CN1325456C - Perfluoroallyloxy compound and liquid-crystal composition containing the compound - Google Patents
Perfluoroallyloxy compound and liquid-crystal composition containing the compound Download PDFInfo
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- CN1325456C CN1325456C CNB200380100305XA CN200380100305A CN1325456C CN 1325456 C CN1325456 C CN 1325456C CN B200380100305X A CNB200380100305X A CN B200380100305XA CN 200380100305 A CN200380100305 A CN 200380100305A CN 1325456 C CN1325456 C CN 1325456C
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- perfluoroallyloxy
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 179
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 23
- -1 4-cyclohexylidene Chemical group 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 210000002858 crystal cell Anatomy 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 3
- 101150065749 Churc1 gene Proteins 0.000 claims description 3
- 102100038239 Protein Churchill Human genes 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 46
- 238000005160 1H NMR spectroscopy Methods 0.000 description 33
- 238000000034 method Methods 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 22
- 239000012071 phase Substances 0.000 description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 20
- DQFMPTUTAAIXAN-UHFFFAOYSA-N 4,4-dimethyl-1h-imidazol-5-one Chemical compound CC1(C)NC=NC1=O DQFMPTUTAAIXAN-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000862 absorption spectrum Methods 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010189 synthetic method Methods 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 11
- CSNDRFCGMABPKG-UHFFFAOYSA-N 3-cyclohexyl-2-fluorophenol Chemical compound C1(CCCCC1)C=1C(=C(C=CC1)O)F CSNDRFCGMABPKG-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- DZRPAXQRFDZBBP-UHFFFAOYSA-N S(O)(O)=O.[F] Chemical compound S(O)(O)=O.[F] DZRPAXQRFDZBBP-UHFFFAOYSA-N 0.000 description 10
- 229910052740 iodine Inorganic materials 0.000 description 10
- 239000011630 iodine Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- 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 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004990 Smectic liquid crystal Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 3
- 229960003132 halothane Drugs 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- FFIXAFACUXWNCV-UHFFFAOYSA-N 4-[4-(4-propylcyclohexyl)cyclohexyl]phenol Chemical compound C1CC(CCC)CCC1C1CCC(C=2C=CC(O)=CC=2)CC1 FFIXAFACUXWNCV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- AUVLKYVTAAKSDM-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenylsulfanyl)ethene Chemical compound FC(F)=C(F)SC(F)=C(F)F AUVLKYVTAAKSDM-UHFFFAOYSA-N 0.000 description 1
- BDRBSCRINVJXKW-UHFFFAOYSA-N 1-bromo-4-(methoxymethoxy)benzene Chemical compound COCOC1=CC=C(Br)C=C1 BDRBSCRINVJXKW-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- AECMQTCXISKOGO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl]phenol Chemical compound CN(C)CCC1=CC=CC=C1O AECMQTCXISKOGO-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- AHAZEMSUUYFDMM-UHFFFAOYSA-N 4-(4-propylcyclohexyl)phenol Chemical compound C1CC(CCC)CCC1C1=CC=C(O)C=C1 AHAZEMSUUYFDMM-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 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
- GZKVWJAFXAUQFK-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.CC=1NC=CN1 Chemical compound N1=CC=CC2=CC=CC=C12.CC=1NC=CN1 GZKVWJAFXAUQFK-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- AESUECJLDNUSMZ-UHFFFAOYSA-N [Li]CCCC.C1CCCCC1 Chemical compound [Li]CCCC.C1CCCCC1 AESUECJLDNUSMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 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
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-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
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- YBYPQJFOHOKLMB-UHFFFAOYSA-N dimethoxyboron Chemical compound CO[B]OC YBYPQJFOHOKLMB-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000007789 gas Substances 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
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 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 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 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
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
A novel perfluoroallyloxy compound represented by general formula (I) and a liquid crystal composition containing the compound are disclosed. The perfluoroallyloxy compound is useful as a liquid crystal material.
Description
Technical field
The present invention relates to a kind of new Perfluoroallyloxy compound and the liquid-crystal composition that contains this compound, Perfluoroallyloxy compound of the present invention is suitable for makes liquid crystal material.
Background technology
Optics (specific refractory power) anisotropy (Δ n) (following abbreviate as sometimes " Δ n ") as the characteristic of liquid crystalline cpd and the liquid crystal display device of dielectric anisotropy (Δ ε) (following abbreviate as sometimes " Δ ε ") have been utilized, created in large quantities up to now, and being widely used in clock and watch, electronic calculator, various surveying instrument, fascia, word processor, electronic notebook, mobile phone, printer, computer, TV etc., its demand also increases progressively every year.Have the solid of being positioned at phase and liquid phase intermediary inherent mesomorphic phase in the liquid crystalline cpd, its phase morphology is divided into nematic phase, smectic type phase and cholesteric mutually, and what wherein be most widely used now is the nematic phase that is used for liquid-crystal display.In addition, in liquid-crystal display in the used display mode and type of drive, as display mode, up to the present many kinds have been designed, for example known have: dynamic scattering mode (DS type), guest-host type (GH type), twisted nematic (TN type), super-twist nematic (STN type), film transistor type (TFT type) and ferroelectric liquid crystals (FLC, be also referred to as strong dielectricity liquid crystal) etc., as type of drive, known have static drive mode, timesharing type of drive, active matrix drive mode and a double frequency type of drive etc.
In general, the anisotropy (Δ ε) that adopts specific inductivity is inversely proportional to for the square root of the Δ ε of the threshold voltage of the field effect mode liquid crystal indicator of positive liquid-crystal composition and this liquid-crystal composition, and this is that people are known.Particularly in recent years, battery-operated mode is becoming main flow for twisted nematic (TN type), particularly requires the lower liquid crystal material of threshold values, and for this reason, the liquid crystal material with bigger positive Δ ε is very important.
Because nitrile compound such as 4-(to alkyl-cyclohexyl) benzonitrile has bigger Δ ε, it is used as the liquid crystal material that TN liquid crystal cell or super-twist nematic (STN) element are used.Yet because these nitrile compounds are brought ionic impurity easily into, so it can not be used for requirement high resistivity (10
12Ω cm or more than) active matrix drive in.Therefore, need a kind of have high resistivity, liquid crystal material that Δ ε is bigger.
In addition, the viscosity influence response speed of liquid crystal of liquid crystalline cpd, the low more then response speed of its viscosity is fast more.Therefore, as the Synergist S-421 95 of liquid crystalline cpd, preferably low viscous.
And then, the anisotropy of specific refractory power has very big influence to the visual characteristics of liquid crystal display device, and contrast gradient increases to it is characterized in that becoming anisotropy greatly then, and anisotropy diminishes then that field range enlarges, in recent years, the tendency that has the liquid crystal material that preferred use field range is wide, Δ n is less.
In addition, the influence of NI point shows the temperature range of mesomorphic state, at high temperature also can demonstrate mesomorphic state even the NI point uprises then.
Because containing the compound of fluothane (oxygen) base as end group has positive dielectric anisotropy and is difficult to bring into ionic impurity, therefore in the active matrix drive mode, need especially, it is known as a kind of material that shows high resistivity, high voltage holding ratio (VHR), low ion density etc., has proposed various schemes about the compound of introducing fluothane (oxygen) base up to now.For example open clear 55-72143 communique the spy, the spy opens clear 55-40660 communique, the spy opens clear 61-197563 communique, the spy opens clear 56-12322 communique, the spy opens clear 58-154532 communique, the spy opens clear 58-177939 communique, the spy opens clear 58-210045 communique, the spy opens clear 59-78129 communique, in the Te Biaoping 6-500343 communique etc. various compounds with perfluoroalkyl have been proposed, and shown to propose in the flat 1-503145 communique to use the scheme of the electron optics display device of the compound that contains fluoroalkyl the spy, and then show flat 3-502942 communique and the spy opens in flat 10-67989 number the spy, proposed to use the compound active matrix drive liquid crystal display device that contains fluothane (oxygen) base.
Yet compounds that contain fluoroalkyl of these concrete records can't meet the demands aspect low viscosity and the wide nematic phase scope having.
Summary of the invention
The purpose of this invention is to provide a kind of may be mixed in in the nematic liquid crystalline material, have the new liquid crystal material of the liquid-crystal composition of the anisotropy (Δ ε) of anisotropy (Δ n), high-k of low-refraction and high NI point (wide nematic phase scope) with formation.
