CN1158142A - Process for producing liquid cyrstal mixtures - Google Patents
Process for producing liquid cyrstal mixtures Download PDFInfo
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- CN1158142A CN1158142A CN95195144A CN95195144A CN1158142A CN 1158142 A CN1158142 A CN 1158142A CN 95195144 A CN95195144 A CN 95195144A CN 95195144 A CN95195144 A CN 95195144A CN 1158142 A CN1158142 A CN 1158142A
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- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 title claims description 14
- 230000008569 process Effects 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- -1 amino, carboxyl Chemical group 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000004615 ingredient Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000002837 carbocyclic group Chemical group 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000005277 alkyl imino group Chemical group 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000012071 phase Substances 0.000 description 15
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical class CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- CDZAAIHWZYWBSS-UHFFFAOYSA-N 2-bromoethyl prop-2-enoate Chemical class BrCCOC(=O)C=C CDZAAIHWZYWBSS-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- DQQOONVCLQZWOY-UHFFFAOYSA-N 4-hexoxybenzoyl chloride Chemical class CCCCCCOC1=CC=C(C(Cl)=O)C=C1 DQQOONVCLQZWOY-UHFFFAOYSA-N 0.000 description 1
- WWKZTBLUGXLBSQ-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1.COC1=CC=C(C(O)=O)C=C1 WWKZTBLUGXLBSQ-UHFFFAOYSA-N 0.000 description 1
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical class CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- DLRFDDKZTOPCKE-UHFFFAOYSA-N 6-(4-carbonochloridoylphenoxy)hexyl prop-2-enoate Chemical class ClC(=O)C1=CC=C(OCCCCCCOC(=O)C=C)C=C1 DLRFDDKZTOPCKE-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000003820 Medium-pressure liquid chromatography Methods 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical class OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000005911 haloform reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N para-methoxy benzoic acid Natural products COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical class CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical class Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical class CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JUKPJGZUFHCZQI-UHFFFAOYSA-N undecanoyl chloride Chemical compound CCCCCCCCCCC(Cl)=O JUKPJGZUFHCZQI-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
- C09K19/3458—Uncondensed pyrimidines
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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- Liquid Crystal Substances (AREA)
Abstract
Disclosed is a process for producing mixtures of liquid crystal compounds, wherein at least one of the starting components consists of a mixture of at least two compounds and this mixture is reacted, with at least one other starting component to form a random mixture.
Description
The present invention relates to a kind of method for preparing the mixture of liquid crystalline cpd, wherein at least a starting ingredient contains the mixture of at least two kinds of compounds, this mixture with known method and the reaction of at least a other starting ingredient, is generated a kind of mixture at random.
Liquid crystal material does not have performance required when using during as pure substance usually.Have only different liquid crystalline cpd is mixed, also mix if desired with non-liquid crystalline cpd, the application that just can make the character of liquid crystal material be suitable for being intended to, described character for example is mesomorphic phase temperature, electro-optic response time, double refraction or viscosity.For the application in electrooptics, no matter in nematic phase still in the Application Areas of ferroelectric phase, it is normally necessary to contain the mixture of a large amount of different compounds, usually greatly more than four kinds of compounds.Have the very big liquid crystalline cpd of structural difference, but in many mixtures, the structure of each component is can not difference very big.For example, the mixture of various alkoxyl group cyanobiphenyls, Santosol 360 or phenol benzoate is described, and they are usually only different on the chain length of side chain.Yet, the separately synthetic earlier and purifying of each component in these mixtures, and the mixture with required character only just can make in mixing step subsequently.Many liquid crystal compounds are the mixtures that contain the component of different homologue series, but many components are in fact always arranged from same homologue series.Can adding the non-liquid crystal material of lower molecular weight, to reduce kinetic viscosity also be known.
Therefore, in the known method for preparing liquid crystal compound (for example referring to DE-A2927277, DE-A2636684, DE-A2702598, DE-A2701591, DE-A2747113, DE-A2907332, EP-B14840 and German patent application P4408170.7, P4408171.5 and P4405316.9), each component all must be synthesized respectively, so the synthetic work amount is very big.Particularly, consider and to synthesize all these components that much less the space-time yield of these class methods is very low.
An object of the present invention is to seek a kind of like this novel method for preparing liquid crystal compound, it is fairly simple, have less purification step and synthetic in higher space-time yield is arranged.
We find, and this purpose can realize by the method that the present invention prepares the mixture of liquid crystalline cpd.
