CC=CC=C1 IWZNLKUVIIFUOG-UHFFFAOYSA-N 0.000 description 4
- KVXWKCZRKDPJTB-UHFFFAOYSA-N 2-heptoxypropanoic acid Chemical compound CCCCCCCOC(C)C(O)=O KVXWKCZRKDPJTB-UHFFFAOYSA-N 0.000 description 4
- NTGHUAVUJPIMOC-UHFFFAOYSA-N 2-heptoxypropanoyl chloride Chemical compound CCCCCCCOC(C)C(Cl)=O NTGHUAVUJPIMOC-UHFFFAOYSA-N 0.000 description 4
- MWGLMIHIMAZKRY-UHFFFAOYSA-N 3-[4-(2-methylbutyl)phenyl]-4-(4-octylphenyl)benzoic acid Chemical compound C1=CC(CCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1C1=CC=C(CC(C)CC)C=C1 MWGLMIHIMAZKRY-UHFFFAOYSA-N 0.000 description 4
- GTRZPDPWJYIUOK-UHFFFAOYSA-N [4-[(4-hexoxyphenyl)diazenyl]phenyl] 3-butoxypropanoate Chemical compound C1=CC(OCCCCCC)=CC=C1N=NC1=CC=C(OC(=O)CCOCCCC)C=C1 GTRZPDPWJYIUOK-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- YUAUWEGVKKQBNY-UHFFFAOYSA-N n-hexoxyaniline Chemical compound CCCCCCONC1=CC=CC=C1 YUAUWEGVKKQBNY-UHFFFAOYSA-N 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SKIDNYUZJPMKFC-UHFFFAOYSA-N 1-iododecane Chemical compound CCCCCCCCCCI SKIDNYUZJPMKFC-UHFFFAOYSA-N 0.000 description 3
- KWYKRCFXFADWBK-UHFFFAOYSA-N 4-[(4-octylphenyl)diazenyl]phenol Chemical compound CCCCCCCCc1ccc(cc1)N=Nc1ccc(O)cc1 KWYKRCFXFADWBK-UHFFFAOYSA-N 0.000 description 3
- ORKQJTBYQZITLA-UHFFFAOYSA-N 4-octylaniline Chemical compound CCCCCCCCC1=CC=C(N)C=C1 ORKQJTBYQZITLA-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- DLFJETOVZQERCN-UHFFFAOYSA-N [4-[(4-hexoxyphenyl)diazenyl]phenyl] 3-heptoxypropanoate Chemical compound C1=CC(OC(=O)CCOCCCCCCC)=CC=C1N=NC1=CC=C(OCCCCCC)C=C1 DLFJETOVZQERCN-UHFFFAOYSA-N 0.000 description 3
- SYTSGMLYKFXQQP-UHFFFAOYSA-N [4-[(4-octylphenyl)diazenyl]phenyl] 3-heptoxypropanoate Chemical compound C1=CC(CCCCCCCC)=CC=C1N=NC1=CC=C(OC(=O)CCOCCCCCCC)C=C1 SYTSGMLYKFXQQP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- HMONIZCCNGYDDJ-UHFFFAOYSA-N ethyl 2-butoxypropanoate Chemical compound CCCCOC(C)C(=O)OCC HMONIZCCNGYDDJ-UHFFFAOYSA-N 0.000 description 3
- PXEPVAGEOGKOQY-UHFFFAOYSA-N ethyl 2-heptoxypropanoate Chemical compound CCCCCCCOC(C)C(=O)OCC PXEPVAGEOGKOQY-UHFFFAOYSA-N 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical group C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- LMHCYRULPLGEEZ-UHFFFAOYSA-N 1-iodoheptane Chemical compound CCCCCCCI LMHCYRULPLGEEZ-UHFFFAOYSA-N 0.000 description 2
- ZNJOCVLVYVOUGB-UHFFFAOYSA-N 1-iodooctadecane Chemical compound CCCCCCCCCCCCCCCCCCI ZNJOCVLVYVOUGB-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical group OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- XXUQUCMOXUDEIL-UHFFFAOYSA-N 4-[(4-heptylphenyl)diazenyl]phenol Chemical compound OC1=CC=C(C=C1)N=NC1=CC=C(C=C1)CCCCCCC XXUQUCMOXUDEIL-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BTVKCKPPLDCXBK-UHFFFAOYSA-N C(CCCCCCC)C1=CC=C(C=C1)N=NC1=CC=C(C=C1)O.[K] Chemical compound C(CCCCCCC)C1=CC=C(C=C1)N=NC1=CC=C(C=C1)O.[K] BTVKCKPPLDCXBK-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- YCHUYYQXVGWKSS-UHFFFAOYSA-N [4-(3-butoxypropanoyloxy)phenyl]-(4-hexoxyphenyl)imino-oxidoazanium Chemical compound C(CCCCC)OC1=CC=C(C=C1)N=[N+]([O-])C1=CC=C(C=C1)OC(CCOCCCC)=O YCHUYYQXVGWKSS-UHFFFAOYSA-N 0.000 description 2
- 150000003862 amino acid derivatives Chemical group 0.000 description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001841 cholesterols Chemical group 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- LIZTWFPKQKLMQT-UHFFFAOYSA-N ethyl 2-decoxypropanoate Chemical compound CCCCCCCCCCOC(C)C(=O)OCC LIZTWFPKQKLMQT-UHFFFAOYSA-N 0.000 description 2
- KCSRTDYOUZASCX-UHFFFAOYSA-N ethyl 2-dodecoxypropanoate Chemical compound CCCCCCCCCCCCOC(C)C(=O)OCC KCSRTDYOUZASCX-UHFFFAOYSA-N 0.000 description 2
- HLNIJAXCYZAJNK-UHFFFAOYSA-N ethyl 2-octadecoxypropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(C)C(=O)OCC HLNIJAXCYZAJNK-UHFFFAOYSA-N 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 150000003903 lactic acid esters Chemical class 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- VYPCMVCNMJQSKV-UHFFFAOYSA-N 1-heptyl-4-phenyldiazenylcyclohexa-2,4-dien-1-ol Chemical compound CCCCCCCC1(CC=C(C=C1)N=NC2=CC=CC=C2)O VYPCMVCNMJQSKV-UHFFFAOYSA-N 0.000 description 1
- BTUGGGLMQBJCBN-UHFFFAOYSA-N 1-iodo-2-methylpropane Chemical compound CC(C)CI BTUGGGLMQBJCBN-UHFFFAOYSA-N 0.000 description 1
- BUZZUHJODKQYTF-UHFFFAOYSA-N 1-iodo-3-methylbutane Chemical compound CC(C)CCI BUZZUHJODKQYTF-UHFFFAOYSA-N 0.000 description 1
- ZQUIJUNLTMQRAA-UHFFFAOYSA-N 1-iodo-3-methylcyclohexane Chemical compound CC1CCCC(I)C1 ZQUIJUNLTMQRAA-UHFFFAOYSA-N 0.000 description 1
- GCDPERPXPREHJF-UHFFFAOYSA-N 1-iodododecane Chemical compound CCCCCCCCCCCCI GCDPERPXPREHJF-UHFFFAOYSA-N 0.000 description 1
- SWGRLCBZNPROCQ-UHFFFAOYSA-N 1-iodoheptadecane Chemical compound CCCCCCCCCCCCCCCCCI SWGRLCBZNPROCQ-UHFFFAOYSA-N 0.000 description 1
- KMWHQYDMBYABKL-UHFFFAOYSA-N 1-iodohexadecane Chemical compound CCCCCCCCCCCCCCCCI KMWHQYDMBYABKL-UHFFFAOYSA-N 0.000 description 1
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 description 1
- UYBWORFIJZQKEP-UHFFFAOYSA-N 1-iodoicosane Chemical compound CCCCCCCCCCCCCCCCCCCCI UYBWORFIJZQKEP-UHFFFAOYSA-N 0.000 description 1
- LXFODWIENIOBLX-UHFFFAOYSA-N 1-iodononadecane Chemical compound CCCCCCCCCCCCCCCCCCCI LXFODWIENIOBLX-UHFFFAOYSA-N 0.000 description 1
- OGSJMFCWOUHXHN-UHFFFAOYSA-N 1-iodononane Chemical compound CCCCCCCCCI OGSJMFCWOUHXHN-UHFFFAOYSA-N 0.000 description 1
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 description 1
- HHXJMIXXUWDKIA-UHFFFAOYSA-N 1-iodopentadecane Chemical compound CCCCCCCCCCCCCCCI HHXJMIXXUWDKIA-UHFFFAOYSA-N 0.000 description 1
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 description 1
- FHQCFGPKNSSISL-UHFFFAOYSA-N 1-iodotetradecane Chemical compound CCCCCCCCCCCCCCI FHQCFGPKNSSISL-UHFFFAOYSA-N 0.000 description 1
- XGAMQNYEIPCUIZ-UHFFFAOYSA-N 1-iodotridecane Chemical compound CCCCCCCCCCCCCI XGAMQNYEIPCUIZ-UHFFFAOYSA-N 0.000 description 1
- FKUQOQPBCHJHAP-UHFFFAOYSA-N 1-iodoundecane Chemical compound CCCCCCCCCCCI FKUQOQPBCHJHAP-UHFFFAOYSA-N 0.000 description 1
- IQRUSQUYPCHEKN-UHFFFAOYSA-N 2-iodobutane Chemical compound CCC(C)I IQRUSQUYPCHEKN-UHFFFAOYSA-N 0.000 description 1
- HQZFWVYLQAPSHX-UHFFFAOYSA-N 3-iodocyclohexene Chemical compound IC1CCCC=C1 HQZFWVYLQAPSHX-UHFFFAOYSA-N 0.000 description 1
- OOJNHQQNTIEJDO-UHFFFAOYSA-N 4-(2-methylbutyl)benzoic acid Chemical compound CCC(C)CC1=CC=C(C(O)=O)C=C1 OOJNHQQNTIEJDO-UHFFFAOYSA-N 0.000 description 1
- YWILTCMUUXDNMA-UHFFFAOYSA-N 4-[(4-hexylphenyl)diazenyl]phenol Chemical compound CCCCCCc1ccc(cc1)N=Nc1ccc(O)cc1 YWILTCMUUXDNMA-UHFFFAOYSA-N 0.000 description 1
- BNEWZYZRLNNWNR-UHFFFAOYSA-N 4-heptylaniline Chemical compound CCCCCCCC1=CC=C(N)C=C1 BNEWZYZRLNNWNR-UHFFFAOYSA-N 0.000 description 1
- OVEMTTZEBOCJDV-UHFFFAOYSA-N 4-hexylaniline Chemical compound CCCCCCC1=CC=C(N)C=C1 OVEMTTZEBOCJDV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GFOAHCQVVPDRKF-UHFFFAOYSA-N C(CCCCC)OC1=CC=C(C=C1)N=[N+]([O-])C1=CC=C(C=C1)OC(CCOCCCCCCC)=O Chemical compound C(CCCCC)OC1=CC=C(C=C1)N=[N+]([O-])C1=CC=C(C=C1)OC(CCOCCCCCCC)=O GFOAHCQVVPDRKF-UHFFFAOYSA-N 0.000 description 1
- BOUKHIOVTCSXQI-UHFFFAOYSA-N C(CCCCCCC)C1=CC=C(C=C1)N=[N+]([O-])C1=CC=C(C=C1)OC(CCOCCCCCCC)=O Chemical compound C(CCCCCCC)C1=CC=C(C=C1)N=[N+]([O-])C1=CC=C(C=C1)OC(CCOCCCCCCC)=O BOUKHIOVTCSXQI-UHFFFAOYSA-N 0.000 description 1
- MOYCUFHKIBNXIC-UHFFFAOYSA-N CCCCCCC1(CC=C(C=C1)N=NC2=CC=CC=C2)O Chemical compound CCCCCCC1(CC=C(C=C1)N=NC2=CC=CC=C2)O MOYCUFHKIBNXIC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000582320 Homo sapiens Neurogenic differentiation factor 6 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 102100030589 Neurogenic differentiation factor 6 Human genes 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- GULPWNWOAWSWGS-UHFFFAOYSA-N [4-[(4-heptylphenyl)diazenyl]phenyl] 3-butoxypropanoate Chemical compound C1=CC(CCCCCCC)=CC=C1N=NC1=CC=C(OC(=O)CCOCCCC)C=C1 GULPWNWOAWSWGS-UHFFFAOYSA-N 0.000 description 1
- KUNFWFITKVJDGD-UHFFFAOYSA-N [4-[(4-hexylphenyl)diazenyl]phenyl] 3-butoxypropanoate Chemical compound C1=CC(CCCCCC)=CC=C1N=NC1=CC=C(OC(=O)CCOCCCC)C=C1 KUNFWFITKVJDGD-UHFFFAOYSA-N 0.000 description 1
- DBXALYWKOHHVLL-UHFFFAOYSA-N [4-[(4-octylphenyl)diazenyl]phenyl] 3-butoxypropanoate Chemical compound C1=CC(CCCCCCCC)=CC=C1N=NC1=CC=C(OC(=O)CCOCCCC)C=C1 DBXALYWKOHHVLL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000006480 iodobenzyl group Chemical group 0.000 description 1
- ZQCXCNPOYCQOEW-UHFFFAOYSA-N iodocycloheptane Chemical compound IC1CCCCCC1 ZQCXCNPOYCQOEW-UHFFFAOYSA-N 0.000 description 1
- FUCOMWZKWIEKRK-UHFFFAOYSA-N iodocyclohexane Chemical compound IC1CCCCC1 FUCOMWZKWIEKRK-UHFFFAOYSA-N 0.000 description 1
- LDKYPRVLJQWKBI-UHFFFAOYSA-N iodocyclooctane Chemical compound IC1CCCCCCC1 LDKYPRVLJQWKBI-UHFFFAOYSA-N 0.000 description 1
- PCEBAZIVZVIQEO-UHFFFAOYSA-N iodocyclopentane Chemical compound IC1CCCC1 PCEBAZIVZVIQEO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001572 propyl (E)-3-phenylprop-2-enoate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は分子構造の変更が容易な
乳酸誘導体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lactic acid derivatives whose molecular structure can be easily changed.