The present inventor etc. found that by deep research the Perfluoroallyloxy compound can reach above-mentioned purpose.
The present invention just is being based on above-mentioned discovery and is finishing, the invention provides a kind of shown in following general formula (I) the Perfluoroallyloxy compound and the liquid-crystal composition that contains this compound.
(R in the formula
1Expression R, RO, ROCO or RCOO, R represents alkyl.This alkyl can contain unsaturated link(age), in this group-and CH
2-can by-O-,-CO-or-COO-replaces, and the hydrogen atom of part or all can be replaced by halogen atom or cyano group.A
1And A
2Represent 1 independently of one another, 4-phenylene [CH=can be replaced by-N=, and the hydrogen atom of part or all can be replaced by halogen atom or cyano group], 1,4-cyclohexylidene [CH
2-can by-O-or-S-replaces, and the hydrogen atom of part or all can be replaced by halogen atom or cyano group], 2,6-naphthylidene or 2, the inferior naphthane base of 6-.Z1 represent singly-bound ,-COO-,-OCO-,-CH
2CH
2-,-CH=CH-,-(CH
2)
4-,-CH
2O-,-OCH
2-,-(CH
2)
3O-,-O (CH
2)
3-,-CH=CHCH
2O-,-OCH
2CH=CH-,-C ≡ C-,-CF
2O-or-OCF
2-.B represents that a part of hydrogen atom can be replaced by halogen atom or cyano group in singly-bound or alkylidene group, this group.N is 1～3 integer, A when n is 2 or 3
1And Z
1Can be different mutually.)
Embodiment
In the aforementioned formula (I) of expression Perfluoroallyloxy compound of the present invention, R
1Expression R, RO, ROCO or RCOO.The alkyl of representing as R, can list for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, vinyl, allyl group, butenyl, ethynyl, proyl, butynyl, methoxymethyl, ethoxyl methyl, the propoxy-methyl, butoxymethyl, methoxy ethyl, ethoxyethyl group, perfluoro-methyl, the perfluor ethyl, perfluoro propyl, one methyl fluoride, difluoromethyl, 2,2, the 2-trifluoromethyl, perfluorovinyl sulfide, the perfluor allyl group, sec.-propyl, the 1-methyl-propyl, the 2-methyl-propyl, the 2-butyl methyl, the 3-methyl butyl, the 2-methyl amyl, the 3-methyl amyl, the 2-ethylhexyl, 2-propyl group amyl group, 1-methyl amyl etc.R
1Preferably unsubstituted alkyl, unsubstituted alkenyl or-O-CF
2CF=CF
2Base.
In the aforementioned formula (I)-(A
1-Z
1) n-A
2The structure more specifically of-Ji is as follows, but Perfluoroallyloxy compound of the present invention is not limited to these.
-CY-CY-
-CY-PH-
-PH-PH-
-CY-PH3F-
-CY-PH3，5-diF-
-CY-PH2，3-diF-
-CY-CY-CY-
-CY-CY-PH-
-CY-PH-PH-
-PH-PH-PH-
-CY-CY-PH3F-
-CY-CY-PH3，5-diF-
-CY-CY-PH2，3-diF-
-CY-PH3F-PH-
CY-PH3，5-diF-PH-
CY-PH2，3-diF-PH-
-CY-PH-PH-CY-
-PH-CH
2CH
2-CY-CY-
-CY-PH-CH
2CH
2-PH-
-CY-CY-CH
2CH
2-PH-
-CY-CH
2CH
2-CY-
-PH-CH
2CH
2-CY-
-PH-C≡C-PH-
-CY-PH-C≡C-PH-
-PH-COO-PH-
-CY-COO-PH-
-CY-CY-COO-PH-
-PH-COO-PH-PH-
-Pym-PH-
-Dio-PH-
-PH-Pym-
-PH-Dio-
-PH-Pyr-
-PH-CF
2O-PH-
-PH-CH
2O-PH-
-PH-CH＝CHCH
2O-PH-
-PH-(CH
2)
3O-PH-
-CY-COO-Nap-
-CY-COO-DHN-
What in addition, the breviary mark in the above-mentioned formula was represented respectively is following ring structure.
In aforementioned formula (1), A
1And A
2Preferably be unsubstituted 1 independently of one another, 4-phenylene, unsubstituted 1, the 4-cyclohexylidene is perhaps preferably at A
1And A
2In replaced one of at least by the fluorine atom list or dibasic 1, the 4-phenylene.In addition, Z
1Preferably singly-bound or-CF
2O-.
In addition, the alkylidene group as B in the aforementioned formula (I) represents can list methylene radical, ethylidene, a fluorine methylene radical, a fluorine ethylidene, 1,2-difluoro ethylidene, 1,1,2-trifluoro ethylidene etc.
O.1～21 the preferred object lesson of Perfluoroallyloxy compound of the present invention as aforementioned formula (I) expression can list following compound N, but is not limited to these compounds.In addition, the R in following compound
1The same with the situation in the aforementioned formula (I).
Compound N o.3
Compound N o.5
Compound N o.8
Compound N o.10
Compound N o.13
Compound N o.19
Compound N o.20
In Perfluoroallyloxy compound of the present invention, the compound that is made of unsubstituted phenyl ring and/or unsubstituted cyclohexane ring (for example compound N o.1～4,11 and 12) viscosity is low and have a high NI point.This external lateral location is replaced by fluorine and the compound that contains phenyl ring (for example compound N o.13～21) that forms is favourable in the device of the mesomorphic phase scope that shows broad, wherein 2, the compound that contains phenyl ring (for example compound N o.21) that the 3-position is replaced by fluorine simultaneously is suitable for the electro-optical device material of making vertical orientating type and guest-host type owing to have negative Δ ε.Other compound also is the compound with various advantageous feature.
There is no particular limitation for the manufacture method of Perfluoroallyloxy compound of the present invention, for example can make by the manufacture method shown in following reaction formula.
(in the above-mentioned reaction formula, R
1, A
1, A
2, Z
1, n and B represent and the same group of general formula (I) that X represents halogen atom or FSO
2O-, BASE represents alkali, solv. represents solvent.)
Wherein, can list metal hydroxidess such as sodium hydroxide, potassium hydroxide as the alkali that in above-mentioned reaction formula, uses; Metal hydride such as lithium hydride, sodium hydride; Triethylamine, ethyl dimethyl amine, propyl-dimethyl amine, N, N '-lupetazin, pyridine, picoline, 1,8-diazabicyclo (5.4.0) undecene-1 (DBU), benzyl dimethyl amine, 2-(dimethylamino ethyl) phenol (DMP-10), 2,4, the amine of 6-three (dimethylamino methyl) phenol (DMP-30) etc. etc.
In this etherification procedure shown in the above-mentioned reaction formula, widely used is the sodium alkylate (sodium phenylate) that preparation is earlier formed by alkylol cpd (phenol) and sodium hydroxide etc., with its Williamson method with the halogenated alkyl reaction, in the present invention, preferably at amine compound, particularly in the presence of tertiary amines such as triethylamine, halogenide or the reaction of fluorine sulfite with phenolic compound and perfluoropropane can obtain high conversion like this.In when reaction, preferably with temperature of reaction in-80～80 ℃ scope, the reaction times is selected respectively in 0～20 hour scope aptly.
In addition,, can list, for example methylimidazole quinoline, tetrahydrofuran (THF), dimethyl formamide, diethyl ether, dimethyl sulfone isopolarity solvent as operable solvent in above-mentioned reaction formula; Low polar solvent such as toluene, ethyl acetate etc.
In the manufacture method shown in the above-mentioned reaction, oxy-compound (1) and perfluorochemical (2) are 20/1～1/20 at mass ratio (the former/latter) preferably, more preferably use in 1/1～1/10 the scope.
Alkali is to be preferably 0.1～5.0 mole of %, the amount use of 1.0～2.0 moles of % more preferably with respect to oxy-compound (I).
The consumption of solvent has no particular limits, and with respect to 100 mass parts of the total amount of oxy-compound (1) and perfluorochemical (2), preferably uses solvent aptly in the scope of 10～500 mass parts.
Perfluoroallyloxy compound of the present invention by being engaged in present known liquid crystalline cpd or liquid crystal similar compound or their mixture (mother liquor crystalline substance) thus in constitute liquid-crystal composition of the present invention.In addition, liquid-crystal composition of the present invention also can only be made of Perfluoroallyloxy compound of the present invention.