This method is particularly suitable for the mixture of the liquid crystalline cpd of preparation formula I
(Z
1-Y
1)
m-A
1-Y
2-M-Y
3-A
2-(Y
4-Z
2)
nIn the I formula, Z
1And Z
2Be polymerisable group; Y
1, Y
2, Y
3And Y
4For chemical bond or-O-,-S-,-CO-O-,-O-CO-,-O-CO-O-,-CO-NR-or-NR-CO-bridging unit; R is hydrogen or C
1～C
4Alkyl; M and n are 0 or 1; A
1Under the situation of m=0 hydrogen, can be by Sauerstoffatom or non-conterminous imino-or C
1～C
4The C that alkyl imino cuts off
1～C
30Alkyl or halogen, nitro, cyano group, trifluoromethyl or difluoromethyl, or it is can be by Sauerstoffatom or non-conterminous imino-or C under the situation of m=1
1～C
4The C that alkyl imino cuts off
2～C
20Alkylidene group; A
2Be A
1The group of defined, wherein the condition for m is replaced by corresponding condition for n; And M is the mesomorphic group of being made up of 2～5 saturated or unsaturated 5～7 yuan of carbocyclic rings or heterocyclic group, and carbocyclic ring or heterocycle are by as Y
1～Y
4Identical or the different bridgings unit of regulation links to each other.
These compounds can contain polymerisable group Z
1Or Z
2Preferred group Z
1Or Z
2For example be H
2C=CH-, HC ≡ C-,
-N=C=O ,-N=C=S ,-O-C ≡ N, preferred especially CH
2=CH-,
(terminal short-term is represented free valence bond) wherein R be hydrogen or C
1～C
4Alkyl can be identical or different.
Various group Z in formula I compound
1, Z
2, A
1, A
2With M by bridging unit Y
1, Y
2, Y
3And Y
4Link to each other.Preferred bridging unit be oxygen ,-O-CO-and-CO-O-.
Under the situation of m and/or n=0, A
1And A
2Can be respectively hydrogen or C
1～C
30Alkyl.
This class A that is fit to
1And A
2The example of group is a methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, hexyl, the 2-methyl amyl, heptyl, octyl group, the 2-ethylhexyl, iso-octyl, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl (term iso-octyl, different nonyl, isodecyl and isotridecyl are popular name, derive from the alcohol that makes by oxo process (referring to the Ullmann industrial chemistry encyclopaedia, the 5th edition, the A1 volume, the 290th～293 and A10 volume, the 284th and 285 page)).
Preferably have the alkyl of 1～18 carbon atom, preferably have the alkyl of 4～12 carbon atoms especially.
Further preferred straight chained alkyl.
Alkyl also can be by Sauerstoffatom or non-conterminous imino-or C
1～C
4Alkyl imino cuts off.This class A that is fit to
1And A
2The example of group is the 2-methoxy ethyl, the 2-ethoxyethyl group, 2-propoxy-ethyl, the 2-butoxyethyl group, 2-or 3-methoxy-propyl, 2-or 3-ethoxycarbonyl propyl, 2-or 3-propoxy-propyl group, 2-or 3-butoxy propyl group, 2-or 4-methoxyl group butyl, 2-or 4-oxyethyl group butyl, 2-or 4-butoxy butyl, 3, the 6-dioxaheptyl, 3,6-two oxa-octyl groups, 4,8-two oxa-nonyls, 3,7-two oxa-octyl groups, 3,7-two oxa-nonyls, 4,7-two oxa-octyl groups, 4,7-two oxa-nonyls, 4,8-two oxa-decyls, 3,6,9-trioxa decyl, 3,6,9-trioxa undecyl, 3,6,9,12-four oxa-tridecyls or 3,6,9,12-four oxa-tetradecyls and accordingly with imino-, methyl-imino, the ethyl imino-, propyl group imino-or butyl imino-replace the group of oxygen.
A
1And A
2Also can be halogen, preferred fluorine, chlorine or bromine.But, if A
1And A
2In one be halogen or other little groups, as cyano group, nitro, methyl, ethyl or propyl group, another A so
1Or A
2Be preferably alkyl or alkylidene group than long-chain.
Under the situation of m and/or n=1, A
1Or A
2Be respectively C
2～C
20Alkylidene group, it can be by Sauerstoffatom or non-conterminous imino-or C
1～C
4Alkyl imino cuts off.This class A that is fit to
1And A
2The example of group all is the C that mentions in the situation of m and/or n=0
2～C
20Alkylidene group deutero-group and the alkyl deutero-group of wherein mentioning by oxygen, imino-or alkyl imino partition.
M can be all known mesomorphic groups.Particularly suitable is the group of following formula.
-(T-Y
5) in the r-T formula, T is saturated or unsaturated 5～7 yuan of carbocyclic rings or heterocyclic group, Y
5For as Y
1～Y
4The bridging unit and the r of regulation are 1～4, wherein T and Y
5Can be identical or different.R is preferably 1 or 2.