【０００２】0002
【従来の技術】光学活性を有することを特徴とする光学
素子としては、具体的には、
１）液晶状態においてコレステリック・ネマティック相
転移効果を利用するもの（Ｊ．Ｊ．Ｗｙｓｏｋｉ，Ａ．
Ａｄａｍｓ ａｎｄ Ｗ．Ｈａａｓ；Ｐｈｙｓ．Ｒ
ｅｖ．Ｌｅｔｔ．，２０，１０２４（１９６８））、２
）液晶状態においてホワイト・テイラー形ゲスト・ホス
ト効果を利用するもの（Ｄ．Ｌ．Ｗｈｉｔｅ ａｎｄ
Ｇ．Ｎ．Ｔａｙｌｏｒ；Ｊ．Ａｐｐｌ．Ｐｈｙｓ．
，４５，４７１８（１９７４））、
３）液晶状態においてカイラル・スメクチックＣ相，Ｈ
相，Ｆ相，Ｉ相，Ｇ相の強誘電性効果を利用するもの（
Ｎ．Ａ．Ｃｌａｒｋ ａｎｄ Ｓ．Ｔ．Ｌａｇｅｒ
ｗａｌｌ；Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，３６，８
９９（１９８０））、
４）液晶状態においてコレステリック相を持つものをマ
トリックス中へ固定することにより、その選択散乱特性
を利用し、ノッチフィルターやバンドパスフィルターと
して利用するもの（Ｆ．Ｊ．Ｋａｈｎ，Ａｐｐｌ．Ｐｈ
ｙｓ．Ｌｅｔｔ．，１８，２３１（１９７１））、円偏
光特性を利用した円偏光ビームスプリッターとして利用
するもの（Ｓ．Ｄ．Ｊａｃｏｂｓ，ＳＰＩＥ，３７，９
８（１９８１））等が知られている。個々の方式につい
ての詳細な説明は省略するが、表示素子・変調素子とし
て重要である。BACKGROUND OF THE INVENTION Optical elements characterized by optical activity include: 1) those that utilize the cholesteric-nematic phase transition effect in a liquid crystal state (J. J. Wysoki, A.;
Adams and W. Haas; Phys. R
ev. Lett. , 20, 1024 (1968)), 2
) that utilizes the White-Taylor type guest-host effect in the liquid crystal state (D.L. White and
G. N. Taylor; J. Appl. Phys.
, 45, 4718 (1974)), 3) Chiral smectic C phase, H
Those that utilize the ferroelectric effect of phase, F phase, I phase, and G phase (
N. A. Clark and S. T. Lager
wall; Appl. Phys. Lett. ,36,8
99 (1980)), 4) By fixing a substance having a cholesteric phase in a liquid crystal state in a matrix, its selective scattering properties are utilized to utilize it as a notch filter or a bandpass filter (F.J. Kahn, Appl.Ph
ys. Lett. , 18, 231 (1971)), and one used as a circularly polarized beam splitter using circular polarization characteristics (S.D. Jacobs, SPIE, 37, 9
8 (1981)) etc. are known. Although detailed explanations of individual methods will be omitted, they are important as display elements and modulation elements.
【０００３】従来、光学活性を有することを特徴とする
光学素子に必要な機能性材料を合成するための光学活性
中間体としては、２−メチルブタノール、２級オクチル
アルコール、２級ブチルアルコール、塩化ｐ−（２−メ
チルブチル）安息香酸、２級フェネチルアルコール、ア
ミノ酸誘導体、ショウノウ誘導体、コレステロール誘導
体等が知られている。[0003] Conventionally, optically active intermediates for synthesizing functional materials necessary for optical elements characterized by optical activity include 2-methylbutanol, secondary octyl alcohol, secondary butyl alcohol, and chloride. Known examples include p-(2-methylbutyl)benzoic acid, secondary phenethyl alcohol, amino acid derivatives, camphor derivatives, and cholesterol derivatives.
【０００４】しかし、これらは次のような欠点を有して
いる。光学活性な鎖状炭化水素誘導体は構造の変更が困
難で、しかも一部のものを除き非常に高価なものである
。アミノ酸誘導体は比較的安価な上に構造の変更も容易
であるがアミンの水素基が化学的に活性が強く、水素結
合や化学反応を生じやすいために機能性材料の特性を制
限してしまいやすい。ショウノウ誘導体・コレステロー
ル誘導体は構造の変更が困難なうえに立体的な障害によ
って機能性材料の特性に悪影響を与えやすい。However, these have the following drawbacks. It is difficult to change the structure of optically active chain hydrocarbon derivatives and, with the exception of some, they are very expensive. Amino acid derivatives are relatively inexpensive and their structures can be easily changed, but the hydrogen groups of amines are chemically active and easily cause hydrogen bonds and chemical reactions, which tends to limit the properties of functional materials. . It is difficult to change the structure of camphor derivatives and cholesterol derivatives, and they tend to adversely affect the properties of functional materials due to steric hindrance.
【０００５】上記のような欠点は、種々の材料を開発す
る上で大きな制約となっていた。[0005] The above-mentioned drawbacks have been a major constraint on the development of various materials.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記の点に
鑑みなされたものである。すなわち、本発明は、適度な
分子間力と形状をもった機能性材料中間体と光学活性を
損うことなく結合させることができ、分子設計を自由に
行うことができる化合物を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above points. That is, the present invention aims to provide a compound that can be bonded to a functional material intermediate having appropriate intermolecular force and shape without impairing optical activity, and allows for free molecular design. purpose.
【０００７】本発明はアルキル基の長さを変更すること
が容易で、このことによりＨ．Ａｒｎｏｌｄ，Ｚ．Ｐｈ
ｙｓ．Ｃｈｅｍ．，２２６，１４６（１９６４）に示さ
れるように液晶状態において発現する液晶相の種類や温
度範囲を制御することが可能な液晶性化合物及びそれを
少なくとも１種類配合成分として含有する液晶組成物を
提供することを目的とする。またＬＢ膜法により単分子
累積膜を作製する場合には容易に疎水基を制御すること
が出来、安定に成膜することが可能な化合物の提供を目
的とする。[0007] In the present invention, it is easy to change the length of the alkyl group, and this makes it possible to easily change the length of the alkyl group. Arnold, Z. Ph
ys. Chem. , 226, 146 (1964), provides a liquid crystal compound capable of controlling the type and temperature range of a liquid crystal phase developed in a liquid crystal state, and a liquid crystal composition containing at least one compound thereof as a compounded component. The purpose is to Another object of the present invention is to provide a compound whose hydrophobic groups can be easily controlled and which can be stably formed into a film when a monomolecular cumulative film is produced by the LB film method.
【０００８】[0008]
【課題を解決するための手段及び作用】本発明は、一般
式（Ｉ’）：[Means and effects for solving the problems] The present invention provides general formula (I'):
【０００９】[0009]
【化２】
［一般式（Ｉ’）中、Ｒは炭素数４〜２０の直鎖状飽和
炭化水素基を示す。Ｒ”はアゾベンゼン誘導体、アゾキ
シベンゼン誘導体、ビフェニル誘導体、ターフェニル誘
導体、フェニルシクロヘキサン誘導体、安息香酸誘導体
、ピリミジン誘導体、ピラジン誘導体、ピリジン誘導体
、スチルベン誘導トラン誘導体、カルコン誘導体、ビシ
クロヘキサン誘導体、あるいはケイ皮酸誘導体のいずれ
かの中から選ばれる残基。Ｃ＊は光学活性な不斉炭素原
子を示す。］で表される乳酸誘導体である。[In the general formula (I'), R represents a linear saturated hydrocarbon group having 4 to 20 carbon atoms. R” is an azobenzene derivative, an azoxybenzene derivative, a biphenyl derivative, a terphenyl derivative, a phenylcyclohexane derivative, a benzoic acid derivative, a pyrimidine derivative, a pyrazine derivative, a pyridine derivative, a stilbene derivative, a tolan derivative, a chalcone derivative, a bicyclohexane derivative, or a cinnamic derivative. A lactic acid derivative represented by a residue selected from any of acid derivatives.C* represents an optically active asymmetric carbon atom.
【００１０】この一般式（Ｉ’）で表わされる乳酸誘導
体は、Ｒ”に係る誘導体と下記一般式（Ｉ）で表わされ
る光学活性な乳酸誘導体との合成により得られる。[0010] The lactic acid derivative represented by the general formula (I') can be obtained by synthesis of the derivative related to R'' and the optically active lactic acid derivative represented by the following general formula (I).
【００１１】[0011]
【化３】
［一般式（Ｉ）中、Ｒは炭素数４〜２０の直鎖状飽和炭
化水素基を示す。embedded image [In general formula (I), R represents a linear saturated hydrocarbon group having 4 to 20 carbon atoms.
【００１２】Ｒ’はＯＨ基、ハロゲン原子、アルコキシ
基、フェノキシ基等の着脱可能な化学的に活性な置換基
を示す。］上記一般式中、Ｒは炭素数４〜２０の直鎖状
飽和炭化水素基である。炭素数３以下では末端基として
の特性が損われやすく、２１以上では最終的な機能材料
としたときの粘度やモル体積が増加するため好ましくな
い。また、好ましいＲの炭素数は６〜１６である。Ｒの
具体例としては直鎖状アルキル基、直鎖状アルケニル基
、直鎖状アルカディエニル基、直鎖状アルカトリエニル
基、直鎖状アルキニル基、アラルキル基がある。又、＊
は不斉炭素原子を示す。R' represents a removable chemically active substituent such as an OH group, a halogen atom, an alkoxy group, or a phenoxy group. ] In the above general formula, R is a linear saturated hydrocarbon group having 4 to 20 carbon atoms. If the number of carbon atoms is less than 3, the properties as a terminal group are likely to be impaired, and if it is more than 21 carbon atoms, the viscosity and molar volume of the final functional material will increase, which is not preferable. Moreover, the preferable carbon number of R is 6 to 16. Specific examples of R include a linear alkyl group, a linear alkenyl group, a linear alkadienyl group, a linear alkatrienyl group, a linear alkynyl group, and an aralkyl group. or,*
indicates an asymmetric carbon atom.