As this mother liquor crystalline substance, can list, for example the compound shown in following general formula (II) or its mixture.
(in the formula, R represents that hydrogen atom, carbonatoms are 1～8 alkyl, alkoxyl group, alkenyl, alkenyloxy, alkynyl, alkynyloxy group, alkoxyalkyl, chain alkoxy or alkoxy carbonyl, and perhaps they also can be replaced Y by halogen atom, cyano group
2Group shown in expression cyano group, halogen atom or the R, Y
1, Y
3And Y
4Be hydrogen atom, halogen atom or cyano group, Z
1And Z
2Represent independently of one another singly-bound (Direct Bonding) ,-CO-O-,-O-CO-,-CH
2O-,-OCH
2-,-CH
2CH
2-,-CH=CHCHCH
2O-,-CF
2O-,-OCF
2-or-C ≡ C-, p represents 0,1 or 2, ring D, ring E and ring F represent phenyl ring, cyclohexane ring, cyclohexene ring, pyrimidine ring or two alkane rings independently of one another.)
Thereby the object lesson as compound shown in the above-mentioned general formula (II) can list following compound etc.In addition, R, Y in following compound
1, Y
2, Y
3And Y
4Has same implication with the group in the above-mentioned general formula (II).
The content of Perfluoroallyloxy compound of the present invention in liquid-crystal composition of the present invention has no particular limits, can select suitable amount according to target property, preferably in the scope of 1～100 quality %, select, select in the scope particularly preferably in 5～90 quality %.
The liquid-crystal composition that contains Perfluoroallyloxy compound of the present invention is enclosed in the liquid crystal cell (liquid crystal cell), can constitute various electron optics display element devices.As electron optics display element device, for example go for, dynamic scattering mode (DS), guest-host type (GH), twisted nematic (TN), super-twist nematic (STN), film transistor type (TFT), thin film diode type (TFD), ferroelectric liquid crystals type (FLC), anti ferroelectric liquid crystal type (AFLC), high polymer dispersed liquid crystal type (PDLC), vertical orientating type (VA), copline is switched various display formats such as (IPS), also goes for the static drive mode in addition, the timesharing type of drive, various type of drive such as active matrix drive mode and double frequency type of drive.
Perfluoroallyloxy compound of the present invention and known various material compounding can be used for the diverse various electron optics display devices of various characteristics values such as torsion(al)angle, pitch angle, dielectric anisotropy (Δ ε), resistance value, nematic phase range, viscosity, average dielectric constant, coefficient of viscosity, voltage retention, alignment films.
About electron optics display device or used therein liquid-crystal composition, for example be disclosed in the spy and open flat 10-67989 communique, Te Biaoping 3-502942 communique, Te Kaiping 3-85532 communique, Te Kaiping 4-296387 communique, Te Biaoping 6-501517 communique, Te Biaoping 10-512914 communique, Te Kaiping 9-125063 communique, Te Kaiping 11-29771 communique, Te Kaiping 10-245559 communique, the spy opens the 2000-351972 communique, the spy opens the 2002-285157 communique, the spy opens the 2002-302673 communique, special table 2002-533526 communique, the spy opens the 2002-114978 communique, Te Biaoping 5-501735 communique, the spy opens the 2002-193853 communique, the spy opens the 2002-193852 communique, special table 5-500683 communique, the spy opens the 2002-201474 communique, Te Kaiping 10-204016 communique, the spy opens the 2000-73062 communique, the spy opens the 2000-96056 communique, the spy opens the 2001-31971 communique, the spy opens the 2000-80371 communique, the spy opens the 2001-354967 communique, the spy opens the 2000-351972 communique, the international brochure that discloses No. 99/21815, the international brochure that discloses No. 99/21816, the international brochure that discloses No. 97/36847, No. 5456860 specification sheets of United States Patent (USP), No. 5578241 specification sheets of United States Patent (USP), No. 662502 specification sheetss of European patent, in No. 10117224 specification sheetss of German Patent etc., Perfluoroallyloxy compound of the present invention can be used in combination with these electro-optical devices that proposed or liquid-crystal composition.
Use the electron optics display device of Perfluoroallyloxy compound of the present invention can be used for the purposes of clock and watch, electronic calculator, surveying instrument, automobile instrument, duplicating machine, camera, office automation instrument, laptop computer, mobile phone etc.In addition, can also be used for purposes in addition, for example light modulation window, optical gate, polarization beam apparatus etc.
Below by embodiment the present invention is described in more detail.But the present invention is not limited to following examples.
＜embodiment 1〉compound N (R o.1
1=n-C
3H
7) synthetic method
Reaction formula 1 according to shown in following carries out o.1 (R of compound N by following method
1=n-C
3H
7) synthetic.
Reaction formula 1
Under nitrogen gas stream, add 1.2g (4 mmole) 4-[4-(4-n-propyl cyclohexyl) cyclohexyl] after phenol (1) and 7g dimethyl-imidazolinone (DMI) dissolve, add 1.03g (4 mmole) 3-iodine perfluor 1-propylene (2), to wherein adding 0.48g (4.8 mmole) triethylamine (TEA), reacted 2 hours again.
Try to achieve reaction conversion ratio from the area percentage of the gas-chromatography of reaction solution, the area percentage of raw material (1) is 9%, and the area percentage of target product (3) is 91%.
Adding ethyl acetate and hydrochloric acid neutralize in reaction solution then, confirm as neutrality after the washing, with the sal epsom dehydration, after the filtration, use the toluene replacement solvent then, after silica treatment, concentrating under reduced pressure carries out Tim Koogle-Luo Er (Kugel-rohr) distillation and crystallization successively and separates out (the 1st stage: ethyl acetate/methanol=1/18, the 2 stage: acetone), make with extra care, obtain target product (3) (white crystal, output 0.8g (productive rate 47%), purity 99.9%).
The target product that obtains (3) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.1 (R of compound N according to its result
1=n-C
3H
7).Analytical results is as follows.
[IR]
2920cm
-1, 2850cm
-1, 1794cm
-1, 1609cm
-1, 1508cm
-1, 1447cm
-1, 1389cm
-1, 1319cm
-1, 1223cm
-1, and 1196cm
-1
[
1H-NMR]
7.3-7.0(m，4H)，2.6-2.3(m，1H)，2.2-0.4(m，26H)
＜embodiment 2〉compound N (R o.1
1=n-C
3H
7) synthetic method
Reaction formula 2 according to shown in following carries out o.1 (R of compound N by following method
1=n-C
3H
7) synthetic.
Reaction formula 2
Under nitrogen gas stream, add 2.71g (5.65 mmole) sodium hydroxide and 30ml tetrahydrofuran (THF) (THF), drip and be dissolved with 13g (43.5 mmole) 4-[4-(4-n-propyl cyclohexyl) cyclohexyl] 120ml tetrahydrofuran (THF) (THF) solution of phenol (1).Stir after 30 minutes, drip 11.2g (43.5 mmole) 3-iodine perfluor 1-propylene (2), reacted 2 hours, be warming up to 70 ℃ of reactions 1 hour again.
Try to achieve reaction conversion ratio from the area percentage of the gas-chromatography of reaction solution, the area percentage of raw material (1) is 53%, and the area percentage of target product (3) is 47%.
Refining according to method similarly to Example 1, from reaction solution, make target product (3).To the target product (3) that obtains with infrared absorption spectrum (IR) and
1H-NMR analyzes, and analytical results is identical in fact with embodiment 1, and assertive goal product (3) is o.1 (R of compound N thus
1=n-C
3H
7).
＜embodiment 3〉compound N (R o.1
1=n-C
3H
7) synthetic method
Reaction formula 3 according to shown in following carries out o.1 (R of compound N by following method
1=n-C
3H
7) synthetic.
Reaction formula 3
Under nitrogen gas stream, add 13g (43.5 mmole) 4-[4-(4-n-propyl cyclohexyl) cyclohexyl] phenol (1), add after 24g (200 mmole) triethylamine and 84g dimethyl-imidazolinone (DMI) be warmed up to 40 ℃ and dissolving, drip 9.2g (40 mmole) 3-iodine perfluor 1-propylene (2), reacted 3 hours.
Try to achieve reaction conversion ratio from the area percentage of the gas-chromatography of reaction solution, the area percentage of raw material (1) is 0%, and the area percentage of target product (3) is 100%.