T also can be the ring system that is replaced by fluorine, chlorine, bromine, cyano group, hydroxyl or nitro.Preferred T is
Particularly preferred mesomorphic group M for example is:
In the formula, R
1, R
2And R
3Be hydrogen, OCH
3, CH
3, F, Cl or Br, particularly preferably be:
The method of the mixture of preparation formula I liquid crystalline cpd for example may further comprise the steps:
A) make the compound of one or more formulas IIa
HY
2-M-Y
3H IIa is with known method and multiple formula III a compound (if only using the compound of a kind of formula IIa) or at least a formula III a compound (if using the compound of multiple formula IIa) reaction
(Z
1-Y
1)
m-A
1-X
1In the IIIa formula, X
1But be hydroxyl, amino, carboxyl or other condensation groups or halogen or other leavings groups, or
B) make one or more formulas IIb compound
(Z
1-Y
1)
m-A
1-Y
2-M
1-X
2H IIb is by compound (if only using a kind of formula IIb compound) or at least a formula III b compound (if using multiple formula IIb compound) reaction of known method and multiple formula III b
X
3-OC-M
2-CO-X
3In the IIIb formula, M
1And M
2For containing the component of 1 or 2 saturated or unsaturated 5～7 yuan of carbocyclic rings or heterocyclic mesomorphic group M, wherein M
1And/or M
2Contain under the situation of two such groups, they pass through as Y
1The bridging unit of regulation links to each other, X
2Be O, S or NR and X
3Be halogen or OH, or
C) make one or more formulas IIc compound
(Z
1-Y
1)
m-A
1-Y
2-M
1-CO-X
3IIc is by known method and multiple formula III c compound (if only using a kind of formula IIc compound) or at least a formula III c compound (if using multiple formula IIc compound) reaction
HX
2-M
2-X
2H IIIc。
Three kinds of methods a), b) and c) the common feature is arranged, promptly at least a starting ingredient contains more than one compounds, but these compounds have given homologue structure formula.Multiple starting ingredient preferably contains 2～10, preferred especially 3～8 kinds of different homologue compounds.
The required performance of ratio in various ingredients between the compound and liquid crystal compound is relevant.Preferably recently optimize required performance by changing consumption.By the total amount of each compound in the component, the consumption of each simplification compound is generally 1～99% (mole), preferred 5～95% (moles), more preferably 10～90% (moles).
The ratio of component I Ia and IIIa, IIb and IIIb and IIc and IIIc is generally 20: 1 to 1: 20, and preferred 5: 1 to 1: 5, more preferably near stoichiometric ratio.
Reaction is carried out in the presence of solvent usually.Particularly suitable solvent is the aprotonic solvent of middle polarity, as pyridine, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, acetone, methylethylketone and propyl group ethyl ketone.
Reaction is preferably carried out at 10～150 ℃, and preferred 30～100 ℃, more preferably 40～80 ℃, and under normal pressure, carry out usually.
The character of the liquid crystal compound that makes is by number and the ratio of mixture and the decision of the structural difference between them of used compound.The structural changes of particularly suitable for example has been to use different lengths A
1And A
2Compound or the compound of different substitute modes.
Method a), b) and c) distinguish by synthesis step, wherein by using multiple initial set to assign to make the random mixture of different compounds.
Method a) in, by by Y
2H and Y
3Mesomorphic group that H replaces and formula III a compound react and make random mixture
(Z
1-Y
1)
m-A
1-X
1IIIaX
1But be the condensation group, as hydroxyl, amino or carboxyl; Or the group for being easy to leave away by nucleophilic substitution reaction, as Br, I or toluenesulphonic acids ester group.Condensation reaction can be carried out with common known method, for example uses carbodiimide or other condensing agents, and this reaction is particularly suitable for generating ester bond or amido linkage.
At method b) in, in mesomorphic group M building-up process, generate random mixture, wherein the centre portions of mesomorphic group M is by carboxyl or the dibasic M of acid halide group
2As starting ingredient.Second component is at M
1Have hydroxyl, sulfydryl, amino or alkylamino on the part, these groups can be in the known manner and M
2Carboxyl or acyl halide group reaction.
At method c) in, in mesomorphic group M building-up process, generate random mixture equally, but with method b) compare M
1And M
2On reactive group reverse.
The inventive method for example also is suitable for the compound of preparation formula IV
In the formula, Z
1, Y
1, Y
2, Y
3, A
1, M and m be as above regulation, and s is 0 or 1, A
3Be C
2～C
20Alkylidene group, it can be by Sauerstoffatom or non-conterminous imino-or C
1～C
4Alkyl imino cuts off, because Z
1, Y
1, Y
2, Y
3, A
1, A
3, M, m and s occur 6 times in formula IV, they can be identical or different.Under the situation of m=1, A
3Can be identical as A
1And A
2Described in group.The mesomorphic group of mentioning in formula I compound, M is preferably benzo [9, the 10] phenanthrene of replacement especially.