【００１３】Ｒ’はＯＨ基、ハロゲン原子、アルコキシ
基、フェノキシ基等の脱着可能な化学的に活性な置換基
を示す。すなわち、Ｒは、適当な反応条件下で、反応試
薬と反応して他の基によって容易に置き換えることがで
きる。この場合反応試薬を種々変化させることにより、
液晶性化合物その他の機能性化合物を得ることができる
。R' represents a removable chemically active substituent such as an OH group, a halogen atom, an alkoxy group, or a phenoxy group. That is, R can be easily replaced by another group by reacting with a reaction reagent under appropriate reaction conditions. In this case, by varying the reaction reagent,
Liquid crystalline compounds and other functional compounds can be obtained.
【００１４】次に、一般式（Ｉ）で示される光学活性な
乳酸誘導体のうち、Ｒ’が着脱可能な化学的に活性な置
換基である化合物の合成方法の例を示す。Next, an example of a method for synthesizing an optically active lactic acid derivative represented by the general formula (I), in which R' is a removable chemically active substituent, will be shown.
【００１５】[0015]
【化４】[C4]
【００１６】すなわち、Ｒ’がアルコキシ基である化合
物［上記式（ａ）の化合物］を合成するには、乳酸エス
テルと炭化水素ヨウ化物とをＡｇ２Ｏ存在下に反応させ
ることにより得られる。この場合、乳酸エステルと炭化
水素を容器に入れて混合しておき、この混合物中にＡｇ
２Ｏを添加する方法が好ましい。That is, the compound in which R' is an alkoxy group [the compound of formula (a) above] can be synthesized by reacting a lactic acid ester and a hydrocarbon iodide in the presence of Ag2O. In this case, lactic acid ester and hydrocarbon are mixed in a container, and Ag
A method of adding 2O is preferred.
【００１７】またＲ’がヒドロキシ基である化合物［上
記式（ｂ）の化合物］を合成するには、上記式（ａ）の
化合物を塩基で加水分解した後、酸で中和する方法がと
られる。[0017] In addition, in order to synthesize a compound in which R' is a hydroxy group [the compound of the above formula (b)], there is a method of hydrolyzing the compound of the above formula (a) with a base and then neutralizing it with an acid. It will be done.
【００１８】更に、Ｒ’がハロゲン原子の場合には、上
記式（ｂ）の化合物にＳＯＣｌ２，ＰＣｌ５の如きハロ
ゲン化剤を作用せしめる方法が採用される。Furthermore, when R' is a halogen atom, a method is employed in which the compound of formula (b) is treated with a halogenating agent such as SOCl2 or PCl5.
【００１９】上記反応式におけるＲＩは炭素数の広い範
囲にわたって選択することが可能であり、具体的にはヨ
ードブタン、ヨードペンタン、ヨードヘキサン、ヨード
ヘプタン、ヨードオクタン、ヨードノナン、ヨードデカ
ン、ヨードウンデカン、ヨードドデカン、ヨードトリデ
カン、ヨードテトラデカン、ヨードペンタデカン、ヨー
ドヘキサデカン、ヨードヘプタデカン、ヨードオクタデ
カン、ヨードノナデカン、ヨードエイコサン等の直鎖状
飽和炭化水素ヨウ化物；２−ヨードブタン、１−ヨード
−２−メチルプロパン、１−ヨード−３−メチルブタン
等の分岐状飽和炭化水素ヨウ化物；ヨードベンジル、ヨ
ードフェナシル、３−ヨード−１−シクロヘキセン等の
環状不飽和炭化水素ヨウ化物；ヨードシクロペンタン、
ヨードシクロヘキサン、１−ヨード−３−メチルシクロ
ヘキサン、ヨードシクロヘプタン、ヨードシクロオクタ
ン等の環状飽和炭化水素ヨウ化物がある。RI in the above reaction formula can be selected from a wide range of carbon numbers, and specifically includes iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, iodoundecane, and iododecane. , iodotridecane, iodotetradecane, iodopentadecane, iodohexadecane, iodoheptadecane, iodooctadecane, iodononadecane, iodoeicosane, and other linear saturated hydrocarbon iodides; 2-iodobutane, 1-iodo-2-methylpropane, Branched saturated hydrocarbon iodides such as 1-iodo-3-methylbutane; cyclic unsaturated hydrocarbon iodides such as iodobenzyl, iodophenacil, and 3-iodo-1-cyclohexene; iodocyclopentane,
There are cyclic saturated hydrocarbon iodides such as iodocyclohexane, 1-iodo-3-methylcyclohexane, iodocycloheptane, and iodocyclooctane.
【００２０】以上のようなヨウ化物から自由に選択する
ことにより光学活性な乳酸誘導体を得ることができる。
表１に直鎖状飽和炭化水素ヨウ化物より得られた光学活
性な乳酸誘導体の例を示す。Optically active lactic acid derivatives can be obtained by freely selecting from the above iodides. Table 1 shows examples of optically active lactic acid derivatives obtained from linear saturated hydrocarbon iodides.
【００２１】[0021]
【表１】[Table 1]
【００２２】このような方法により得られた種々の乳酸
誘導体より次に示す合成経路によって下記一般式（ＩＩ
）又は（ＩＩＩ）に示される液晶性化合物を得た。From the various lactic acid derivatives obtained by such methods, the following general formula (II
) or (III) was obtained.
【００２３】[0023]
【化５】
［但し、上記一般式（ＩＩ），（ＩＩＩ）において、Ｒ
は炭素数４〜２０の直鎖状、分岐状または環状の飽和も
しくは不飽和の炭化水素基を示し、Ｒ’’’は炭素数４
〜２０のアルキル基またはアルコキシ基を示す。］本発
明によれば、アゾベンゼン基、アゾキシベンゼン基の側
鎖の長さ、分子量、形状を自由に変更した光学活性な液
晶性化合物を得ることが可能となり、目的の化合物の物
性値を制御することができる。従来は不斉炭素から離れ
た側鎖を変更することのみ可能であったが本発明により
、両末端基を変更することが可能となった。このことは
液晶やＬＢ膜を機能素子として使用する上で非常に重要
な問題であり、目的に応じた分子設計に道を開くもので
ある。[However, in the above general formulas (II) and (III), R
represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 to 20 carbon atoms;
~20 alkyl or alkoxy groups. ] According to the present invention, it is possible to obtain an optically active liquid crystal compound in which the length, molecular weight, and shape of the side chain of an azobenzene group or azoxybenzene group can be freely changed, and the physical property values of the target compound can be controlled. can do. Conventionally, it was only possible to change the side chain away from the asymmetric carbon, but the present invention has made it possible to change both end groups. This is a very important problem when using liquid crystals or LB films as functional elements, and opens the way to molecular design according to purposes.
【００２４】また本発明の乳酸誘導体は不斉炭素原子と
永久双極子モーメントをもつカルボニル基が非常に接近
しているため、スメクチック液晶における強誘電性の自
発分極の増加に有効である。Furthermore, in the lactic acid derivative of the present invention, since the asymmetric carbon atom and the carbonyl group having a permanent dipole moment are very close to each other, it is effective in increasing the ferroelectric spontaneous polarization in smectic liquid crystals.
【００２５】本発明によって得られる液晶組成物は、上
記一般式（ＩＩ）の化合物または一般式（ＩＩＩ）の化
合物を少なくとも１種類配合成分として含有する。この
組成物のうち、一般式（ＩＩ），（ＩＩＩ）で示される
化合物の少なくとも１種と強誘電性液晶化合物とを含有
する組成物は、自発分極の増大等強誘電性液晶の性質の
改良という観点から本発明における殊に好ましい態様を
なすものである。この液晶組成物において使用される強
誘電性液晶化合物の具体例を以下に掲げる。The liquid crystal composition obtained by the present invention contains at least one compound of the above general formula (II) or general formula (III) as a compounding component. Among these compositions, the composition containing at least one of the compounds represented by the general formulas (II) and (III) and a ferroelectric liquid crystal compound improves the properties of the ferroelectric liquid crystal, such as increasing spontaneous polarization. From this point of view, this is a particularly preferred embodiment of the present invention. Specific examples of the ferroelectric liquid crystal compound used in this liquid crystal composition are listed below.
【００２６】Ａ．Ｓｃｈｉｆｆ塩基型強誘電性液晶化合
物：
（１）ＤＯＢＡＭＢＣ（ｐ−デシルオキシベンジリデン
ｐ’−アミノ−２−メチルブチルシンナメート）（この
系統でｐ−ヘキシルオキシ乃至ｐ−デシルオキシの炭素
原子数のアルコキシ基を有する化合物は強誘電性があり
、本発明の組成物に使用できる。）
（２）ＤＯＢＡＭＢＣＣ（ｐ−デシルオキシベンジリデ
ンｐ’−アミノ−２−メチルブチル−α−シアノシンナ
メート）（この系統でｐ−デシルオキシ基がｐ−テトラ
ジシルオキシ基で置き換わった化合物も強誘電性がある
。）
（３）ＯＯＢＡＭＢＣＣ（ｐ−オクチルオキシベンジリ
デン ｐ’−アミノ−２−アミノメチルブチル−α−
クロロシンナメート）
（４）ＨＯＢＡＣＰＣ（ｐ−ヘキシルオキシベンジリデ
ンｐ’−アミノ−２−クロロ−α−プロピルシンナメー
ト）（この系統でｐ−ヘキシルオキシ乃至ｐ−ドデシル
オキシの炭素原子数のアルコキシ基を有する化合物は強
誘電性がある。）
（５）ＯＯＢＡＭＢＭＣ（ｐ−オクチルオキシベンジリ
デンｐ’−アミノ−２−メチルブチル−α−メチルシン
ナメート）
（６）ＤＯＢＭＢＡ［ｐ−デシルオキシベンジリデンｐ
’−（２−メチルブチルオキシカルボニル）アニリン］
（この系統でｐ−ヘプチルオキシ乃至ｐ−テトラデシル
オキシの炭素原子数のアルコキシ基を有する化合物は強
誘電性がある。）
（７）ＭＢＲＡ ｎ＝８［Ｓ−４−ｏ−（２−メチル
）ブチルレゾルシリデン−４’−アルキルアニリン］A. Schiff base-type ferroelectric liquid crystal compound: (1) DOBAMBC (p-decyloxybenzylidene p'-amino-2-methylbutylcinnamate) (in this series, an alkoxy group having the number of carbon atoms from p-hexyloxy to p-decyloxy) (2) DOBAMBCC (p-decyloxybenzylidene p'-amino-2-methylbutyl-α-cyanocinnamate) (in this series, the compound has ferroelectricity and can be used in the composition of the present invention). Compounds in which the -decyloxy group is replaced with a p-tetradisyloxy group are also ferroelectric.) (3) OOBAMBCC (p-octyloxybenzylidene p'-amino-2-aminomethylbutyl-α-
(chlorocinnamate) (4) HOBACPC (p-hexyloxybenzylidene p'-amino-2-chloro-α-propyl cinnamate) (in this system, an alkoxy group having the number of carbon atoms from p-hexyloxy to p-dodecyloxy) (5) OOBAMBMC (p-octyloxybenzylidene p'-amino-2-methylbutyl-α-methylcinnamate) (6) DOBMBA [p-decyloxybenzylidene p'-amino-2-methylbutyl-α-methylcinnamate]
'-(2-methylbutyloxycarbonyl)aniline]
(In this series, compounds having an alkoxy group with the number of carbon atoms from p-heptyloxy to p-tetradecyloxy are ferroelectric.) (7) MBRA n=8[S-4-o-(2-methyl ) Butyl resol cylidene-4'-alkylaniline]
【
００２７】[
0027
【化６】 分子式：Ｃ２６Ｈ３３Ｏ２Ｎ 分子量：３９１．５５ 転移温度（℃）：[C6] Molecular formula: C26H33O2N Molecular weight: 391.55 Transition temperature (℃):
【００２８】[0028]
【数１】
（８）ＭＯＲＡ ８［Ｓ−４−ｏ−（６−メチル）オ
クチルレゾルシリデン−４’−オクチルアニリン］[Math. 1] (8) MORA 8 [S-4-o-(6-methyl)octylresolcylidene-4'-octylaniline]
【０
０２９】0
029]
【化７】 分子式：Ｃ３０Ｈ４５Ｏ２Ｎ 転移温度（℃）：[C7] Molecular formula: C30H45O2N Transition temperature (℃):
【００３０】[0030]
【数２】[Math 2]
【００３１】Ｂ．エステル型強誘電性液晶化合物：（１
）４−ｎ−ヘキシルオキシフェニル−４−（２”−メチ
ルブチル）ビフェニル−４’−カルボキシレート（２）
４−（２’−メチルブチル）フェニル−４’−オクチル
ビフェニル−４−カルボキシレート（３）４−（２’−
メチルブチルオキシ）フェニル４’−ドデシルオキシフ
ェニル４−カルボキシレート（上記の２’−メチルブチ
ルオキシ基が４’−ノニルオキシ基で置き換わった化合
物も強誘電性を示す。）B. Ester type ferroelectric liquid crystal compound: (1
) 4-n-hexyloxyphenyl-4-(2''-methylbutyl)biphenyl-4'-carboxylate (2)
4-(2'-methylbutyl)phenyl-4'-octylbiphenyl-4-carboxylate (3) 4-(2'-
Methylbutyloxy) phenyl 4'-dodecyloxyphenyl 4-carboxylate (Compounds in which the above 2'-methylbutyloxy group is replaced with a 4'-nonyloxy group also exhibit ferroelectricity.)