Refining according to method similarly to Example 1, from reaction solution, make target product (3).To the target product (3) that obtains with infrared absorption spectrum (IR) and
1H-NMR analyzes, and analytical results is identical in fact with embodiment 1, and assertive goal product (3) is o.1 (R of compound N thus
1=n-C
3H
7).
＜embodiment 4〉compound N (R o.1
1=n-C
3H
7) synthetic method
Reaction formula 4 according to shown in following carries out o.1 (R of compound N by following method
1=n-C
3H
7) synthetic.
Reaction formula 4
Under nitrogen gas stream, add 12g (40 mmole) 4-[4-(4-n-propyl cyclohexyl) cyclohexyl] phenol (1), after 19g (40 mmole) sodium hydroxide and 50g dimethyl-imidazolinone (DMI) and the dissolving, drip 10.3g (40 mmole) 3-iodine perfluor 1-propylene (2), reacted 3 hours.
Try to achieve reaction conversion ratio from the area percentage of the gas-chromatography of reaction solution, the area percentage of raw material (1) is 66%, and the area percentage of target product (3) is 34%.
Refining according to method similarly to Example 1, from reaction solution, make target product (3).To the target product (3) that obtains with infrared absorption spectrum (IR) and
1H-NMR analyzes, and analytical results is identical in fact with embodiment 1, and assertive goal product (3) is o.1 (R of compound N thus
1=n-C
3H
7).
＜embodiment 5〉compound N (R o.2
1=n-C
3H
7) synthetic method
Reaction formula 5 according to shown in following carries out o.2 (R of compound N by following method
1=n-C
3H
7) synthetic.
Reaction formula 5
With 2.35g (8 mmole) 4-[4-(4-n-propyl cyclohexyl) phenyl] after phenol (1) is dissolved in dimethyl-imidazolinone (DMI), add 2.41g (9.36 mmoles, 1.17 equivalent), 3-iodine perfluor 1-propylene (2) is under water-cooled, in 5 minutes, drip 1.37g (13.5 mmoles, 1.7 equivalent) behind the triethylamine, reacted 2 hours.
Add ethyl acetate and hydrochloric acid neutralization then in reaction solution, the washing back after the filtration, obtains dark brown solid with the sal epsom dehydration after the filtering and concentrating.To this dark brown solid, carry out post successively and handle (toluene/hexane=1/1), Tim Koogle-Luo Er distillation and crystallization and separate out (ethyl acetate/methanol=4/6) and make with extra care, obtain target product (3) (white crystal, output 1.5g (productive rate 44%), purity 100%).
The target product that obtains (3) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.2 (R of compound N according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
[IR]
2923cm
-1, 2851cm
-1, 1790cm
-1, 1609cm
-1, 1497cm
-1, 1385cm
-1, 1315cm
-1, 1219cm
-1, 1153cm
-1, 1011cm
-1, 826cm
-1, and 791cm
-1
[
1H-NMR]
7.7-7.1(m，8H)，2.7-2.3(m，1H)，2.1-0.8(m，16H)
＜embodiment 6〉compound N (R o.3
1=n-C
3H
7) synthetic method
Reaction formula 6 according to shown in following carries out o.3 (R of compound N by following method
1=n-C
3H
7) synthetic.
Reaction formula 6
In argon metathetical flask, add 2.0g (9.2 mmole) 4-(4-n-propyl cyclohexyl) phenol (1), 2.37g (9.2 mmoles, 1.0 equivalent) 3-iodine perfluor 1-propylene (2) and 10g dimethyl-imidazolinone (DMI) are made into mixed solution, in the above-mentioned mixed solution in ice-cooled stirring down, drip 1.2g (1.2 mmoles, 1.3 equivalent) behind the triethylamine, again ice-cooled reaction down 10 minutes.Use water treatment, extract hexane after, the washing until becoming neutrality, after dried over mgso, heat up in a steamer and desolvate.Carry out post successively and handle (hexane), distillation and crystallization and separate out (methyl alcohol) and make with extra care, obtain target product (3) (colourless liquid, output 0.7g, purity 99.8%, productive rate 24.1%).
The target product that obtains (3) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.3 (R of compound N according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
[IR]
2859cm
-1, 2924cm
-1, 1851cm
-1, 1790cm
-1, 1670cm
-1, 1593cm
-1, 1508cm
-1, 1450cm
-1, 1385cm
-1, 1315cm
-1, 1219cm
-1, 1157cm
-1, and 1018cm
-1
[
1H-NMR]
7.3-7.1(m，4H)，1.9-0.9(m，17H)
＜embodiment 7 〉
Add to any one in o.1～3 of the compound N that in embodiment 1,5 and 6, obtains respectively in the mother liquor brilliant 1 or mother liquor crystalline substance 2 of following composition with 10 quality %, form liquid-crystal composition, the liquid-crystal composition that obtains is measured NI point, optical anisotropy (Δ n), viscosity (η), dielectric anisotropy (Δ ε) respectively, and then obtain their extrapolated value.Measurement result is shown in [table 1], and extrapolated value is shown in [table 2].In addition, in [table 1] and [table 2], the NI point when " NI ↑ " expression heats up, the NI point during " NI ↓ " expression cooling.
Mother liquor crystalline substance 1
Mass parts
Mother liquor crystalline substance 2
[table 1]
| The mother liquor crystalline substance | Compound N o. | NI↑ | NI↓ | Δn | η | Δε |
| 2 | - | 52 | 52 | 0.119 | 23 | 10.8 |
| 2 | No.1 (embodiment 1) | 58 | 57 | 0.112 | 22 | 10.2 |
| 1 | - | 84.3 | 83.4 | 0.0866 | 23.3 | 4.95 |
| 1 | No.1 (embodiment 1) | 91.8 | 91.0 | 0.0872 | 21.4 | 4.88 |
| 1 | No.2 (embodiment 5) | 90.1 | 89.6 | 0.0939 | 22.2 | 4.96 |
| 1 | No.3 (embodiment 6) | 73.9 | 73.0 | 0.0837 | 18.5 | 4.72 |
[table 2]
| The mother liquor crystalline substance | Compound N o. | NI↑ | NI↓ | Δn | η | Δε |
| 1 | No.1 (embodiment 1) | 159 | 159 | 0.0926 | 4.14 | 4.3 |
| 2 | No.1 (embodiment 1) | 110 | 102 | 0.049 | 12.6 | 4.8 |
| 1 | No.2 (embodiment 5) | 142 | 145 | 0.1596 | 12.5 | 5.0 |
| 1 | No.3 (embodiment 6) | -19.7 | -20.7 | 0.0576 | -25.5 | 2.7 |
According to the result of [table 1] and [table 2], can confirm that in Perfluoroallyloxy compound of the present invention, 3 cyclic cpds viscosity are low and have high NI point, and 2 cyclic cpdss are expected to have the effect of the viscosity that reduces the mother liquor crystalline substance.
＜embodiment 8〉compound N (R o.4
1=C
2H
5) synthetic method
Reaction formula 7 according to shown in following carries out o.4 (R of compound N by following method
1=C
2H
5) synthetic.
Reaction formula 7
In argon metathetical flask, add 0.57g (2.71 mmole) 4-(4-ethyl cyclohexyl) hexalin (1) and 1.65g (16.3 mmoles, 6.0 equivalents) triethylamine (TEA), reflux 1 hour.Be cooled to-20 ℃ then, in 1 hour, drip 1ml dimethyl-imidazolinone (DMI) solution that has dissolved 0.70g (11.6 mmoles, 4.3 equivalents) 3-iodine perfluor 1-propylene (2), at room temperature stirred 14 hours.Add then after 4% aqueous hydrochloric acid and toluene carries out separatory, washing, clean, wash again, confirm as neutrality with sodium hydrogen carbonate solution.After dried over mgso, heat up in a steamer and desolvate.It is refining to carry out silicagel column processing (hexane), obtains target product (3) (colourless liquid, output 0.26g, purity 99.9%, productive rate 27.3%).
The target product that obtains (3) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.4 (R of compound N according to its result
1=C
2H
5).Analytical results is as follows respectively.