The random mixture of various formula IV compounds is by multiple formula IVa compound and 2,3,6,7,10, and 11-hexahydroxy-benzo [9,10] luxuriant and rich with fragrance (IVb) reacts by known method and makes,
(Z
1-Y
1)
m-A
1-(Y
2-M-Y
3-A
3-)
sX
1In the IVa formula, X
1For what as above stipulate,
Reacting available reacts described same procedure suc as formula IIa and IIIa compound and carries out.
The other method that changes liquid crystal compound character is to make random mixture hydrogenation.Hydrogenation can be undertaken by common known method.Hydrogenation is particularly suitable for the aromatic ring structure among the mesomorphic group M is changed into the saturated rings structure.
Beat all is to have now found that there is not the shortcoming of the mixture of conventional preparation by the mixture of the present invention's preparation, even because with regard to purification process, in fact they be equivalent to the purification of simplification compound, particularly in chromatography, in HPLC and MPLC method.
The method that prepare earlier the simplification compound when preparing mixture is compared, the main advantages of the inventive method be simplified synthetic because only need usually prepare single mixture, rather than many single compounds.So space-time yield and solvent-oil ratio significantly descend in the methods of the invention.
The inventive method can also prepare and can not prepare with ordinary method at all, perhaps can only use the mixture of very high expense preparation, because relate to the complexity of the synthetic expense of one-component synthetic ordinary method with mixture, (for example different many starting ingredients) index increases.
On the contrary, the inventive method can be easy to make has the complex mixture of optimizing performance, for example viscosity, time of response, phase scope, double refraction or dielectric anisotropy to application.
Embodiment
Several normally used abbreviations are as follows:
The C crystallization phases
The S smectic phase
The N nematic phase
The I isotropic phase.
Use Mettler microscope warm table (FP800/84) to measure phase transition temperature in conjunction with Leitz polarizing microscope (Ortholux Pol II).
The percentage ratio that provides in mixture is formed all is weight percentage, unless the concrete unit of providing.
All raw materials all have description in the literature, so do not need to illustrate in greater detail the synthetic of them.The present invention only describes the synthesis step of preparation mixture in detail.
Embodiment 1
Synthesizing of mixture 1, it contains 66.7%4-hexyloxybenzoate 4 '-amyl group phenylester and 33.3%4-methoxybenzoic acid 4 '-amyl group phenylester
1.64 gram (0.01 mole) 4-amyl phenols are dissolved in 50 milliliters of toluene and 0.95 gram (0.012 mole) pyridine.Be added dropwise to 1.60 gram (0.00667 mole) 4-hexyloxy benzoyl chlorides and the solution of 0.566 gram (0.00333 mole) 4-methoxy benzoyl chloride in 40 milliliters of toluene under 50 ℃ then.When reacting completely, reaction mixture is transferred in 50 ml waters, tell organic phase then, with dense potassium hydroxide solution one oscillates, make it neutralization.Again organic phase is told, used anhydrous magnesium sulfate drying, remove and desolvate.The output of mixture 1 is 2.8 grams (theoretical value 87%).
Phase behaviour: N 49.1 I
Embodiment 2
Mixture 2 synthetic, it contain 29%4-[anti--4-propyl group cyclohexyl] benzonitrile, 41%4-[be anti--4-amyl group cyclohexyl] benzonitrile and 30%4-[be anti--4-heptyl cyclohexyl] benzonitrile
A) under agitation, will be dissolved in the gram of 3.61 in the ether (0.0258 mole) 4-propyl group pimelinketone, 5.5 gram (0.03272 mole) amyl group pimelinketone and 4.22 gram (0.022 mole) heptyl pimelinketone and be added drop-wise to 18.1 gram (0.1 mole) phenyl-magnesium-bromides in the solution of 200 milliliters of ether.Mixture was heated in water-bath 2 hours, by adding 200 gram trash ices its cooling and hydrolysis.Add fully saturated ammonium chloride then, precipitation is just dissolved.Tell the ether layer, use twice of extracted with diethyl ether water again.With the ethereal solution that dried over sodium sulfate merges, underpressure distillation subsequently.(eluent: sherwood oil, 50～70 ℃ of boiling ranges, the ratio that contains ether is increased to 15%) separates the 4-alkyl-1-benzyl ring hexanone near 1: 1 ratio that generates on the post that silica gel 60 is housed suitable/trans isomer.Cis-product is used H in ethanol
2The hydrogenation of/Raney nickel, and trans product is used palladium/gac (10%Pd) hydrogenation in ethanol.Output: 12.51 grams.