【００３２】Ｃ．アゾキシ型強
誘電性液晶化合物：（１）ＰＡＣＭＢ（ｐ−アゾキシシ
ンナメートメチル２ブタノール）強誘電性液晶と一般式
（ＩＩ）または（ＩＩＩ）の化合物とを含有する組成物
においては、強誘電性液晶化合物１００重量部に対し、
一般式（ＩＩ）で示される化合物または一般式（ＩＩＩ
）で示される化合物０．０１〜１００重量部が配合され
る。０．０１重量部未満では強誘電性液晶の改良効果（
例えば、強誘電性液晶性を示す温度域を変化させたり、
動作寿命を延長させたりする）が発現せず、１００重量
部を超える場合は強誘電性液晶が希釈されるため強誘電
性液晶としての特性が低下する。C. Azoxy-type ferroelectric liquid crystal compound: (1) In a composition containing a PACMB (p-azoxycinnamate methyl 2-butanol) ferroelectric liquid crystal and a compound of general formula (II) or (III), a ferroelectric For 100 parts by weight of liquid crystal compound,
A compound represented by the general formula (II) or a compound represented by the general formula (III)
0.01 to 100 parts by weight of the compound represented by ) is blended. If it is less than 0.01 part by weight, the improvement effect of ferroelectric liquid crystal (
For example, by changing the temperature range that exhibits ferroelectric liquid crystallinity,
If the amount exceeds 100 parts by weight, the ferroelectric liquid crystal will be diluted and its properties as a ferroelectric liquid crystal will deteriorate.
【００３３】[0033]
【実施例】以下、実施例により本発明の化合物の製造法
について更に詳細に説明する。EXAMPLES The method for producing the compounds of the present invention will be explained in more detail with reference to Examples below.
【００３４】なお、以下の実施例において、相転移温度
は、ＤＳＣ（セイコー電子ＳＳＣ５８０ＤＳ）により測
定を行い、温度制御した銅ブロック中へガラス板に封入
した液晶を挿入し、偏光顕微鏡で観察することで観察し
た。In the following examples, the phase transition temperature was measured by DSC (Seiko Electronics SSC580DS), and a liquid crystal sealed in a glass plate was inserted into a temperature-controlled copper block and observed with a polarizing microscope. I observed it.
【００３５】参考例１［（−）−エチル−２−ブトキシ
プロピオネート］
Ｌ−（＋）−乳酸エチル３１．５ｇと１−ヨードブタン
１０７．３ｇを四ツ口フラスコへ混合し、新しく合成し
たＡｇ２Ｏを２時間で加える。室温にて１５時間放置後
２００ｍｌのエーテルにて希釈し、濾過したのちエーテ
ルを留去する。残分を５％ＫＯＨ水溶液１００ｍｌにて
洗浄後、無水Ｎａ２ＳＯ４にて乾燥して減圧蒸留、１１
０℃／５４ｍｍＨｇの留分を集めると２３ｇの（−）−
エチル−２−ブトキシプロピオネートが得られる。施光
度［α］Ｄ２４°＝−７３°，ＩＲ：１７５０，１１４
０ｃｍ−１。Reference Example 1 [(-)-Ethyl-2-butoxypropionate] 31.5 g of L-(+)-ethyl lactate and 107.3 g of 1-iodobutane were mixed in a four-necked flask to newly synthesize. Add Ag2O in 2 hours. After standing at room temperature for 15 hours, the mixture was diluted with 200 ml of ether, filtered, and the ether was distilled off. The residue was washed with 100 ml of 5% KOH aqueous solution, dried over anhydrous Na2SO4, and distilled under reduced pressure.
When the fraction at 0℃/54mmHg is collected, 23g of (-)-
Ethyl-2-butoxypropionate is obtained. Light intensity [α] D24°=-73°, IR: 1750, 114
0cm-1.
【００３６】参考例２［（−）−エチル−２−ヘプチル
オキシプロピオネート］
Ｌ−（＋）−乳酸エチル６４．７ｇと１−ヨードヘプタ
ン９５．２ｇを混合し、新しく合成したＡｇ２Ｏを１時
間で加える。室温にて７２時間放置後４００ｍｌのエー
テルにて希釈し、濾過後、エーテルを留去する。５％Ｋ
ＯＨ水溶液２００ｍｌにて洗浄後、無水Ｎａ２ＳＯ４に
て乾燥して減圧蒸留する。１２２℃／１２ｍｍＨｇの留
分を集めると３０ｇの（−）−エチル−２−ヘプチルオ
キシプロピオネートが得られる。旋光度［α］Ｄ２５°
＝−５１°，ＩＲ：１７５０，１１３０ｃｍ−１。Reference Example 2 [(-)-Ethyl-2-heptyloxypropionate] 64.7 g of L-(+)-ethyl lactate and 95.2 g of 1-iodoheptane were mixed, and the newly synthesized Ag2O was mixed with 1 Add in time. After standing at room temperature for 72 hours, the mixture was diluted with 400 ml of ether, filtered, and the ether was distilled off. 5%K
After washing with 200 ml of OH aqueous solution, drying with anhydrous Na2SO4 and distillation under reduced pressure. Collecting the 122° C./12 mmHg fraction yields 30 g of (-)-ethyl-2-heptyloxypropionate. Optical rotation [α] D25°
=-51°, IR: 1750, 1130 cm-1.
【００３７】参考例３［（−）−エチル−２−ドデシル
オキシプロピオネート］
Ｌ−（＋）−乳酸エチル４７．０ｇと１−ヨードドデカ
ン８８．４ｇをフラスコへ加えＮ２気流下混合する。新
しく合成したＡｇ２Ｏ ４２．１ｇを３時間で加える
。
室温にて５０時間放置後、ｗａｔｅｒｂａｔｈにて６０
〜７０℃に４時間加熱する。エーテル２００ｍｌにて希
釈して濾過後エーテルを留去する。５％ＫＯＨ水溶液１
００ｍｌにて洗浄後、無水Ｎａ２ＳＯ４にて乾燥して減
圧蒸留、１６９℃／９ｍｍＨｇの留分を集めると２２ｇ
の（−）−エチル−２−ドデシルオキシプロピオネート
が得られる。旋光度［α］Ｄ２３°＝−４２°，ＩＲ：
２９２０，１７５０，１１５０ｃｍ−１。Reference Example 3 [(-)-Ethyl-2-dodecyloxypropionate] 47.0 g of L-(+)-ethyl lactate and 88.4 g of 1-iodododecane were added to a flask and mixed under a stream of N2. Add 42.1 g of freshly synthesized Ag2O in 3 hours. After being left at room temperature for 50 hours, it was placed in a water bath for 60 hours.
Heat to ~70°C for 4 hours. Dilute with 200 ml of ether, filter, and then distill off the ether. 5% KOH aqueous solution 1
After washing with 00ml, drying with anhydrous Na2SO4, distillation under reduced pressure, and collecting the fraction at 169℃/9mmHg, 22g
(-)-ethyl-2-dodecyloxypropionate is obtained. Optical rotation [α] D23°=-42°, IR:
2920, 1750, 1150 cm-1.
【００３８】
参考例４［（−）−２−ブトキシプロピオン酸］参考例
１の方法により合成した（−）−エチル−２−ブトキシ
−プロピオネート１５．５ｇを５ＭのＮａＯＨ水溶液４
０ｍｌへ滴下し室温にて４時間攪拌する。次にＨ２ＳＯ
４２０ｇを加え、酸性として、エーテルで抽出する。エ
ーテルを留去し無水Ｎａ２ＳＯ４にて乾燥する。旋光度
［α］Ｄ２５°＝−７４°。ＩＲスペクトル（ＫＢｒデ
ィスク法）を図１に示す。なお、特徴的な吸収ピークは
３１００，２９６０，２６５０，２５５０，１７２０，
１１３０ｃｍ−１であった。Reference Example 4 [(-)-2-Butoxypropionic acid] 15.5 g of (-)-ethyl-2-butoxy-propionate synthesized by the method of Reference Example 1 was added to 5M NaOH aqueous solution 4
Add dropwise to 0 ml and stir at room temperature for 4 hours. Next, H2SO
Add 420 g, acidify and extract with ether. The ether was distilled off and the mixture was dried over anhydrous Na2SO4. Optical rotation [α] D25° = -74°. The IR spectrum (KBr disk method) is shown in FIG. Note that the characteristic absorption peaks are 3100, 2960, 2650, 2550, 1720,
It was 1130 cm-1.
【００３９】
参考例５［（−）−２−ヘプチルオキシプロピオン酸］
参考例２の方法により合成した（−）−エチル−２−ヘ
プチルオキシプロピオネート１５．１ｇを３．８ＭのＮ
ａＯＨ水溶液４０ｍｌへ滴下して室温にて１０時間攪拌
する。濃硫酸７．５ｇを加え攪拌する。エーテルにて抽
出し無水Ｎａ２ＳＯ４にて乾燥し、エーテルを留去する
。
施光度［α］Ｄ２４°＝−６１°，ＩＲ：２９４０，１
７３０，１１３０ｃｍ−１。Reference Example 5 [(-)-2-heptyloxypropionic acid]
15.1 g of (-)-ethyl-2-heptyloxypropionate synthesized by the method of Reference Example 2 was mixed with 3.8 M N
The mixture was added dropwise to 40 ml of aOH aqueous solution and stirred at room temperature for 10 hours. Add 7.5 g of concentrated sulfuric acid and stir. Extract with ether, dry over anhydrous Na2SO4, and distill off the ether. Light intensity [α]D24°=-61°, IR:2940,1
730,1130 cm-1.
【００４０】参考例６［（−）−エチル−２−オクタデ
シルオキシプロピオネート］
Ｌ−（＋）−乳酸エチル６０．５ｇと１−ヨードオクタ
デカン９５．４ｇを混合し、新しく合成したＡｇ２Ｏ
７１．７ｇを約３０分間で加える。攪拌しつつ４０〜
５０℃に８時間保ち、さらに６０〜７０℃に１４時間保
ち、室温にて約１００時間放置したのち約３００ｍｌの
エーテルにて希釈し、濾過後エーテルを留去する。５％
ＫＯＨ水溶液約１００ｍｌにて洗浄後、無水Ｎａ２ＳＯ
４にて乾燥する。ヘキサンにて再結晶し精製して２０．
５ｇの（−）−エチル−２−オクタデシルオキシプロピ
オネートが得られる。旋光度［α］Ｄ２５°＝−３２°
，ＩＲ：２９３０，２８５０，１７５５，１１４０ｃｍ
−１。Reference Example 6 [(-)-Ethyl-2-octadecyloxypropionate] 60.5 g of L-(+)-ethyl lactate and 95.4 g of 1-iodooctadecane were mixed to produce newly synthesized Ag2O.
Add 71.7 g over approximately 30 minutes. 40~ while stirring
The mixture was kept at 50°C for 8 hours, further kept at 60-70°C for 14 hours, left at room temperature for about 100 hours, diluted with about 300ml of ether, filtered, and the ether was distilled off. 5%
After washing with about 100 ml of KOH aqueous solution, anhydrous NaSO
Dry at step 4. Recrystallize with hexane and purify 20.