[IR]
2924cm
-1, 2855cm
-1, 2360cm
-1, 2341cm
-1, 1790cm
-1, 1450cm
-1, 1381cm
-1, 1315cm
-1, 1223cm
-1, 1173cm
-1, 1026cm
-1, 991cm
-1, 960cm
-1, 934cm
-1, 899cm
-1, 795cm
-1, and 664cm
-1
[
1H-NMR]
4.5-4.0(m，1H)，2.2-0.4(m，24H)
＜embodiment 9〉compound N (R o.19
1=n-C
5H
11) synthetic method
Reaction formula 8 according to shown in following carries out o.19 (R of compound N by following method
1=n-C
5H
11) synthetic.
Reaction formula 8
In the flask of thorough drying, add 2g (5.77 mmole) 4-[4-(4-n-pentyl cyclohexyl)] cyclohexyl-2-fluorophenol (1) and 14g dimethyl-imidazolinone (DMI) and 4g (3.95 mmole) triethylamine (TEA), stir down ice-cooled.Be cooled to 3 ℃, the 2.4g that slowly drips (1.8 equivalent) perfluor allyl group fluorine sulfite (2).Drip after 15 minutes, ethyl acetate and water are mixed carry out oily water separation.After dried over mgso, slough solvent, add hexane and filter out useless material, carry out post processing and alcohol crystal successively and separate out and make with extra care, obtain target product (3) (colorless solid, output 0.6g, purity 99.9%, productive rate 21.5%).
The target product that obtains (3) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.19 (R of compound N according to its result
1=n-C
5H
11).Analytical results is as follows respectively.
[IR]
2920cm
-1, 2851cm
-1, 1790cm
-1, 1597cm
-1, 1512cm
-1, 1447cm
-1, 1385cm
-1, 1319cm
-1, 1265cm
-1, 1211cm
-1, 1150cm
-1, 1115cm
-1, 1018cm
-1, 953cm
-1, 864cm
-1, and 795cm
-1
[
1H-NMR]
7.2-6.8(m，3H)，2.6-2.2(m，1H)，2.1-0.7(m，1H)
＜embodiment 10〉compound N (R o.18
1=n-C
5H
11) synthetic method
Reaction formula 9 according to shown in following carries out o.18 (R of compound N by following method
1=n-C
5H
11) synthetic.
Reaction formula 9
With 5g (13.7 mmoles, 1.00 4-[4-(4-n-pentyl cyclohexyl) cyclohexyl equivalent)]-1,6-fluorophenol (1) and 2.08g (20.6 mmoles, 1.50 triethylamine and 25g dimethyl-imidazolinone (DMI) dissolving becoming mixed solution equivalent), with ice-cooled this mixed solution, 3.54g (13.7 mmoles, 1.00 equivalents) 3-iodine perfluor 1-propylene (2) is added drop-wise in ice-cooled above-mentioned mixed solution in stirring down, again ice-cooled reaction down 10 minutes.Dripping hydrochloric acid then, the oily water separation after washing again with dried over mgso, is sloughed solvent.It is carried out silicagel column processing (hexane), Tim Koogle-Luo Er distill (158-215 ℃, 0.7-1.0mmHg), carry out crystallization with ethyl acetate/methanol (1/1) and separate out, obtain target product (3) (colorless solid, output 2.07g, purity 99.8%, productive rate 30.5%).
The target product that obtains (3) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.18 (R of compound N according to its result
1=n-C
5H
11).Analytical results is as follows respectively.
[IR]
2924cm
-1, 2853cm
-1, 1790cm
-1, 1630cm
-1, 1601cm
-1, 1514cm
-1, 1447cm
-1, 1385cm
-1, 1346cm
-1, 1319cm
-1, 1202cm
-1, 1148cm
-1, 1113cm
-1, 1018cm
-1, 959cm
-1, 943cm
-1, 895cm
-1, 851cm
-1, 824cm
-1, 725cm
-1, 708cm
-1, 665cm
-1, 646cm
-1, 619cm
-1, and 527cm
-1
[
1H-NMR]
6.9-6.7(d，2H)，2.6-0.5(m，31H)
＜embodiment 11〉compound N (R o.14
1=n-C
5H
11) synthetic method
Reaction formula 10 according to shown in following carries out o.14 (R of compound N by following method
1=n-C
5H
11) synthetic.
Reaction formula 10
In argon metathetical flask, add 7.98g (0.03 mole) 5-(4-n-pentyl cyclohexyl)-1,3-phenyl-difluoride (1) and 65ml tetrahydrofuran (THF) (THF), be cooled to below-50 ℃ with methyl alcohol-carbonic acid, add (2.6 moles/l) stirred 1 hour of 13.5ml (0.0351 mole) n-Butyl Lithium-cyclohexane solutions.Drip 3.57g (0.0343 mole, 1.14 equivalents) dimethoxy boron down at-50 ℃ then, stirred 1 hour.Get back to room temperature then, drip 11ml aqueous hydrochloric acid (1.2 moles/l) after the oily water separation, with salt washing 3 times, after dried over mgso, slough solvent obtain 6.62g 4-(4-n-pentyl cyclohexyl)-2,6-phenyl-difluoride ylboronic acid (2).
Under argon gas stream, in flask, add 4.56g (0.021 mole) 4-methoxymethoxy-1-bromobenzene (3), 5.3g (0.021 mole) sodium bicarbonate, 0.147g (0.021 mole) Pd[PPh
3]
2Cl
2Complex compound, 20ml toluene and 40ml water are warming up to 75～85 ℃, drip the 20ml ethanol that has dissolved 6.51g (0.021 mole) boric acid (2), react 1 hour again.After the cooling, carry out oily water separation, confirm as neutrality, after dried over mgso, slough solvent, obtain 8.64g4-[4-(4-n-pentyl cyclohexyl)-2,6-phenyl-difluoride base]-1-methoxymethoxy benzene (4).
In flask, add 8.45g methoxymethoxy compound (4), 4.38g hydrochloric acid and 35ml tetrahydrofuran (THF) (THF), 70 ℃ of following stirring reactions 2 hours, carry out oily water separation with toluene-water, confirm as neutrality, after dried over mgso, slough solvent, separate out with the ethyl acetate crystallization, obtain 4.9g 4-[4-(4-n-pentyl cyclohexyl)-2,6-phenyl-difluoride base] phenol (5).
In flask, add the dissolving of 2.87g (8 mmole) phenol body (5) and 15g dimethyl-imidazolinone (DMI), to wherein adding 2.06g (8 mmole) 3-iodine perfluor 1-propylene (6), drip 1.21g (8 mmole) triethylamine (TEA) down at 29～33 ℃, reacted 2 hours down at 25～30 ℃.After the cooling, carry out oily water separation, confirm as neutrality after the washing, use dried over mgso, slough solvent with ethyl acetate-water.They are carried out post is handled (hexane), the Tim Koogle distills (215 ℃, 0.35mmHg), separate out, obtain target product (7) (colorless solid, output 0.44g, purity 99.8%, productive rate 10.2%) with ethyl acetate/methanol (1/3) crystallization.
The target product that obtains (7) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.14 (R of compound N according to its result
1=n-C
5H
11).Analytical results is as follows respectively.
[IR]
2928cm
-1, 2851cm
-1, 1794cm
-1, 1639cm
-1, 1566cm
-1, 1485cm
-1, 1431cm
-1, 1385cm
-1, 1315cm
-1, 1218cm
-1, 1188cm
-1, 1161cm
-1, 1057cm
-1, 1011cm
-1, 949cm
-1, 845cm
-1, 791cm
-1, 725cm
-1, 656cm
-1, 613cm
-1, and 529cm
-1
[
1H-NMR]
7.7-7.1(m，4H)7.0-6.7(m，2H)，2.7-2.3(m，1H)，2.2-0.8(m，20H)
＜embodiment 12〉compound N (R o.11
1=n-C
3H
7) synthetic method
Reaction formula 11 according to shown in following carries out o.11 (R of compound N by following method
1=n-C
3H
7) synthetic.
Reaction formula 11
In the flask of argon replaces, add 6.2g (26.1 mmole) 4-(4-propyl group cyclohexyl)] hexahydrobenzyl alcohol (1) and 15.8g (156 mmoles, 6.0 triethylamine (TEA) equivalent), reflux 1 hour, after being cooled to-20 ℃, 7.9g (30.8 mmoles, 1.18 equivalents) the 3-iodine perfluor 1-propylene (2) that slowly drips at room temperature stirs.Add aqueous hydrochloric acid (hydrochloric acid 9.6g/ water 24g) and 30ml toluene and carry out separatory, washing back dried over mgso, slough solvent, carry out post and handle (hexane), obtain target product (3) (colourless transparent liquid, output 2.1g, purity 99.8%, productive rate 21.6%).