B) will merge by the product mixtures that a) obtains, use Friedel-Crafts method acidylate then.For this reason, 7.21 gram (0.054 mole) aluminum chloride are added to 1, in the 2-ethylene dichloride.Under ice-water cooling 3.7 gram (0.047 mole) Acetyl Chloride 98Min.s are added drop-wise in this suspension carefully, the hydrogenated products that will be dissolved in then in the ethylene dichloride is added dropwise to such speed, always is maintained at about 20 ℃ to cause internal temperature.With mixture at room temperature stir spend the night after, the material in the flask is poured in ice-water carefully, with a small amount of concentrated hydrochloric acid sedimentary aluminium hydroxide is dissolved.Tell organic layer then, with 1, twice of 2-ethylene dichloride aqueous phase extracted.Wash the extract of merging earlier then with water with rare sodium hydroxide solution.After the salt of wormwood drying, remove and desolvate, with column chromatography (silica gel 60, toluene/ethyl acetate 3: 1) purifying.
With haloform reaction the product mixtures that generates is changed into carboxylic acid then.Make carboxyl change into acid amides then, re-use POCl
3Dehydration changes into itrile group.Output: 7.8 grams.
Phase behaviour: N 37 I
Embodiment 3
Synthesizing of mixture 3, it contains 30%2-(4-hexyloxy phenyl)-5-octyl group pyrimidine, 30%2-(4-oxygen in heptan base phenyl)-5-octyl group pyrimidine and 40%2-(4-octyloxyphenyl)-5-octyl group pyrimidine
70.75 (0.25 mole) 2-(4-hydroxy phenyl)-5-octyl group pyrimidine, 9.88 gram (0.082 mole) 1-chlorohexane, 10.63 gram (0.079 mole) 1-chloroheptane, 14.85 gram (0.1 mole) 1-chloro-octane, 41.5 gram (0.3 mole) salt of wormwood and 1 gram potassiumiodide are dissolved in 500 milliliters of dimethyl formamides (DMF), then solution were stirred 4 hours down at 80 ℃.For aftertreatment, reaction mixture is poured in the water, tell organic phase, earlier with half concentrated hydrochloric acid, then with sodium carbonate solution one oscillates, use dried over sodium sulfate.Chromatographic separation on silica gel, as eluent, distillation obtains 94.7 gram mixtures 3 with toluene/ethyl acetate (3: 1).
Embodiment 4
Synthesizing of mixture 4, it contains 11.12%1-[4 '-(4 "-acryloyl-oxy base oxethyl) benzoyloxy]-4-[4 '-(2 "-the acryloxy butoxy) benzoyloxy]-the 3-chlorobenzene, 11.11%1-[4 '-(4 "-the acryloxy butoxy) benzoyloxy]-4-[4 '-(2 "-the acryloxy butoxy) benzoyloxy]-the 3-chlorobenzene, 11.11%1-[4 '-(4 "-the acryloyl-oxy base oxethyl) benzoyloxy]-4-[4 '-(2 "-the acryloxy hexyloxy) benzoyloxy]-the 3-chlorobenzene, 11.11%1-[4 '-(4 "-the acryloxy hexyloxy) benzoyloxy]-4-[4 '-(2 "-the acryloyl-oxy base oxethyl) benzoyloxy]-the 3-chlorobenzene, 11.11%1-[4 '-(4 "-the acryloxy butoxy) benzoyloxy]-4-[4 '-(2 "-the acryloxy hexyloxy) benzoyloxy]-the 3-chlorobenzene, 11.11%1-[4 '-(4 "-the acryloxy hexyloxy) benzoyloxy]-4-[4 '-(2 "-the acryloxy butoxy) benzoyloxy]-the 3-chlorobenzene, 11.11% pair-1,4-[4 '-(4 "-acryloxy butoxy) benzoyloxy]-the 3-chlorobenzene; 11.11% pair-1; 4-[4 '-(4 "-acryloxy hexyloxy) benzoyloxy]-3-chlorobenzene and 11.11% pair-1,4-[4 '-(4 "-the acryloyl-oxy base oxethyl) benzoyloxy]-the 3-chlorobenzene
14.4 gram (0.1 mole) 2-chlorohydroquinones are dissolved in 100 milliliters of pyridines.At room temperature 19.92 gram (0.0666 mole) 4-(O-acryloyl-oxy base oxethyl) Benzoyl chlorides, 18.78 gram (0.0666 mole) 4-(O-acryloxy butoxy) Benzoyl chlorides and the solution of 20.65 gram (0.0666 mole) 4-(O-acryloxy hexyloxy) Benzoyl chlorides in 100 milliliters of toluene slowly are added dropwise to.After adding, when reaction mixture is heated to 60 ℃, and under this temperature, stirred 4 hours.With tlc monitoring reaction process.When reaction is finished, reaction mixture is poured in the mixture of ice and concentrated hydrochloric acid, isolate organic phase, neutralization is then with potassium hydroxide solution one oscillates several.At last, in and organic phase, use dried over sodium sulfate, remove and to desolvate.The output of mixture 4 is 54.1 grams (theoretical value 85%).