5 g of (-)-ethyl-2-octadecyloxypropionate are obtained. Optical rotation [α] D25° = -32°
,IR:2930,2850,1755,1140cm
-1.
【００４１】参考例７［（−）−エチル−２−デシルオ
キシプロピオネート］
Ｌ−（＋）−乳酸エチル４７．４ｇと１−ヨードデカン
９３．９ｇを混合し、新しく合成したＡｇ２Ｏ ６０
．１ｇを約１時間３０分で加える。攪拌しつつ４０〜５
０℃へ１時間保ち、室温にて２４時間放置したのち約３
００ｍｌのエーテルにて希釈し、濾過後エーテルを留去
する。５％ＫＯＨ水溶液約１００ｍｌにて洗浄後、無水
Ｎａ２ＳＯ４にて乾燥して減圧蒸留する。１４１〜１４
６℃／５ｍｍＨｇの留分を集めると１３．６ｇの（−）
−エチル−２−デシルオキシプロピオネートが得られる
。旋光度［α］Ｄ２３°＝−４８°。ＩＲ：２９２０，
２８５０，１７５０，１１５０ｃｍ−１。Reference Example 7 [(-)-Ethyl-2-decyloxypropionate] Ag2O 60 was newly synthesized by mixing 47.4 g of L-(+)-ethyl lactate and 93.9 g of 1-iododecane.
．． Add 1 g in about 1 hour and 30 minutes. 40-5 while stirring
After keeping it at 0℃ for 1 hour and leaving it at room temperature for 24 hours, about 3
Dilute with 00 ml of ether, filter and distill off the ether. After washing with about 100 ml of 5% KOH aqueous solution, drying with anhydrous Na2SO4 and distillation under reduced pressure. 141-14
When the fraction at 6℃/5mmHg is collected, 13.6g (-)
-Ethyl-2-decyloxypropionate is obtained. Optical rotation [α] D23° = -48°. IR:2920,
2850, 1750, 1150 cm-1.
【００４２】実施例１［４’−ヘキシル４−α−ブトキ
シプロパノイルオキシアゾベンゼン］
４−ヘキシルアニリン３０．１ｇ（０．１７Ｍ）を０℃
以下に冷却し１０％塩酸水溶液８５ｇを加え、次に亜硝
酸ナトリウム１１．６ｇを６８ｇの水に溶解したものを
加えた。滴下中は０℃以上とならないように冷却した。
滴下終了後３０分間反応させたものを滴下ロートへ移し
、フェノール１６ｇを含む８％ＮａＯＨ水溶液１７０ｇ
へ滴下した。滴下中は５℃以下に保った。滴下終了後０
．５時間攪拌を続け、その後ｐＨ５〜６となるまで１０
％塩酸水溶液を加え、反応物を析出させた。析出物を濾
別し水にて洗浄後、減圧乾燥を１夜行った。乾燥後石油
エーテル５００ｍｌで洗浄し、さらに減圧乾燥して２９
．６ｇ（０．１０Ｍ）の４−ハイドロキシ−４’−ヘキ
シルアゾベンゼンを得た。収率は５９％であった。Example 1 [4'-hexyl 4-α-butoxypropanoyloxyazobenzene] 30.1 g (0.17 M) of 4-hexylaniline was heated to 0°C.
After cooling, 85 g of a 10% aqueous hydrochloric acid solution was added, and then 11.6 g of sodium nitrite dissolved in 68 g of water was added. During the dropping, the solution was cooled so that the temperature did not exceed 0°C. After the dropwise addition was completed, the mixture was reacted for 30 minutes and transferred to a dropping funnel, and 170g of an 8% NaOH aqueous solution containing 16g of phenol was added.
dripped into. The temperature was kept below 5° C. during the dropping. 0 after completion of dripping
．． Continue stirring for 5 hours, then continue stirring for 10 hours until the pH reaches 5-6.
% aqueous hydrochloric acid solution was added to precipitate the reaction product. The precipitate was filtered off, washed with water, and then dried under reduced pressure overnight. After drying, wash with 500 ml of petroleum ether and further dry under reduced pressure to obtain 29
．． 6g (0.10M) of 4-hydroxy-4'-hexylazobenzene was obtained. The yield was 59%.
【００４３】（−）−２−ブトキシプロピオン酸２．４
ｇをフラスコへ加え次に塩化チオニル２．５ｇを徐々に
加え３０分間反応後塩化チオニルを留去する。得られた
２−ブトキシプロピオン酸クロライドを４−ハイドロキ
シ−４−ヘキシルアゾベンゼン３．０ｇを乾燥ピリジン
２０ｍｌとともに混合したものへ加える。室温にて約２
０時間反応させた後、イオン交換水へ投入し冷却して析
出物を濾別する。エタノールにて再結晶し減圧乾燥する
と１．１ｇの４’−ヘキシル４−α−ブトキシプロパノ
イルオキシアゾベンゼンが得られた。(-)-2-butoxypropionic acid 2.4
Then, 2.5 g of thionyl chloride was gradually added to the flask, and after reacting for 30 minutes, the thionyl chloride was distilled off. The obtained 2-butoxypropionic acid chloride is added to a mixture of 3.0 g of 4-hydroxy-4-hexylazobenzene and 20 ml of dry pyridine. Approximately 2 at room temperature
After reacting for 0 hours, the mixture was poured into ion-exchanged water, cooled, and the precipitate was filtered off. Recrystallization from ethanol and drying under reduced pressure yielded 1.1 g of 4'-hexyl 4-α-butoxypropanoyloxyazobenzene.
【００４４】[0044]
【数３】
ＩＲ：２９４０，１７７５，１６００，１５００，１２
００，１１４０，８４０ｃｍ−１。[Math 3] IR: 2940, 1775, 1600, 1500, 12
00,1140,840 cm-1.
【００４５】実施例２［４’−ヘプチル４−α−ブトキ
シプロパノイルオキシアゾベンゼン］
４−ヘプチルアニリン３２．９ｇ（０．１７Ｍ）を０℃
以下に冷却し１０％塩酸水溶液８５ｇを加え、次に亜硝
酸ナトリウム１２．１ｇを７０ｍｌの水に溶解したもの
を加えた。滴下中は０℃以上とならないように冷却した
。滴下終了後３０分間反応させたものを滴下ロートへ移
し、フェノール１６ｇを含む８％ＮａＯＨ水溶液３００
ｍｌへ滴下した。滴下中は５℃以下に保った。滴下終了
後１時間攪拌を続け、その後ｐＨ５〜６となるまで１０
％塩酸水溶液を加え、反応物を析出させた。析出物を濾
別し水にて洗浄後、減圧乾燥を１夜行った。乾燥後石油
エーテル５００ｍｌで洗浄し、さらに減圧乾燥して３４
．７ｇ（０．１２Ｍ）の４−ハイドロキシ４’−ヘプチ
ルアゾベンゼンを得た。収率は７１％であった。Example 2 [4'-heptyl 4-α-butoxypropanoyloxyazobenzene] 32.9 g (0.17 M) of 4-heptylaniline was heated to 0°C.
After cooling, 85 g of a 10% aqueous hydrochloric acid solution was added, and then 12.1 g of sodium nitrite dissolved in 70 ml of water was added. During the dropping, the solution was cooled so that the temperature did not exceed 0°C. After the dropwise addition was completed, the reaction mixture was allowed to react for 30 minutes, then transferred to a dropping funnel, and 300 g of an 8% NaOH aqueous solution containing 16 g of phenol was added.
ml was added dropwise. The temperature was kept below 5° C. during the dropping. After dropping, continue stirring for 1 hour, then stir for 1 hour until the pH reaches 5-6.
% aqueous hydrochloric acid solution was added to precipitate the reaction product. The precipitate was filtered off, washed with water, and then dried under reduced pressure overnight. After drying, it was washed with 500 ml of petroleum ether and further dried under reduced pressure.
．． 7 g (0.12 M) of 4-hydroxy 4'-heptyl azobenzene was obtained. The yield was 71%.
【００４６】（−）−２−ブトキシプロピオン酸２．４
ｇをフラスコへ加え次に塩化チオニル２．５ｇを徐々に
加え３０分間反応後塩化チオニルを留去する。得られた
２−ブトキシプロピオン酸クロライドを４−ハイドロキ
シ−４−ヘプチルアゾベンゼン３．２ｇを乾燥ピリジン
２０ｍｇとともにフラスコへ加え攪拌したものへ加える
。室温にて５時間反応させた後、イオン交換水へ投入し
冷却して析出物を濾別する。エタノールにて再結晶した
ものをシリカゲルカラムクロマトグラフ（溶媒：ベンゼ
ン）にて精製して１．２ｇの４’−ヘプチル４−α−ブ
トキシプロパノイルオキシアゾベンゼンを得た。(-)-2-butoxypropionic acid 2.4
Then, 2.5 g of thionyl chloride was gradually added to the flask, and after reacting for 30 minutes, the thionyl chloride was distilled off. The obtained 2-butoxypropionic acid chloride and 3.2 g of 4-hydroxy-4-heptyl azobenzene and 20 mg of dry pyridine were added to a flask and stirred. After reacting at room temperature for 5 hours, the mixture was poured into ion-exchanged water, cooled, and the precipitate was filtered off. The product was recrystallized from ethanol and purified by silica gel column chromatography (solvent: benzene) to obtain 1.2 g of 4'-heptyl 4-α-butoxypropanoyloxyazobenzene.
【００４７】[0047]
【数４】
ＩＲスペクトル（ＫＢｒディスク法）を図２に示す。特
徴的な吸収ピークは２９３０，１７７５，１６００，１
５００，１２０５，１１４０，８４０ｃｍ−１であった
。[Formula 4] The IR spectrum (KBr disk method) is shown in FIG. Characteristic absorption peaks are 2930, 1775, 1600, 1
They were 500, 1205, 1140, and 840 cm-1.
【００４８】実施例３［４’−オクチル４−α−ブトキ
シプロパノイルオキシアゾベンゼン］
４−オクチルアニリン３５ｇ（０．１７Ｍ）を０℃以下
に冷却し１０％塩酸水溶液８５ｇを加え、次に亜硝酸ナ
トリウム１２．０ｇを６８ｍｌの水に溶解したものを加
えた。滴下中は０℃以上とならないように冷却した。滴
下終了後３０分間反応させたものを滴下ロートへ移し、
フェノール１６ｇを含む８％ＮａＯＨ水溶液１７０ｇへ
滴下した。滴下中は５℃以下に保った。滴下終了後１時
間攪拌を続け、その後ｐＨ５〜６となるまで１０％塩酸
水溶液を加え、反応物を析出させた。析出物を濾別し水
にて洗浄後、減圧乾燥を１夜行った。乾燥後石油エーテ
ル５００ｍｌで洗浄し、さらに減圧乾燥して３０．８ｇ
（０．１０Ｍ）の４−ハイドロキシ４’−ヘプチルアゾ
ベンゼンを得た。収率は５９％であった。Example 3 [4'-Octyl 4-α-butoxypropanoyloxyazobenzene] 35 g of 4-octylaniline (0.17 M) was cooled to below 0°C, 85 g of a 10% aqueous hydrochloric acid solution was added, and then nitrous acid A solution of 12.0 g of sodium dissolved in 68 ml of water was added. During the dropping, the solution was cooled so that the temperature did not exceed 0°C. After the dropping was completed, the mixture was allowed to react for 30 minutes and then transferred to the dropping funnel.
The mixture was added dropwise to 170 g of an 8% NaOH aqueous solution containing 16 g of phenol. The temperature was kept below 5° C. during the dropping. After the completion of the dropwise addition, stirring was continued for 1 hour, and then 10% aqueous hydrochloric acid solution was added until the pH reached 5 to 6 to precipitate the reaction product. The precipitate was filtered off, washed with water, and then dried under reduced pressure overnight. After drying, wash with 500ml of petroleum ether and dry under reduced pressure to give 30.8g.
(0.10M) of 4-hydroxy 4'-heptyl azobenzene was obtained. The yield was 59%.