The target product that obtains (3) through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as o.11 (R of compound N according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
[IR]
2920cm
-1, 2851cm
-1, 2623cm
-1, 1790cm
-1, 1450cm
-1, 1412cm
-1, 1377cm
-1, 1315cm
-1, 1211cm
-1, 1173cm
-1, 1033cm
-1, 964cm
-1, 941cm
-1, 899cm
-1, 806cm
-1, 783cm
-1, 741cm
-1, 664cm
-1, 613cm
-1, and 513cm
-1
[
1H-NMR]
3.9-3.7(d，2H)，2.2-0.5(m，27H)
＜embodiment 13 〉
Show in following [table 3] be Perfluoroallyloxy compound of the present invention phase transition temperature (℃), optical anisotropy (Δ n) and dielectric anisotropy (Δ ε).Optical anisotropy (Δ n) and dielectric anisotropy (Δ ε) are that the liquid-crystal composition that obtains add the test compound of 10 quality % in above-mentioned mother liquor crystalline substance 1 is measured the extrapolated value that obtains.
In addition, in following [table 3], compound N is (R o.1
1=n-C
5H
11), 5,8,9 and 10 be that method according to previous embodiment 1 obtains.Compound N o.17,19 (R
1=n-C
3H
7) and 21 be that method according to previous embodiment 9 obtains.Compound N o.15,16,18 (R
1=n-C
3H
7) and 20 be that method according to previous embodiment 10 obtains.
[table 3]
| Compound N o. | R 1 | Phase transition temperature (℃) | Δn | Δε |
| No.1 (embodiment 1) | n-C 3H 7 | Sm→157.3→N→174.2→I | 0.0926 | 4.3 |
| No.1 | n-C 5H 11 | Sm→171.7→N→178.7→I | 4.3 | |
| No.2 (embodiment 5) | n-C 3H 7 | C→45.5→Sm→169.6→N→ 180.4→1 | 0.1596 | 5.0 |
| No.3 (embodiment 6) | n-C 3H 7 | Liquid | 0.0576 | 2.7 |
| No.4 (embodiment 8) | C 2H 5 | Liquid | 0.0331 | 2.97 |
| No.5 | n-C 3H 7 | C→77→I | ||
| No.8 | n-C 4H 9 | C→59.6→I | ||
| No.9 | n-C 6H 13 | C→33→Sm→53.4→I | ||
| No.10 | n-C 8H 17 | Sm→195→I | ||
| No.11 (embodiment 12) | n-C 3H 7 | Liquid | 0.0141 | 0.238 |
| No.14 (embodiment 11) | n-C 5H 11 | C→67.1→Sm→84.9→N→ 114.1→1 | 0.126 | 8.47 |
| No.15 | n-C 3H 7 | C→31.8→N→132.4→1 | 0.1458 | 8.00 |
| No.16 | n-C 5H 11 | Liquid | 0.0536 | 5.24 |
| No.17 | n-C 5H 11 | Liquid | 0.061 | 4.55 |
| No.18 | n-C 3H 7 | Sm→41.2→N→166.6→1 | 0.1006 | 7.3 |
| No.18 (embodiment 10) | n-C 5H 11 | N→165.2→1 | 0.0916 | 7.35 |
| No.19 | n-C 3H 7 | Sm→49.8→N→170.8→1 | 0.1036 | 5.0 |
| No.19 (embodiment 9) | n-C 5H 11 | Sm→44.4→N→170.3→1 | 0.101 | 6.0 |
| No.20 | n-C 3H 7 | N→146.2→1 | ||
| No.21 | n-C 5H 11 | Sm→101.5→N→168.3→1 |
C: solid phase, Sm: smectic type phase, N: nematic phase, I: isotropic liquid phase
Can confirm that from the result of [table 3] Perfluoroallyloxy compound of the present invention is suitable for makes liquid crystal material.
＜embodiment 14 〉
Use Perfluoroallyloxy compound of the present invention according to the preparation of the blending ratio shown in [table 4] liquid-crystal composition, measure NI point, optical anisotropy (Δ n), dielectric anisotropy (Δ ε) and viscosity (η).These measurement results are shown in [table 4].
[table 4]
| Liquid crystalline cpd | Liquid-crystal composition *1 | ||||
| 1 | 2 | 3 | 4 | ||
| C2-CY-CY-PH-3，4-diF | 16 | 13 | 11 | ||
| C3-CY-CY-PH-3，4-diF | 17 | 14 | 12 | ||
| C5-CY-CY-PH-3，4-diF | 16 | 13 | 12 | ||
| C3-CY-PH-PH-3，4-diF | 14 | 5 | |||
| C5-CY-PH-PH-3，4-diF | 14 | 5 | |||
| C2-CY-C≡C-PH-3，4-diF | 2 | ||||
| C5-CY-PH-Cl | 7 | ||||
| C3-CY-PH-OCH 3 | 5 | ||||
| C7-CY-PH-F | 4 | ||||
| C5-CY-PH-F | 5 | ||||
| C3-CY-PH-OCF 2CF＝CF 2(compound N o.3) | 14 | 10 | 5 | ||
| C3-CY-PH3F-OCF 2CF＝CF 2(compound N o.17) | 15 | ||||
| C5-CY-PH3F-OCF 2CF＝CF 2(compound N o.17) | 13 | 15 | 25 | ||
| C3-CY-CY-PH3F-OCF 2CF＝CF 2(compound N o.19) | 16 | ||||
| C5-CY-CY-PH3F-OCF 2CF＝CF 2(compound N o.19) | 16 | ||||
| C3-CY-CY-PH3，5-diF-OCF 2CF＝CF 2(compound N o.18) | 14 | 11 | |||
| C5-CY-CY-PH3，5-diF-OCF 2CF＝CF 2(compound N o.18) | 3 | 18 | 14 | 12 | |
| C3-CY-PH-PH3，5-diF-OCF 2CF＝CF 2(compound N o.15) | 2 | 12 | |||
| Measurement result | The NI point (℃) | 83.0 | 94.7 | 88.8 | 85.2 |
| Δn(25℃) | 0.0991 | 0.0870 | 0.0852 | 0.0872 | |
| Δε(25℃) | 5.1 | 4.9 | 4.9 | 5.4 | |
| η(mPa·s) | 20 | 17 | 14 | 17 | |
CY:1,4-cyclohexylidene, PH:1, the 4-phenylene, Cn: carbonatoms is the straight chained alkyl of n, does not replace if specify the position of substitution then to be meant in the 4-position.
*1; The numeric representation mass parts.
From [table 4] as can be seen, the Perfluoroallyloxy compound of the application of the invention, can form have low viscosity, the liquid-crystal composition of low optical anisotropy (Δ n), high dielectric anisotropy (Δ ε) and high NI point (wide nematic phase scope).
＜embodiment 15〉compound N 0.22 (R
1=n-C
3H
7) synthetic method and phase transition temperature
According to＜embodiment 9〉the compound N of method shown in being prepared as follows (R o.22
1=n-C
3H
7).The compound that obtains through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as target compound No.22 (R according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
[IR]
2924cm
-1, 2851cm
-1, 1794cm
-1, 1593cm
-1, 1566cm
-1, 1497cm
-1, 1323cm
-1, 1146cm
-1, 1018cm
-1, 903cm
-1, 829cm
-1, 802cm
-1, and 544cm
-1
[
1H-NMR]
7.6-7.2(m，7H)，2.8-2.3(m，1H)，2.1-0.8(m，16H)
The compound N that obtains is (R o.22
1=n-C
3H
7) phase transition temperature (℃) as follows.
C→46→Sm→129→N→152→I
＜embodiment 16〉compound N (R o.23
1=n-C
5H
11) synthetic
According to＜embodiment 9〉the compound N of method shown in being prepared as follows (R o.23
1=n-C
5H
11).The compound that obtains through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as target compound No.23 (R according to its result
1=n-C
5H
11).Analytical results is as follows respectively.