91～98 ℃ of I of phase behaviour: N
Embodiment 5
Synthesizing of mixture 5, it contains 15%4 '-n-propyl-4-cyanobiphenyl, 53%4 '-n-pentyl-4-cyanobiphenyl and 32%4 '-n-heptyl-4-cyanobiphenyl
23.31 gram (0.1 mole) 4-bromo biphenyls and 17.5 gram (0.125 mole) aluminum chlorides are dispersed in the anhydrous oil of mirbane.The mixture of 1.57 gram (0.017 mole) propionyl chlorides, 6.5 gram (0.054 mole) valeryl chlorides and 4.31 gram (0.029 mole) oenanthyl chloros is added drop-wise in this mixture with such speed: make temperature be no more than 20 ℃.Reaction mixture was at room temperature stirred 18 hours, pour into subsequently in the mixture of ice and water.The suspension that generates was stirred 30 minutes, add chloroform, tell nitrobenzene layer then.Remove with distillation or vapor distillation and to desolvate.Residue is absorbed in the toluene, uses dried over sodium sulfate.Under reduced pressure remove toluene with distillation.With column chromatography purified product on silica gel 60, use petrol ether/ethyl acetate to make eluent at 9: 1.Output is 18 grams.Spectroscopic data is corresponding to the mixture of compound.
15 grams are dissolved in the Diethylene Glycol with this method synthetic mixture, add 7 milliliter of 90% hydrazine hydrate and 9 and restrain potassium hydroxide, with mixture heating up to 100 ℃.With reaction mixture refluxed 1 hour.Remove 180 ℃ of distillations and to desolvate, until volume is near 14 milliliters.In process of cooling, organism is absorbed in the toluene, washes solution with water, and uses the dried over sodium sulfate organic phase.Distillation under reduced pressure removes desolvates, and residue is absorbed in the ethanol.In order to remove faint yellow impurity,, under reduced pressure remove ethanol then with the solution filtered while hot.
Output: 12.1 grams.
11 grams are dissolved among the DMF with this method synthetic mixture, refluxed 12 hours with 5.57 gram cupric cyanides (I) then.In process of cooling, iron(ic) chloride, concentrated hydrochloric acid and water are added in the reaction mixture, and under 60～75 ℃ with the mixture stir about that generates 20 minutes.Use CH
2Cl
2Extracted organic phase.Wash the organic phase several of generation with water, use dried over sodium sulfate subsequently.With chromatography purified mixture (chloroform give eluent) on silica gel 60.Be further purified with subsequently vacuum distilling.Isolate 120～130 ℃ of cuts.The output of colourless product is 6.1 grams.
Phase behaviour: N 51.7 I
Embodiment 6
Synthesizing of mixture 6, it contains
R in the formula
1Be 43%-CH
2-CH
2-CH
2-CH
2-CH
2-CH
3With 57%
4.86 gram (0.015 mole) hexahydroxy-benzo [9,10] phenanthrene are dissolved in the anaerobic dry DMF.8.66 gram (0.0525 mole) bromohexanes, 9.4 gram (0.0525 mole) vinylformic acid bromo-ethyl esters, 14.4 gram (0.105 mole) salt of wormwood and 0.19 gram thiodiphenylamine are added in this solution, then mixture were stirred 6 hours down at 80 ℃.When reacting completely, make mixture precipitation by adding cold dilute hydrochloric acid, filter out solid with suction filtration, dry in moisture eliminator, and use chromatogram purification, stripping goes out solvent under high vacuum.
Output: 10.9 grams.
Analyze according to NMR, mixture contains 43% hexyloxy and 57% ethyl propenoate side chain, and they all connect at random.
Mixture has plate-like six side's ordered phases.
Embodiment 7
Synthesizing of mixture 7, it contains
R wherein
2Be
Or
6.6 gram (0.02 mole) hexahydroxy-benzo [9,10] phenanthrene are dissolved in the deoxygenated toluene.Then 0.12 mole of pyridine and the solution that are dissolved in gram (0.066 mole) the undecanoyl chlorine of 14.4 in 100 milliliters of toluene and 11.6 gram (0.066 mole) capryl(yl)chlorides are added in this solution.When reacting completely, carefully reaction mixture is poured in the frozen water, filter out the precipitation of generation with suction filtration.Obtain 16.4 gram mixture (productive rates: 63%) through chromatography purification.
Mixture has the discotic mesogenic phase.
Claims (6)
1. method for preparing the mixture of liquid crystalline cpd, wherein at least a starting ingredient contains the mixture of at least two kinds of compounds, makes this mixture with known method and another kind of at least starting ingredient reaction, obtains random mixture.