【００４９】５ｇのＫＯＨを５０ｍｌのエタノールに溶
解したものへ４−ハイドロキシ−４’−オクチルアゾベ
ンゼン１２．４ｇを加え室温にて６時間反応させる。エ
タノールを留去し、析出した結晶をアセトンで洗浄し減
圧乾燥すると８．８ｇのカリウム４’−オクチル４ハイ
ドロキシアゾベンゼンが得られた。（−）−２−ブトキ
シプロピオン酸２．１ｇへ塩化チオニル２．８ｇを少し
づつ滴下する。室温にて３０分間反応後塩化チオニルを
留去する。得られた２−ブトキシプロピオン酸クロライ
ドをカリウム−４’−オクチル４ハイドロキシアゾベン
ゼン３．６ｇを１６ｍｌのアセトンと０．８４ｇのＮａ
ＨＣＯ３に混合したものへ滴下し、滴下終了後イオン交
換水を加え、析出した結晶を濾別しエタノールにて再結
晶すると、１．８ｇの４’−オクチル４−αブトキシプ
ロパノイルオキシアゾベンゼンが得られた。To a solution of 5 g of KOH in 50 ml of ethanol, 12.4 g of 4-hydroxy-4'-octylazobenzene was added and reacted at room temperature for 6 hours. Ethanol was distilled off, and the precipitated crystals were washed with acetone and dried under reduced pressure to obtain 8.8 g of potassium 4'-octyl 4-hydroxyazobenzene. 2.8 g of thionyl chloride is gradually added dropwise to 2.1 g of (-)-2-butoxypropionic acid. After reacting for 30 minutes at room temperature, thionyl chloride is distilled off. The obtained 2-butoxypropionic acid chloride was mixed with 3.6 g of potassium-4'-octyl 4-hydroxyazobenzene, 16 ml of acetone, and 0.84 g of Na.
Add dropwise to the mixture with HCO3, add ion-exchanged water after the dropwise addition, separate the precipitated crystals by filtration, and recrystallize with ethanol to obtain 1.8 g of 4'-octyl 4-α butoxypropanoyloxyazobenzene. It was done.
【００５０】[0050]
【数５】
ＩＲ：２９３０，１７７５，１６００，１５００，１２
０５，１１４０，８４０ｃｍ−１。[Math. 5] IR: 2930, 1775, 1600, 1500, 12
05,1140,840 cm-1.
【００５１】実施例４［４’ヘキシルオキシ４−α−ブ
トキシプロパノイルオキシアゾベンゼン］ｎ−ヘキシル
オキシアニリン１６．５ｇを５０ｍｌのイオン交換水と
ともに冷却したものへ１０％塩酸水溶液４３ｇを加える
。次にＮａＮＯ２５．９ｇを３４ｍｌの水に溶解したも
のを冷却しつつ滴下する。フェノール８．０ｇを８％Ｎ
ａＯＨ水溶液８６．６ｇへ溶解したものへ上記の反応さ
せたものを加える。滴下中は５℃以下に保った。滴下終
了後１時間放置し、１０％塩酸水溶液を加えｐＨ１とし
た。析出した微結晶を濾別し減圧乾燥した。乾燥後石油
エーテルで洗浄し、さらに減圧乾燥し、１２．１ｇの４
−ハイドロキシ−４’−ヘキシルオキシアゾベンゼンを
得た。Example 4 [4'Hexyloxy 4-α-butoxypropanoyloxyazobenzene] 16.5 g of n-hexyloxyaniline was cooled with 50 ml of ion-exchanged water, and 43 g of a 10% aqueous hydrochloric acid solution was added thereto. Next, 25.9 g of NaNO dissolved in 34 ml of water was added dropwise while cooling. 8.0g of phenol in 8%N
The above reacted material was added to the solution dissolved in 86.6 g of aOH aqueous solution. The temperature was kept below 5° C. during the dropping. After the dropwise addition was completed, the mixture was left to stand for 1 hour, and a 10% aqueous hydrochloric acid solution was added to adjust the pH to 1. The precipitated microcrystals were filtered off and dried under reduced pressure. After drying, it was washed with petroleum ether, further dried under reduced pressure, and 12.1 g of 4
-Hydroxy-4'-hexyloxyazobenzene was obtained.
【００５２】（−）−２−ブトキシプロピオン酸２．４
ｇをフラスコへ加え次に塩化チオニル２．５ｇを徐々に
加え３０分間反応後塩化チオニルを留去する。得られた
２−ブトキシプロピオン酸クロライドを４−ハイドロキ
シ−４’−ヘキシルオキシアゾベンゼン３．２ｇを乾燥
ピリジン２０ｍｌとともにフラスコへ加え攪拌したもの
へ加える。室温にて２０時間放置したのちイオン交換水
へ投入し、析出物を濾別する。シリカゲルカラムクロマ
トグラフ（溶媒：ベンゼン）にて精製して２．０ｇの４
’−ヘキシルオキシ−４−α−ブトキシプロパノイルオ
キシアゾベンゼンを得た。(-)-2-butoxypropionic acid 2.4
Then, 2.5 g of thionyl chloride was gradually added to the flask, and after reacting for 30 minutes, the thionyl chloride was distilled off. The obtained 2-butoxypropionic acid chloride was added to a stirred flask together with 3.2 g of 4-hydroxy-4'-hexyloxyazobenzene and 20 ml of dry pyridine. After being left at room temperature for 20 hours, it was poured into ion-exchanged water and the precipitate was filtered off. Purified by silica gel column chromatography (solvent: benzene) and 2.0 g of 4
'-hexyloxy-4-α-butoxypropanoyloxyazobenzene was obtained.
【００５３】[0053]
【数６】
ＩＲ：２９４０，１７６０，１６００，１４９０，１２
００，１１３０，８４０ｃｍ−１。[Math. 6] IR: 2940, 1760, 1600, 1490, 12
00,1130,840 cm-1.
【００５４】実施例５［４’−オクチル４−α−ヘプチ
ルオキシプロパノイルオキシアゾベンゼン］４−オクチ
ルアニリン３５ｇ（０．１７Ｍ）を０℃以下に冷却し１
０％塩酸水溶液８５ｇを加え、次に亜硝酸ナトリウム１
２．０ｇを６８ｍｌの水に溶解したものを加えた。滴下
中は０℃以上とならないように冷却した。滴下終了後３
０分間反応させたものを滴下ロートへ移し、フェノール
１６ｇを含む８％ＮａＯＨ水溶液１７０ｇへ滴下した。
滴下中は５℃以下に保った。滴下終了後１時間攪拌を続
け、その後ｐＨ５〜６となるまで１０％塩酸水溶液を加
え、反応物を析出させた。析出物を濾別し水にて洗浄後
、減圧乾燥を１夜行った。乾燥後石油エーテル５００ｍ
ｌで洗浄し、さらに減圧乾燥して３０．８ｇ（０．１０
Ｍ）の４−ハイドロキシ４’−オクチルアゾベンゼンを
得た。収率は５９％であった。Example 5 [4'-octyl 4-α-heptyloxypropanoyloxyazobenzene] 35 g (0.17 M) of 4-octylaniline was cooled to below 0°C.
Add 85 g of 0% aqueous hydrochloric acid solution, then add 1 portion of sodium nitrite.
A solution of 2.0 g dissolved in 68 ml of water was added. During the dropping, the solution was cooled so that the temperature did not exceed 0°C. After finishing dropping 3
After 0 minutes of reaction, the mixture was transferred to a dropping funnel and added dropwise to 170 g of an 8% NaOH aqueous solution containing 16 g of phenol. The temperature was kept below 5° C. during the dropping. After the completion of the dropwise addition, stirring was continued for 1 hour, and then 10% aqueous hydrochloric acid solution was added until the pH reached 5 to 6 to precipitate the reaction product. The precipitate was filtered off, washed with water, and then dried under reduced pressure overnight. Petroleum ether 500m after drying
Wash with 30.8 g (0.10
M) 4-hydroxy 4'-octyl azobenzene was obtained. The yield was 59%.
【００５５】（−）−２−ヘプチルオキシプロピオン酸
３．８ｇをフラスコへ加え、次に塩化チオニル３．６ｇ
を加え３０分間反応後塩化チオニルを留去する。得られ
た２−ヘプチルオキシプロピオン酸クロライドを実施例
１０に示した４’−カリウムオキシ−４−オクチルアゾ
ベンゼン５．３ｇと２０ｍｌのアセトンと１．３ｇのＮ
ａＨＣＯ３とを混合したものへ滴下する。滴下終了後１
時間反応させ水を２０ｍｌ加え分離した油層を冷却して
固化したものを濾別した。シリカゲルカラムクロマトグ
ラフ（溶媒：ベンゼン）にて精製して３．１ｇの４’−
オクチル４−α−ヘプチルオキシプロパノイルオキシア
ゾベンゼンを得た。Add 3.8 g of (-)-2-heptyloxypropionic acid to the flask, then add 3.6 g of thionyl chloride.
After reaction for 30 minutes, thionyl chloride was distilled off. The obtained 2-heptyloxypropionic acid chloride was mixed with 5.3 g of 4'-potassiumoxy-4-octylazobenzene shown in Example 10, 20 ml of acetone, and 1.3 g of N.
Add dropwise to the mixture with aHCO3. After finishing dropping 1
After reacting for a time, 20 ml of water was added, and the separated oil layer was cooled and solidified, which was filtered. Purified by silica gel column chromatography (solvent: benzene) to produce 3.1 g of 4'-
Octyl 4-α-heptyloxypropanoyloxyazobenzene was obtained.
【００５６】[0056]
【数７】
ＩＲスペクトル（バルク法）を図３に示す。特徴的な吸
収ピークは、２９３０，１７８０，１６００，１５００
，１２００，１１１０，８４０ｃｍ−１であった。[Formula 7] The IR spectrum (bulk method) is shown in FIG. Characteristic absorption peaks are 2930, 1780, 1600, 1500
, 1200, 1110, 840 cm-1.
【００５７】実施例６［４’−ヘキシルオキシ４−α−
ヘプチルオキシプロパノイルオキシアゾベンゼン］ｎ−
ヘキシルオキシアニリン１６．５ｇを５０ｍｌのイオン
交換水とともに冷却したものへ１０％塩酸水溶液４３ｇ
を加える。次にＮａＮＯ２５．９ｇを３４ｍｌの水に溶
解したものを冷却しつつ滴下する。フェノール８．０ｇ
を８％ＮａＯＨ水溶液８６．６ｇへ溶解したものへ上記
の反応させたものを加える。滴下中は５℃以下に保った
。滴下終了後１時間放置し、１０％塩酸水溶液を加えｐ
Ｈ１とした。析出した微結晶を濾別し減圧乾燥した。乾
燥後石油エーテルで洗浄し、さらに減圧乾燥し１２．１
ｇの４−ハイドロキシ４’−ヘキシルオキシアゾベンゼ
ンを得た。Example 6 [4'-hexyloxy 4-α-
heptyloxypropanoyloxyazobenzene]n-
16.5 g of hexyloxyaniline was cooled with 50 ml of ion-exchanged water, and 43 g of 10% hydrochloric acid aqueous solution was added.
Add. Next, 25.9 g of NaNO dissolved in 34 ml of water was added dropwise while cooling. Phenol 8.0g
To a solution of 86.6 g of 8% NaOH aqueous solution, the above reacted material was added. The temperature was kept below 5° C. during the dropping. After dropping, leave for 1 hour, add 10% hydrochloric acid aqueous solution
It was set as H1. The precipitated microcrystals were filtered off and dried under reduced pressure. After drying, wash with petroleum ether and further dry under reduced pressure 12.1
g of 4-hydroxy4'-hexyloxyazobenzene was obtained.
【００５８】（−）−２−ヘプチルオキシプロピオン酸
３．８ｇをフラスコへ加え、次に塩化チオニル３．６ｇ
を加え３０分間反応後塩化チオニルを留去する。得られ
た２−ヘプチルオキシプロピオン酸クロライドを４−ハ
イドロキシ−４’−ヘキシルオキシアゾベンゼン４．５
ｇを乾燥ピリジン２０ｍｌとともにフラスコへ加え攪拌
したものへ加える。室温にて５時間放置したのちイオン
交換水へ投入し析出物を濾別する。シリカゲルカラムク
ロマトグラフ（溶媒：ベンゼン）にて精製して２．８ｇ
の４’−ヘキシルオキシ４−α−ヘプチルオキシプロパ
ノイルオキシアゾベンゼンを得た。Add 3.8 g of (-)-2-heptyloxypropionic acid to the flask, then add 3.6 g of thionyl chloride.