[IR]
3437cm
-1, 2932cm
-1, 2858cm
-1, 1909cm
-1, 1794cm
-1, 1609cm
-1, 1497cm
-1, 1462cm
-1, 1385cm
-1, 1319cm
-1, 1153cm
-1, 1064cm
-1, 1011cm
-1, 818cm
-1, 787cm
-1, 733cm
-1, 694cm
-1, 664cm
-1, 629cm
-1, 574cm
-1, and 502cm
-1
[
1H-NMR]
7.7-7.1(m，8H)，2.8-2.5(t，2H)，1.9-0.7(m，9H)
＜embodiment 17〉compound N (R o.24
1=n-C
3H
7) synthetic
According to＜embodiment 9〉the compound N of method shown in being prepared as follows (R o.24
1=n-C
3H
7).The compound that obtains through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as target compound No.24 (R according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
[IR]
2963cm
-1, 2936cm
-1, 2874cm
-1, 1790cm
-1, 1628cm
-1, 1601cm
-1, 1567cm
-1, 1528cm
-1, 1501cm
-11443cm
-1, 1385cm
-1, 1319cm
-1, 1277cm
-1, 1234cm
-1, 1207cm
-1, 1146cm
-1, 1111cm
-1, 1042cm
-1, 1018cm
-1, 895cm
-1, 864cm
-1, 837cm
-1, 667cm
-1, and 536cm
-1
[
1H-NMR]
7.5-7.1(m，6H)，2.7-2.5(t，2H)，1.9-1.5(m，2H)，1.1-0.9(t，3H)
＜embodiment 18〉compound N (R o.25
1=n-C
3H
7) synthetic
According to＜embodiment 9〉the compound N of method shown in being prepared as follows (R o.25
1=n-C
3H
7).The compound that obtains through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as target compound No.25 (R according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
Compound N o.25
[IR]
2963cm
-1, 2936cm
-1, 2874cm
-1, 1790cm
-1, 1593cm
-1, 1566cm
-1, 1497cm
-1, 1466cm
-1, 1431cm
-1, 1385cm
-1, 1319cm
-1, 1265cm
-1, 1200cm
-1, 1150cm
-1, 1119cm
-1, 1018cm
-1, 903cm
-1, 876cm
-1, 833cm
-1, 795cm
-1, 667cm
-1, and 532cm
-1
[
1H-NMR]
7.6-7.1(m，7H)，2.7-2.5(t，2H)，1.9-1.5(m，2H)，1.1-0.9(t，3H)
＜embodiment 19〉compound N (R o.26
1=n-C
3H
7) synthetic
According to＜embodiment 9〉the compound N of method shown in being prepared as follows (R o.26
1=n-C
3H
7).The compound that obtains through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as target compound No.26 (R according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
Compound N o.26
[IR]
3445cm
-1, 2936cm
-1, 2858cm
-1, 1794cm
-1, 1639cm
-1, 1585cm
-1, 1504cm
-1, 1454cm
-1, 1389cm
-1, 1327cm
-1, 1300cm
-1, 1215cm
-1, 1196cm
-1, 1150cm
-1, 1107cm
-1, 1050cm
-1, 1018cm
-1, 949cm
-1, 856cm
-1, 822cm
-1, 799cm
-1, 710cm
-1, 663cm
-1, 629cm
-1, 606cm
-1, 571cm
-1, 544cm
-1, and 525cm
-1
[
1H-NMR]
7.2-6.4(m，4H)，2.7-0.5(m，17H)
＜embodiment 20〉compound N (R o.27
1=n-C
3H
7) synthetic
According to＜embodiment 9〉the compound N of method shown in being prepared as follows (R o.27
1=n-C
3H
7).The compound that obtains through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as target compound No.27 (R according to its result
1=n-C
3H
7).Analytical results is as follows respectively.
[IR]
3437cm
-1, 2924cm
-1, 2851cm
-1, 1794cm
-1, 1593cm
-1, 1504cm
-1, 1389cm
-1, 1319cm
-1, 1261cm
-1, 1207cm
-1, 1150cm
-1, 1099cm
-1, 1022cm
-1, 957cm
-1, 872cm
-1, 795cm
-1, and 621cm
-1
[
1H-NMR]
7.3-6.7(m，4H)，2.9-2.5(m，1H)，2.1-0.5(m，21H)
＜embodiment 21〉o.28 synthetic of compound N
According to＜embodiment 9〉the compound N of method shown in being prepared as follows o.28.The compound that obtains through infrared absorption spectrum (IR) and
1H-NMR analyzes, and regards as target compound No.28 according to its result.Analytical results is as follows respectively.
Compound N o.28
[IR]
3433cm
-1, 1794cm
-1, 1497cm
-1, 1389cm
-1, 1319cm
-1, 1227cm
-1, 1150cm
-1, 1069cm
-1, 1015cm
-1, and 787cm
-1
[
1H-NMR]
7.7-7.1(m，8H)
＜embodiment 22 〉
Show in following [table 5] be Perfluoroallyloxy compound of the present invention phase transition temperature (℃), optical anisotropy (Δ n) and dielectric anisotropy (Δ ε).Optical anisotropy (Δ n) and dielectric anisotropy (Δ ε) are that the liquid-crystal composition that obtains add the compound of 10 quality % in above-mentioned mother liquor crystalline substance 1 is measured the extrapolated value that obtains.
In addition, in following [table 5], compound N o.15, No.18 and No.19 be that method according to previous embodiment 9 obtains.
[table 5]
| Compound N o. | R 1 | Phase transition temperature (℃) | Δn | Δε |
| No.15 | C 2H 5 | C→53.8→N→104.6→I | 0.1374 | 7.1 |
| No.15 | n-C 4H 9 | C→32.4→N→127.1→I | 0.0924 | 6.17 |
| No.15 | n-C 5H 11 | Sm→27.9→N→132.6→I | 0.1508 | 8.27 |
| No.18 | n-C 4H 9 | C→33.6→N→165.8→I | 0.924 | 6.17 |
| No.19 | C 2H 5 | Sm→45.0→N→140.8→I | 0.094 | 4.5 |
| No.23 (embodiment 16) | n-C 5H 11 | C→98.2→I | 0.1174 | 2.15 |
| No.24 (embodiment 17) | n-C 3H 7 | Liquid | 0.1024 | 6.3 |
| No.25 (embodiment 18) | n-C 3H 7 | C→33.4→I | 0.11 | 3.7 |
| No.26 (embodiment 19) | n-C 3H 7 | C→37.6→N→60.4→I | 0.0889 | 12.6 |
| No.27 (embodiment 20) | n-C 3H 7 | Sm→133.7→N→159.1→I | 0.106 | 1.23 |
| No.28 (embodiment 21) | PFA | C→65.9→I | 0.103 | 0.9 |
C: solid phase
Sm: smectic type phase
N: nematic phase
I: isotropic liquid phase
PFA：-OCF
2CF＝CF
2
＜cooperation example 〉
The cooperation example of the liquid-crystal composition that is to use Perfluoroallyloxy compound of the present invention that [table 6]～[table 11] shows.Wherein, in [table 6]～[table 11], CY is 1, and 4-cyclohexylidene, PH are 1, and 4-phenylene, Pym are 5, and 2-pyrimidine, Cn are that carbonatoms is the straight chained alkyl of n, does not replace if specify the position of substitution then to be meant in the 4-position.
All have low viscosity, low-refraction anisotropy (Δ n), high dielectric anisotropy (Δ ε) and high NI point (wide nematic phase scope) according in the liquid-crystal composition that cooperates shown in [table 6]～[table 11] any one.