2. method for preparing the mixture of liquid crystalline cpd, wherein at least a starting ingredient contains the mixture of at least two kinds of compounds, this mixture obtains random mixture with known method and another kind of at least starting ingredient reaction, makes the mixture of generation carry out hydrogenation subsequently.
3. according to the method for the mixture of the liquid crystalline cpd of claim 1 or 2 preparation formula I
(Z
1-Y
1)
m-A
1-Y
2-M-Y
3-A
2-(Y
4-Z
2)
nIn the I formula, Z
1And Z
2Can be the polymeric group; Y
1, Y
2, Y
3And Y
4For chemical bond or-O-,-S-,-CO-O-,-O-CO-,-O-CO-O-,-CO-NR-or-NR-CO-bridging unit; R is hydrogen or C
1～C
4Alkyl; M and n are 0 or 1; A
1Under the situation of m=0, be hydrogen, can be Sauerstoffatom or non-conterminous imino-or C
1～C
4The C that alkyl imino cuts off
1～C
30Alkyl or halogen, nitro, cyano group, trifluoromethyl or difluoromethyl, or be can be by Sauerstoffatom or non-conterminous imino-or C under the situation of m=1
1～C
4The C that alkyl imino cuts off
2～C
20Alkylidene group; A
2Be as above A
1Regulation, wherein use condition to replace to n to the condition of m; And M is the mesomorphic group of being made up of 2～5 saturated or unsaturated 5～7 yuan of carbocyclic rings or heterocyclic group, and carbocyclic ring or heterocyclic group are by as Y
1-Y
4Identical or the different bridgings unit of regulation links to each other, and this method may further comprise the steps:
A) make the compound of one or more formulas IIa
HY
2-M-Y
3If if H IIa is with a kind of formula IIa compound of known method and multiple formula III a compound-only use or at least a formula III a compound-use multiple formula IIa compound-reaction
(Z
1-Y
1)
m-A
1-X
1In the IIIa formula, X
1But be group or halogen or other leavings groups of hydroxyl, amino, carboxyl or other condensations, perhaps
B) make one or more formulas IIb compound
(Z
1-Y
1)
m-A
1-Y
2-M
1-X
2If if H IIb is with a kind of formula IIb compound of known method and multiple formula III b compound-only use or at least a formula III b compound-use multiple formula IIb compound-reaction
X
3-OC-M
2-CO-X
3In the IIIb formula, M
1And M
2Be the component of mesomorphic group M, contain 1 or 2 saturated or unsaturated 5～7 yuan of carbocyclic ring or heterocycle, wherein at M
1And/or M
2Contain under the situation of two such groups, they pass through as Y
1-Y
4The bridging unit of regulation links to each other, X
2Be O, S or NR, and X
3Be halogen or OH, perhaps
C) make one or more formulas IIc compound
(Z
1-Y
1)
m-A
1-Y
2-M
1-CO-X
3If if IIc is with a kind of formula IIc compound of known method and multiple formula III c compound-only use or at least a formula III c compound-use multiple formula IIc compound-reaction
HX
2-M
2-X
2H IIIc。
4. according to the method for claim 3, wherein preparation contains the mixture of the liquid crystalline cpd of formula I, and M is a kind of in the following structural formula in the formula:
In the formula, R
1, R
2And R
3Be hydrogen, OCH
3, CH
3, F, Cl or Br.