After reaction for 30 minutes, thionyl chloride was distilled off. The obtained 2-heptyloxypropionic acid chloride was mixed with 4-hydroxy-4'-hexyloxyazobenzene 4.5
g was added to the flask along with 20 ml of dry pyridine and stirred. After being left at room temperature for 5 hours, it was poured into ion-exchanged water and the precipitate was filtered off. 2.8g purified by silica gel column chromatography (solvent: benzene)
4'-hexyloxy 4-α-heptyloxypropanoyloxyazobenzene was obtained.
【００５９】[0059]
【数８】
ＩＲ：２９４０，１７６０，１６００，１５００，１２
１０，１１３０，８４５ｃｍ−１。[Math. 8] IR: 2940, 1760, 1600, 1500, 12
10,1130,845 cm-1.
【００６０】実施例７［４’−ヘキシルオキシ４−α−
ブトキシプロパノイルオキシアゾキシベンゼン］ｎ−ヘ
キシルオキシアニリン１６．５ｇを５０ｍｌのイオン交
換水とともに冷却したものへ１０％塩酸水溶液４３ｇを
加える。次にＮａＮＯ２５．９ｇを３４ｍｌの水に溶解
したものを冷却しつつ滴下する。フェノール８．０ｇを
８％ＮａＯＨ水溶液８６．６ｇへ溶解したものへ上記の
反応させたものを加える。滴下中は５℃以下に保った。
滴下終了後１時間放置し、１０％塩酸水溶液を加えｐＨ
１とした。析出した微結晶を濾別し減圧乾燥した。乾燥
後石油エーテルで洗浄し、さらに減圧乾燥し１２．１ｇ
の４−ハイドロキシ４’−ヘキシルオキシアゾベンゼン
を得た。Example 7 [4'-hexyloxy 4-α-
Butoxypropanoyloxyazoxybenzene] 16.5 g of n-hexyloxyaniline was cooled with 50 ml of ion-exchanged water, and 43 g of a 10% aqueous hydrochloric acid solution was added thereto. Next, 25.9 g of NaNO dissolved in 34 ml of water was added dropwise while cooling. The above reaction mixture was added to a solution of 8.0 g of phenol in 86.6 g of an 8% NaOH aqueous solution. The temperature was kept below 5° C. during the dropping. After dropping, leave for 1 hour and add 10% hydrochloric acid solution to adjust the pH.
It was set to 1. The precipitated microcrystals were filtered off and dried under reduced pressure. After drying, it was washed with petroleum ether and further dried under reduced pressure to give 12.1g.
4-hydroxy4'-hexyloxyazobenzene was obtained.
【００６１】（−）−２−ブトキシプロピオン酸２．４
ｇをフラスコへ加え、次に塩化チオニル２．５ｇを徐々
に加え３０分間反応後塩化チオニルを留去する。得られ
た２−ブトキシプロピオン酸クロライドを４−ハイドロ
キシ−４’−ヘキシルオキシアゾベンゼン３．２ｇを乾
燥ピリジン２０ｍｌとともにフラスコへ加え攪拌したも
のへ加える。室温にて２０時間放置したのちイオン交換
水へ投入し析出物を濾別する。シリカゲルカラムクロマ
トグラフ（溶媒：ベンゼン）にて精製して２．０ｇの４
’−ヘキシルオキシ４−α−ブトキシプロパノイルオキ
シアゾベンゼンを得た。融点７２．５℃４’−ヘキシル
オキシ−４−α−ブトキシプロパノイルオキシアゾベン
ゼン０．８１ｇを氷酢酸４０ｍｌに溶解攪拌しつつ５０
〜６０℃に保ち、３１％Ｈ２Ｏ２水溶液５ｍｌを約６時
間で滴下する。５０〜６０℃でさらに４時間、室温にて
３０時間放置し、４００ｍｌのイオン交換水ヘ投入しエ
ーテルにて抽出する。５％Ｎａ２ＣＯ３水溶液５０ｍｌ
およびイオン交換水にて洗浄し、無水Ｎａ２ＳＯ４にて
乾燥する。エーテルを留去し得られた黄色結晶をエタノ
ールにて再結晶すると０．３ｇの４’−ヘキシルオキシ
４−α−ブトキシプロパノイルオキシアゾキシベンゼン
が得られた。(-)-2-butoxypropionic acid 2.4
Then, 2.5 g of thionyl chloride was gradually added to the flask, and after reacting for 30 minutes, the thionyl chloride was distilled off. The obtained 2-butoxypropionic acid chloride was added to a stirred flask together with 3.2 g of 4-hydroxy-4'-hexyloxyazobenzene and 20 ml of dry pyridine. After being left at room temperature for 20 hours, it was poured into ion-exchanged water and the precipitate was filtered off. Purified by silica gel column chromatography (solvent: benzene) and 2.0 g of 4
'-Hexyloxy 4-α-butoxypropanoyloxyazobenzene was obtained. Melting point 72.5°C 0.81 g of 4'-hexyloxy-4-α-butoxypropanoyloxyazobenzene was dissolved in 40 ml of glacial acetic acid and heated to 50° C. with stirring.
The temperature is maintained at ~60°C, and 5 ml of 31% H2O2 aqueous solution is added dropwise over about 6 hours. The mixture was left at 50 to 60° C. for an additional 4 hours and at room temperature for 30 hours, poured into 400 ml of ion-exchanged water, and extracted with ether. 50ml of 5% Na2CO3 aqueous solution
and ion-exchanged water, and dried with anhydrous Na2SO4. The yellow crystals obtained by distilling off the ether were recrystallized from ethanol to obtain 0.3 g of 4'-hexyloxy 4-α-butoxypropanoyloxyazoxybenzene.
【００６２】[0062]
【数９】
ＩＲ：２９３０，１７６０，１６００，１５００，１４
６０，１２６０，１１３０，８４０ｃｍ−１。[Math. 9] IR: 2930, 1760, 1600, 1500, 14
60,1260,1130,840 cm-1.
【００６３】実施例８［４’−オクチル４−α−ヘプチ
ルオキシプロパノイルオキシアゾキシベンゼン］４−オ
クチルアニリン３５ｇ（０．１７Ｍ）を０℃以下に冷却
し１０％塩酸水溶液８５ｇを加え、次に亜硝酸ナトリウ
ム１２．０ｇを６８ｍｌの水に溶解したものを加えた。
滴下中は０℃以上とならないように冷却した。滴下終了
後３０分間反応させたものを滴下ロートへ移し、フェノ
ール１６ｇを含む８％ＮａＯＨ水溶液１７０ｇへ滴下し
た。滴下中は５℃以下に保った。滴下終了後１時間攪拌
を続け、その後ｐＨ５〜６となるまで１０％塩酸水溶液
を加え、反応物を析出させた。析出物を濾別し水にて洗
浄後、減圧乾燥を１夜行った。乾燥後石油エーテル５０
０ｍｌで洗浄し、さらに減圧乾燥して３０．８ｇ（０．
１０Ｍ）の４−ハイドロキシ４’−オクチルアゾベンゼ
ンを得た。収率は５９％であった。Example 8 [4'-octyl 4-α-heptyloxypropanoyloxyazoxybenzene] 35 g (0.17 M) of 4-octylaniline was cooled to below 0°C, 85 g of 10% aqueous hydrochloric acid solution was added, and then A solution of 12.0 g of sodium nitrite dissolved in 68 ml of water was added to the solution. During the dropping, the solution was cooled so that the temperature did not exceed 0°C. After the completion of the dropwise addition, the mixture was allowed to react for 30 minutes, then transferred to a dropping funnel, and added dropwise to 170g of an 8% NaOH aqueous solution containing 16g of phenol. The temperature was kept below 5° C. during the dropping. After the completion of the dropwise addition, stirring was continued for 1 hour, and then 10% aqueous hydrochloric acid solution was added until the pH reached 5 to 6 to precipitate the reaction product. The precipitate was filtered off, washed with water, and then dried under reduced pressure overnight. Petroleum ether after drying 50
Washed with 0ml and further dried under reduced pressure to obtain 30.8g (0.
10M) of 4-hydroxy 4'-octylazobenzene was obtained. The yield was 59%.
【００６４】（−）−２−ヘプチルオキシプロピオン酸
３．８ｇをフラスコへ加え、次に塩化チオニル３．６ｇ
を加え３０分間反応後塩化チオニルを留去する。得られ
た２−ヘプチルオキシプロピオン酸クロライドを実施例
１０に示した４’−カリウムオキシ−４−オクチルアゾ
ベンゼン５．３ｇと２０ｍｌのアセトンと１．３ｇのＮ
ａＨＣＯ２とを混合したものへ滴下する。滴下終了後１
時間反応させ水を２０ｍｌ加え分離した油層を冷却して
固化したものを濾別した。シリカゲルカラムクロマトグ
ラフ（溶媒：ベンゼン）にて精製して３．１ｇの４’−
オクチル４−α−ヘプチルオキシプロパノイルオキシア
ゾベンゼンを得た。融点４２．１℃。Add 3.8 g of (-)-2-heptyloxypropionic acid to the flask, then add 3.6 g of thionyl chloride.
After reaction for 30 minutes, thionyl chloride was distilled off. The obtained 2-heptyloxypropionic acid chloride was mixed with 5.3 g of 4'-potassiumoxy-4-octylazobenzene shown in Example 10, 20 ml of acetone, and 1.3 g of N.
Add dropwise to the mixture with aHCO2. After finishing dropping 1
After reacting for a time, 20 ml of water was added, and the separated oil layer was cooled and solidified, which was filtered. Purified by silica gel column chromatography (solvent: benzene) to produce 3.1 g of 4'-
Octyl 4-α-heptyloxypropanoyloxyazobenzene was obtained. Melting point: 42.1°C.
【００６５】４’−オクチル−４−α−ヘプチルオキシ
プロパノイルオキシアゾベンゼン０．８ｇを５０ｍｌの
氷酢酸へ溶解し５０〜６０℃に保ち３１％Ｈ２Ｏ２水溶
液７ｍｌを１時間３０分で滴下する。５０〜６０℃に２
２時間保持したのち５００ｍｌのイオン交換水へ投入し
エーテルにて抽出する。１００ｍｌの５％Ｎａ２ＣＯ３
水溶液と１００ｍｌのイオン交換水で洗浄したものから
エーテルを留去する。シリカゲルカラムクロマトグラフ
（溶媒：ベンゼン）にて精製し０．３ｇの４’−オクチ
ル４−α−ヘプチルオキシプロパノイル−オキシアゾキ
シベンゼンを得た。0.8 g of 4'-octyl-4-α-heptyloxypropanoyloxyazobenzene was dissolved in 50 ml of glacial acetic acid, and the solution was kept at 50 to 60° C. and 7 ml of a 31% H2O2 aqueous solution was added dropwise over 1 hour and 30 minutes. 2 to 50-60℃
After holding for 2 hours, the mixture was poured into 500 ml of ion-exchanged water and extracted with ether. 100ml 5% Na2CO3
Ether is distilled off from the aqueous solution and washed with 100 ml of ion-exchanged water. It was purified by silica gel column chromatography (solvent: benzene) to obtain 0.3 g of 4'-octyl 4-α-heptyloxypropanoyl-oxyazoxybenzene.
【００６６】[0066]
【数１０】
ＩＲ：２９２０，１７７５，１６００，１５００，１４
６５，１２００，１１２０，８３０ｃｍ−１。[Math. 10] IR: 2920, 1775, 1600, 1500, 14
65,1200,1120,830 cm-1.