[table 6]
| Liquid crystalline cpd | Compound N o. | Mass parts |
| C5-CY-PH-OCF 2CF＝CF 2 | No.3 | 13 |
| C7-CY-PH-F | 10 | |
| C2-CY-CY-PH-OCF 3 | 10 | |
| C3-CY-CY-PH-OCF 3 | 13 | |
| C4-CY-CY-PH-OCF 3 | 7 | |
| C5-CY-CY-PH3F-OCF 2CF＝CF 2 | No.19 | 11 |
| C3-CY-CY-CH 2CH 2-PH-3，4-diF | 10 | |
| C5-CY-CY-CH 2CH 2-PH-3，4-diF | 8 | |
| C3-CY-CY-CH 2CH 2-PH-F | 11 | |
| C3-CY-PH-PH2F-CY-C3 | 3 | |
| C5-CY-PH-PH2F-CY-C3 | 2 | |
| C5-CY-PH-PH2F-CY-C5 | 2 |
[table 7]
| Liquid crystalline cpd | Compound N o. | Mass parts |
| C2-CY-CY-PH3F-OCF 2CF＝CF 2 | No.19 | 13 |
| C3-CY-CY-PH3，4-diF | 15 | |
| C2-CY-PH-CN | 12 | |
| C3-CY-PH3，5-F-OCF 2CF＝CF 2 | No.16 | 10 |
| CH 3OCH 2-CY-PH-CN | 6 | |
| C2-PH-COO-PH-CN | 6 | |
| C2-Pym-PH-C2 | 4 | |
| C6-Pym-PH-OCF 2CF＝CF 2 | No.9 | 4 |
| C3-CY-CY-PH-CN | 6 | |
| C2-CY-CY-PH3F-CN | 12 | |
| C3-CY-CY-PH3F-CN | 12 |
[table 8]
| Liquid crystalline cpd | Compound N o. | Mass parts |
| C3-CY-PH-CN | 10 | |
| C3-CY-PH3，5-diF-CN | 10 | |
| C2-PH-COO-PH3F-CN | 2 | |
| C3-PH-COO-PH3F-CN | 3 | |
| C5-CY-CY-CH＝CH 2 | 8 | |
| CH 2＝CH-CY-CY-PH-CH 3 | 14.5 | |
| C5-CY-CY-PH-OCF 2CF＝CF 2 | No.1 | 14 |
| C3-PH-C≡C-PH-OCF 2CF＝CF 2 | No.5 | 5 |
| C2-O-PH-C≡C-PH-CH 3 | 5 | |
| C3-O-PH-C≡C-PH-CH 3 | 5 | |
| C2-O-PH-C≡C-PH-F | 4 | |
| CH 2＝CH-CY-PH-C≡C-PH-C2 | 10 | |
| CH 3CH＝CH-CY-PH-C≡C-PH-C2 | 9.5 |
[table 9]
| Liquid crystalline cpd | Compound N o. | Mass parts |
| C2-CY-CY-PH3，4-diF | 8 | |
| C3-CY-CY-PH3，4-diF | 8 | |
| C5-CY-CY-PH3F-OCF 2CF＝CF 2 | No.19 | 8 |
| C2-CY-PH-CN | 8 | |
| C3-CY-PH-CN | 2 | |
| C3-CY-PH-O-C2 | 7 | |
| C3-CY-PH-OCF 2CF＝CF 2 | No.3 | 7 |
| C3-CY-COO-PH-O-C2 | 6 | |
| CH 3OCH 2-CY-CY-C3 | 5 | |
| C2-CY-CY-PH-CH 3 | 6 | |
| C3-CY-CY-PH-C3 | 14 | |
| C3-CY-CY-PH-OCH 3 | 4 | |
| C3-CY-CY-COO-PH-F | 3 | |
| C5-CY-CY-COO-PH-OCF 2CF＝CF 2 | * | 3 |
| C3-CY-CY-PH-F | 4 |
*Perfluoroallyloxy compound of the present invention
[table 10]
| Liquid crystalline cpd | Compound N o. | Mass parts |
| C3-CY-CY-C2 | 10 | |
| C3-CY-CY-C5 | 10 | |
| C7-CY-PH-F | 5 | |
| C3-CY-PH-C4 | 9 | |
| C3-CY-PH2，3-diF-OCF 2CF＝CF 2 | * | 11 |
| C5-CY-PH2，3-diF-O-C2 | 15 | |
| C3-CY-CY-PH-di2，3-diF-OCF 2CF＝CF 2 | No.21 | 10 |
| C5-CY-CY-PH2，3-diF-O-C2 | 12 | |
| C3-CY-CY-PH2，3-diF-CH 3 | 7 | |
| C5-CY-CY-PH2，3-diF-CH 3 | 11 |
[table 11]
| Liquid crystalline cpd | Compound N o. | Mass parts |
| C3-CY3E-CY-C3 | 5 | |
| C3-CY-CY-CF 3 | 5 | |
| CH 2＝CH-CY-CY-C5 | 8 | |
| C3-CY-PH-O-CF 2CF＝CF 2 | No.3 | 12 |
| C2-CY-CY-PH3F-O-CF 2CF＝CF 2 | No.19 | 11 |
| C3-CY-CY-PH3F-O-CF 2CF＝CF 2 | No.19 | 14 |
| C3-CY-CY-PH3，4-diF | 13 | |
| C3-CY-CY-PH3，5-diF-O-CF 2CF＝CH 2 | No.18 | 17 |
| C4-CY-CY-PH-CF 2H | 10 | |
| C2-CY-PH-PH3，4，5-triF | 5 |
The liquid crystal material of the liquid-crystal composition that the suitable electron optics display device that acts on any display mode and any type of drive of Perfluoroallyloxy compound of the present invention is used.
Claims (10)
1. Perfluoroallyloxy compound shown in following general formula (I),
R in the formula
1Expression R, RO, ROCO or RCOO; R represents alkyl, and this alkyl can contain unsaturated link(age), in this group-and CH
2-can by-O-,-CO-or-COO-replaces, and the hydrogen atom of part or all can be replaced by halogen atom or cyano group; A
1And A
2Expression independently of one another: 1, the 4-phenylene, and this 1, in the 4-phenylene-CH=can be replaced by-N=, and the hydrogen atom of part or all can be replaced by halogen atom or cyano group; 1, the 4-cyclohexylidene, 1, in the 4-cyclohexylidene-CH
2-can by-O-or-S-replaces, and the hydrogen atom of part or all can be replaced by halogen atom or cyano group, 2,6-naphthylidene or 2, the inferior naphthane base of 6-; Z
1The expression singly-bound ,-COO-,-OCO-,-CH
2CH
2-,-CH=CH-,-(CH
2)
4-,-CH
2O-,-OCH
2-,-(CH
2)
3O-,-O (CH
2)
3-,-CH=CHCH
2O-,-OCH
2CH=CH-,-C ≡ C-,-CF
2O-or-OCF
2-; B represents that a part of hydrogen atom can be replaced by halogen atom or cyano group in singly-bound or alkylidene group, this group; N is 1～3 integer, when n is 2 or 3, and each A
1Between can be mutually different, each Z
1Between also can be mutually different.
2. as the Perfluoroallyloxy compound of claim 1 record, wherein in described general formula (I), R
1Be unsubstituted alkyl.
3. as the Perfluoroallyloxy compound of claim 2 record, wherein in described general formula (I), R
1Be unsubstituted alkenyl.
4. as the Perfluoroallyloxy compound of claim 1 record, wherein in described general formula (I), R
1For-O-CF
2CF=CF
2Base.
5. as the Perfluoroallyloxy compound of each record in the claim 1～4, wherein in described general formula (I), A
1And A
2Be unsubstituted 1 independently of one another, 4-phenylene or unsubstituted 1,4-cyclohexylidene.
6. as the Perfluoroallyloxy compound of each record in the claim 1～4, wherein in described general formula (I), at A
1And A
2In at least one replaced or dibasic 1 the 4-phenylene by the fluorine atom list.
7. as the Perfluoroallyloxy compound of each record in the claim 1～4, wherein in described general formula (I), Z
1It is singly-bound.
8. as the Perfluoroallyloxy compound of each record in the claim 1～4, wherein in described general formula (I), Z
1Be-CF
2O-.
9. contain liquid-crystal composition just like the Perfluoroallyloxy compound of each record in the claim 1～8.
10. the electron optics display device of the liquid-crystal composition of claim 9 record being enclosed liquid crystal cell and forming.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4223501A1 (en) * | 1992-07-17 | 1994-01-20 | Merck Patent Gmbh | New di:fluoro-allyl-benzene cpds. and use in liquid crystal media - esp. dielectric for electrical optical display with favourable optical and dielectric anisotropy and good low temp. property |
| CN1263927A (en) * | 2000-03-10 | 2000-08-23 | 中国科学院上海有机化学研究所 | Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process |
-
2003
- 2003-12-04 CN CNB200380100305XA patent/CN1325456C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4223501A1 (en) * | 1992-07-17 | 1994-01-20 | Merck Patent Gmbh | New di:fluoro-allyl-benzene cpds. and use in liquid crystal media - esp. dielectric for electrical optical display with favourable optical and dielectric anisotropy and good low temp. property |
| CN1263927A (en) * | 2000-03-10 | 2000-08-23 | 中国科学院上海有机化学研究所 | Fluoric diphenylacetylene liquid crystal compound containing side chain of olifinic oxygen and its preparing process |
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