5. according to the method for claim 3, wherein preparation contains the mixture of the liquid crystalline cpd of formula I, Z in the formula
1And/or Z
2A kind of in the following structural formula: CH
2=CH-,
6. method according to the mixture of the liquid crystalline cpd of claim 1 or 2 preparation formula IV
In the formula, Z
1, Y
1, Y
2, Y
3, A
1, M and m be that s is 0 or 1, A as regulation in the claim 3
3For can be by Sauerstoffatom or non-conterminous imino-or C
1～C
4The C that alkyl imino cuts off
2-C
20Alkylidene group, wherein Z in formula
1, Y
1, Y
2, Y
3, A
1, A
3, M, m and s occur 6 times, they can be identical or different, wherein
Make multiple formula IVa compound
(Z
1-Y
1)
m-A
1-(Y
2-M-Y
3-A
3-)
sX
1IVa is X wherein
1Be the known method of usefulness and 2,3,6,7,10,11-hexahydroxy-benzo [9,10] luxuriant and rich with fragrance (IVb) reaction as regulation in the claim 3
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4427766.0 | 1994-08-05 | ||
| DE4427766A DE4427766A1 (en) | 1994-08-05 | 1994-08-05 | Process for the preparation of liquid crystalline mixtures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1158142A true CN1158142A (en) | 1997-08-27 |
Family
ID=6525007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95195144A Pending CN1158142A (en) | 1994-08-05 | 1995-07-28 | Process for producing liquid cyrstal mixtures |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0773980A1 (en) |
| JP (1) | JPH10503541A (en) |
| KR (1) | KR970704855A (en) |
| CN (1) | CN1158142A (en) |
| DE (1) | DE4427766A1 (en) |
| WO (1) | WO1996004351A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104662127A (en) * | 2012-09-25 | 2015-05-27 | 富士胶片株式会社 | Liquid crystal composition, method for producing same, and film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0808350B1 (en) * | 1995-02-06 | 2001-07-18 | MERCK PATENT GmbH | Direactive mesogenic compounds and intermediates |
| DE19716822A1 (en) * | 1997-04-22 | 1998-10-29 | Basf Ag | Process for the preparation of polymerizable liquid crystalline compounds |
| DE10061625A1 (en) | 2000-12-11 | 2002-06-13 | Basf Ag | Use of chiral, uncharged metal compounds as dopants for liquid crystalline materials |
| DE10219202A1 (en) | 2002-04-29 | 2003-11-06 | Basf Ag | alkyne compounds |
| DE10229530A1 (en) | 2002-07-01 | 2004-01-15 | Basf Ag | Chiral 3,4-dihydro-2H-pyran compounds |
| CN102066382A (en) | 2008-06-17 | 2011-05-18 | 巴斯夫欧洲公司 | Polymerizable chiral compounds containing 2,6-naphthyl- and isomannite units, and use thereof as chiral dopants |
| EP3053989A4 (en) * | 2013-10-01 | 2017-05-17 | LG Chem, Ltd. | Liquid crystal composition |
| SG11202006971XA (en) | 2018-01-22 | 2020-08-28 | Merck Patent Gmbh | Dielectric materials |
| WO2020078938A1 (en) | 2018-10-18 | 2020-04-23 | Merck Patent Gmbh | Dielectric copolymer materials |
| JP2022505104A (en) | 2018-10-18 | 2022-01-14 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Dielectric copolymer material |
| JP7420502B2 (en) * | 2019-07-24 | 2024-01-23 | 住友化学株式会社 | Polymerizable liquid crystal mixed composition, retardation plate, elliptically polarizing plate, and organic EL display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3872140A (en) * | 1972-07-03 | 1975-03-18 | Eastman Kodak Co | Liquid crystalline compositions and method |
| DE2701591C3 (en) * | 1977-01-15 | 1979-12-20 | Merck Patent Gmbh, 6100 Darmstadt | Hexahydroterphenyl derivatives and their use in liquid crystalline dielectrics |
| ES8800986A1 (en) * | 1985-07-27 | 1987-12-01 | Pfizer | Antiparasitic avermectin and milbemycin derivatives and process for their preparation. |
| JPS62252788A (en) * | 1986-04-25 | 1987-11-04 | Sankyo Co Ltd | 13-hyroxymilbemycin derivative and production thereof |
| US4882084A (en) * | 1986-11-07 | 1989-11-21 | Chisso Corporation | Optically active substituted biphenyl compounds |
| GB8726730D0 (en) * | 1987-11-14 | 1987-12-16 | Pfizer Ltd | Antiparasitic agents |
| GB8815967D0 (en) * | 1988-07-05 | 1988-08-10 | Pfizer Ltd | Antiparasitic agents |
| IT1238230B (en) * | 1989-12-06 | 1993-07-12 | Tecnopart Srl | MIXTURES OF PYRAMID COLUMNAL LIQUID CRYSTALS AND PROCEDURE FOR THEIR PREPARATION |
-
1994
- 1994-08-05 DE DE4427766A patent/DE4427766A1/en not_active Withdrawn
-
1995
- 1995-07-28 KR KR1019970700795A patent/KR970704855A/en not_active Application Discontinuation
- 1995-07-28 JP JP8506181A patent/JPH10503541A/en active Pending
- 1995-07-28 WO PCT/EP1995/003002 patent/WO1996004351A1/en not_active Application Discontinuation
- 1995-07-28 EP EP95927740A patent/EP0773980A1/en not_active Withdrawn
- 1995-07-28 CN CN95195144A patent/CN1158142A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104662127A (en) * | 2012-09-25 | 2015-05-27 | 富士胶片株式会社 | Liquid crystal composition, method for producing same, and film |
| CN104662127B (en) * | 2012-09-25 | 2016-02-24 | 富士胶片株式会社 | Liquid-crystal composition and manufacture method, film, Polarizer and liquid crystal indicator |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970704855A (en) | 1997-09-06 |
| JPH10503541A (en) | 1998-03-31 |
| EP0773980A1 (en) | 1997-05-21 |
| DE4427766A1 (en) | 1996-02-08 |
| WO1996004351A1 (en) | 1996-02-15 |
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