【００６７】実施例９［４’−ヘキシルオキシ４−α−
ヘプチルオキシプロパノイルオキシアゾキシベンゼン］
ｎ−ヘキシルオキシアニリン１６．５ｇを５０ｍｌのイ
オン交換水とともに冷却したものへ１０％塩酸水溶液４
３ｇを加える。次にＮａＮＯ２５．９ｇを３４ｍｌの水
に溶解したものを冷却しつつ滴下する。フェノール８．
０ｇを８％ＮａＯＨ水溶液８６．６ｇへ溶解したものへ
上記の反応させたものを加える。滴下中は５℃以下に保
った。滴下終了後１時間放置し、１０％塩酸水溶液を加
えｐＨ１とした。析出した微結晶を濾別し減圧乾燥した
。乾燥後石油エーテルで洗浄し、さらに減圧乾燥し１２
．１ｇの４−ハイドロキシ４’−ヘキシルオキシアゾベ
ンゼンを得た。Example 9 [4'-hexyloxy 4-α-
heptyloxypropanoyloxyazoxybenzene]
16.5 g of n-hexyloxyaniline was cooled with 50 ml of ion-exchanged water, and 10% aqueous hydrochloric acid solution 4 was added.
Add 3g. Next, 25.9 g of NaNO dissolved in 34 ml of water was added dropwise while cooling. Phenol8.
0g was dissolved in 86.6g of 8% NaOH aqueous solution, and the above reacted product was added. The temperature was kept below 5° C. during the dropping. After the dropwise addition was completed, the mixture was left to stand for 1 hour, and a 10% aqueous hydrochloric acid solution was added to adjust the pH to 1. The precipitated microcrystals were filtered off and dried under reduced pressure. After drying, wash with petroleum ether and further dry under reduced pressure.
．． 1 g of 4-hydroxy4'-hexyloxyazobenzene was obtained.
【００６８】（−）−２−ヘプチルオキシプロピオン酸
３．８ｇをフラスコへ加え、次に塩化チオニル３．６ｇ
を加え３０分間反応後塩化チオニルを留去する。得られ
た２−ヘプチルオキシプロピオン酸クロライドを４−ハ
イドロキシ−４’−ヘキシルオキシアゾベンゼン４．５
ｇを乾燥ピリジン２０ｍｌとともにフラスコへ加え攪拌
したものへ加える。室温にて５時間放置したのちイオン
交換水へ投入し析出物を濾別する。シリカゲルカラムク
ロマトグラフ（溶媒：ベンゼン）にて精製して２．８ｇ
の４’−ヘキシルオキシ４−α−ヘプチルオキシプロパ
ノイルオキシアゾベンゼンを得た。融点６９℃。Add 3.8 g of (-)-2-heptyloxypropionic acid to the flask, then add 3.6 g of thionyl chloride.
After reaction for 30 minutes, thionyl chloride was distilled off. The obtained 2-heptyloxypropionic acid chloride was mixed with 4-hydroxy-4'-hexyloxyazobenzene 4.5
g was added to the flask along with 20 ml of dry pyridine and stirred. After being left at room temperature for 5 hours, it was poured into ion-exchanged water and the precipitate was filtered off. 2.8g purified by silica gel column chromatography (solvent: benzene)
4'-hexyloxy 4-α-heptyloxypropanoyloxyazobenzene was obtained. Melting point: 69°C.
【００６９】４’−ヘキシルオキシ４−α−ヘプチルオ
キシプロパノイルオキシアゾベンゼン０．８２ｇを５５
ｍｌの氷酢酸へ溶解し５０〜６０℃に保ち３１％Ｈ２Ｏ
２水溶液７ｍｌを約１時間で滴下する。５０〜６０℃に
２４時間保持し、さらに室温にて２４時間放置した後、
８００ｍｌのイオン交換水へ投入しエーテルにて抽出す
る。３．３ｇのＮａ２ＣＯ３を含む１００ｍｌの水溶液
および１００ｍｌのイオン交換水で洗浄し、無水Ｎａ２
ＳＯ４にて乾燥する。エーテルを留去したものをシリカ
ゲルカラムクロマトグラム（溶媒：ベンゼン）にて精製
して０．４ｇの４’−ヘキシルオキシ−４α−ヘプチル
オキシプロパノイルオキシアゾキシベンゼンを得た。0.82 g of 4'-hexyloxy 4-α-heptyloxypropanoyloxyazobenzene was added to 55
Dissolve in ml of glacial acetic acid and keep at 50-60℃ in 31% H2O.
7 ml of the aqueous solution of 2 was added dropwise over about 1 hour. After keeping it at 50 to 60°C for 24 hours and leaving it at room temperature for 24 hours,
The mixture was poured into 800 ml of ion-exchanged water and extracted with ether. Washed with 100 ml of aqueous solution containing 3.3 g of Na2CO3 and 100 ml of deionized water, then washed with anhydrous Na2
Dry with SO4. The residue from which the ether was distilled off was purified by silica gel column chromatography (solvent: benzene) to obtain 0.4 g of 4'-hexyloxy-4α-heptyloxypropanoyloxyazoxybenzene.
【００７０】[0070]
【数１１】
ＩＲ：２９４０，１７６０，１６００，１５００，１４
７０，１２００，１１４０，８４０ｃｍ−１。[Math. 11] IR: 2940, 1760, 1600, 1500, 14
70, 1200, 1140, 840 cm-1.
【００７１】参考例８〈実施例５で製造した液晶性化合
物を配合成分とする液晶組成物の特性〉ＤＯＢＡＭＢＣ
８８ｗｔ％と実施例５の液晶性化合物１２ｗｔ％か
らなる液晶組成物を調製したところＳｍＣ＊の温度範囲
を４７℃〜８０℃に低下させることができた。Reference Example 8 <Characteristics of a liquid crystal composition containing the liquid crystal compound produced in Example 5 as a compounding component> DOBAMBC
When a liquid crystal composition consisting of 88 wt% and 12 wt% of the liquid crystal compound of Example 5 was prepared, the temperature range of SmC* could be lowered to 47°C to 80°C.
【００７２】参考例９〈実施例８で製造した液晶性化合
物を配合成分とする液晶組成物の特性〉表１に示すよう
な液晶組成物を調製したところ冷却過程にて４０℃〜５
℃の温度範囲にてＳｍＣ＊を持つものとなった。Reference Example 9 <Characteristics of a liquid crystal composition containing the liquid crystalline compound produced in Example 8 as a compounding component> When a liquid crystal composition as shown in Table 1 was prepared, the temperature ranged from 40°C to 5°C during the cooling process.
It has SmC* in the temperature range of °C.
【００７３】[0073]
【表２】[Table 2]
【００７４】参考例１０〈実施例５で製造した液晶性化
合物を配合成分とする液晶組成物の特性〉ＭＢＲＡ
８ ９８ｗｔ％と実施例５の液晶性化合物２ｗｔ％か
らなる液晶組成物はＳｍＣ相のＴｃ−Ｔ＝１８．２℃に
おいてＭＢＲＡ ８単独の自発分極の２倍の自発分極
を示した。Reference Example 10 (Characteristics of a liquid crystal composition containing the liquid crystal compound produced in Example 5 as a compounding component) MBRA
A liquid crystal composition consisting of 98 wt % of MBRA 8 and 2 wt % of the liquid crystal compound of Example 5 exhibited a spontaneous polarization twice that of MBRA 8 alone at Tc-T of the SmC phase of 18.2°C.
【００７５】
ＭＢＲＡ ８単独 ＰＳ＝３４．６μｃ／
ｍ２（Ｔｃ−Ｔ＝２１．８℃） 参考例
１０ ＰＳ＝６０．１μｃ／ｍ２（Ｔｃ−Ｔ＝１
８．２℃）自発分極は三角波印加による分極反転電流に
より測定した（参考文献１９８３年第９回液晶討論会予
稿集ｐｐ．８２ 宮里、竹添、福田ｅｔ ａｌ）。MBRA 8 alone PS=34.6μc/
m2 (Tc-T=21.8℃) Reference example
10 PS=60.1 μc/m2 (Tc-T=1
(8.2° C.) Spontaneous polarization was measured by polarization inversion current by applying a triangular wave (Reference: Proceedings of the 9th Liquid Crystal Conference, 1983, pp. 82, Miyazato, Takezoe, Fukuda et al.).
【００７６】[0076]
【発明の効果】本発明の乳酸誘導体にあっては上記のよ
うに適度な分子間力と形状をもった機能性材料中間体と
光学活性を損うことなく結合させることができ、分子設
計を自由に行うことができる。また、本発明の乳酸誘導
体のうち特定の化合物はアルキル基の長さを変更するこ
とができ、このことにより、液晶状態において発現する
液晶相の種類や温度範囲は制御することが可能であり、
優れた液晶組成物を与える。また、本発明の乳酸誘導体
はＬＢ膜法により単分子累積膜を作製する場合にも容易
に疎水基を制御することが可能となる。[Effect of the invention] As mentioned above, the lactic acid derivative of the present invention can be combined with a functional material intermediate having appropriate intermolecular force and shape without impairing optical activity, and the molecular design can be improved. You can do it freely. Furthermore, in certain compounds of the lactic acid derivatives of the present invention, the length of the alkyl group can be changed, thereby making it possible to control the type and temperature range of the liquid crystal phase that appears in the liquid crystal state.
Provides an excellent liquid crystal composition. Furthermore, the lactic acid derivative of the present invention allows hydrophobic groups to be easily controlled even when a monomolecular cumulative film is produced by the LB film method.
【図１】参考例４で得られた化合物のＩＲスペクトル（
ＫＢｒディスク法）である。FIG. 1: IR spectrum of the compound obtained in Reference Example 4 (
KBr disk method).
【図２】実施例２で得られた化合物のＩＲスペクトル（
ＫＢｒディスク法）である。FIG. 2: IR spectrum of the compound obtained in Example 2 (
KBr disk method).
【図３】実施例５で得られた化合物のＩＲスペクトル（
バルク法）である。FIG. 3: IR spectrum of the compound obtained in Example 5 (
bulk method).
Claims (1)
炭化水素基を示す。Ｒ”はアゾベンゼン誘導体、アゾキ
シベンゼン誘導体、ビフェニル誘導体、ターフェニル誘
導体、フェニルシクロヘキサン誘導体、安息香酸誘導体
、ピリミジン誘導体、ピラジン誘導体、ピリジン誘導体
、スチルベン誘導トラン誘導体、カルコン誘導体、ビシ
クロヘキサン誘導体、あるいはケイ皮酸誘導体のいずれ
かの中から選ばれる残基。Ｃ＊は光学活性な不斉炭素原
子を示す。］で表される乳酸誘導体。[Claim 1] General formula (I'): [In general formula (I'), R represents a linear saturated hydrocarbon group having 4 to 20 carbon atoms. R” is an azobenzene derivative, an azoxybenzene derivative, a biphenyl derivative, a terphenyl derivative, a phenylcyclohexane derivative, a benzoic acid derivative, a pyrimidine derivative, a pyrazine derivative, a pyridine derivative, a stilbene derivative, a tolan derivative, a chalcone derivative, a bicyclohexane derivative, or a cinnamic derivative. A lactic acid derivative represented by a residue selected from any of the acid derivatives; C* represents an optically active asymmetric carbon atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3131692A JPH0717591B2 (en) | 1991-05-08 | 1991-05-08 | Lactic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3131692A JPH0717591B2 (en) | 1991-05-08 | 1991-05-08 | Lactic acid derivative |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19577084A Division JPS6176438A (en) | 1984-09-20 | 1984-09-20 | Lactic acid derivative and its composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04234837A true JPH04234837A (en) | 1992-08-24 |
| JPH0717591B2 JPH0717591B2 (en) | 1995-03-01 |
Family
ID=15063980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3131692A Expired - Fee Related JPH0717591B2 (en) | 1991-05-08 | 1991-05-08 | Lactic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717591B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410967A (en) * | 2019-01-08 | 2020-07-14 | 国家纳米科学中心 | Circular polarization luminous chiral nematic liquid crystal material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176438A (en) * | 1984-09-20 | 1986-04-18 | Canon Inc | Lactic acid derivative and its composition |
-
1991
- 1991-05-08 JP JP3131692A patent/JPH0717591B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176438A (en) * | 1984-09-20 | 1986-04-18 | Canon Inc | Lactic acid derivative and its composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410967A (en) * | 2019-01-08 | 2020-07-14 | 国家纳米科学中心 | Circular polarization luminous chiral nematic liquid crystal material and preparation method and application thereof |
| CN111410967B (en) * | 2019-01-08 | 2022-04-08 | 国家纳米科学中心 | Circular polarization luminous chiral nematic liquid crystal material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0717591B2 (en) | 1995-03-01 |
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