CN1168378A - 咪唑并噻唑 - Google Patents
咪唑并噻唑 Download PDFInfo
- Publication number
- CN1168378A CN1168378A CN97110015A CN97110015A CN1168378A CN 1168378 A CN1168378 A CN 1168378A CN 97110015 A CN97110015 A CN 97110015A CN 97110015 A CN97110015 A CN 97110015A CN 1168378 A CN1168378 A CN 1168378A
- Authority
- CN
- China
- Prior art keywords
- imidazo
- thiazole
- phenyl
- oxygen
- heptyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UMZCLZPXPCNKML-UHFFFAOYSA-N 2h-imidazo[4,5-d][1,3]thiazole Chemical class C1=NC2=NCSC2=N1 UMZCLZPXPCNKML-UHFFFAOYSA-N 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
- 239000004990 Smectic liquid crystal Substances 0.000 claims abstract description 21
- 239000002019 doping agent Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 82
- 239000001301 oxygen Substances 0.000 claims description 82
- -1 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene Chemical group 0.000 claims description 69
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000004973 liquid crystal related substance Substances 0.000 claims description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 239000011737 fluorine Substances 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims description 2
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- 239000000203 mixture Substances 0.000 abstract description 37
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000003098 cholesteric effect Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract 3
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- UFBBWLWUIISIPW-UHFFFAOYSA-N imidazo[2,1-b][1,3]thiazole Chemical compound C1=CSC2=NC=CN21 UFBBWLWUIISIPW-UHFFFAOYSA-N 0.000 description 90
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 48
- 239000012071 phase Substances 0.000 description 31
- 229910052717 sulfur Inorganic materials 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 150000003254 radicals Chemical group 0.000 description 10
- 208000035126 Facies Diseases 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000013459 approach Methods 0.000 description 6
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- SHKOAJLZFDIOFZ-UHFFFAOYSA-N C(CCCCCCCC)C1=CC=C(C=C1)C1=CN2C(S1)=NC=C2 Chemical compound C(CCCCCCCC)C1=CC=C(C=C1)C1=CN2C(S1)=NC=C2 SHKOAJLZFDIOFZ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- BAKIBSRDBASFAQ-UHFFFAOYSA-N imidazo[2,1-b][1,3]thiazole-6-carboxylic acid Chemical compound C1=CSC2=NC(C(=O)O)=CN21 BAKIBSRDBASFAQ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 3
- SZEXAAJOCGUGDC-UHFFFAOYSA-N octanoyloxidanyl Chemical compound CCCCCCCC([O])=O SZEXAAJOCGUGDC-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- PSEJBIODJNSJNT-UHFFFAOYSA-N CCCCC([O])=O Chemical group CCCCC([O])=O PSEJBIODJNSJNT-UHFFFAOYSA-N 0.000 description 2
- KPOJZODITNLLNF-UHFFFAOYSA-N CCCCCCCCOC(=O)C1=CN2C=CSC2=N1 Chemical compound CCCCCCCCOC(=O)C1=CN2C=CSC2=N1 KPOJZODITNLLNF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229950003476 aminothiazole Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 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 2
- 239000003999 initiator Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YCBSHDKATAPNIA-FNORWQNLSA-N (e)-non-3-ene Chemical compound CCCCC\C=C\CC YCBSHDKATAPNIA-FNORWQNLSA-N 0.000 description 1
- KPADFPAILITQBG-VQHVLOKHSA-N (e)-non-4-ene Chemical compound CCCC\C=C\CCC KPADFPAILITQBG-VQHVLOKHSA-N 0.000 description 1
- IICQZTQZQSBHBY-HYXAFXHYSA-N (z)-non-2-ene Chemical compound CCCCCC\C=C/C IICQZTQZQSBHBY-HYXAFXHYSA-N 0.000 description 1
- YCBSHDKATAPNIA-ALCCZGGFSA-N (z)-non-3-ene Chemical compound CCCCC\C=C/CC YCBSHDKATAPNIA-ALCCZGGFSA-N 0.000 description 1
- KPADFPAILITQBG-CLFYSBASSA-N (z)-non-4-ene Chemical compound CCCC\C=C/CCC KPADFPAILITQBG-CLFYSBASSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- OBLDMTWAUKEKMX-UHFFFAOYSA-N 2-heptylimidazo[2,1-b][1,3]thiazole-6-carboxylic acid Chemical compound C1=C(C(O)=O)N=C2SC(CCCCCCC)=CN21 OBLDMTWAUKEKMX-UHFFFAOYSA-N 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- LYBKDCIFNDPOSC-UHFFFAOYSA-N 5-heptyl-1,3-thiazole Chemical compound CCCCCCCc1cncs1 LYBKDCIFNDPOSC-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- BHHKLTAACFWROS-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)[O].[O] Chemical compound C(C1=CC=CC=C1)(=O)[O].[O] BHHKLTAACFWROS-UHFFFAOYSA-N 0.000 description 1
- FLLHEJPVLSEJRX-UHFFFAOYSA-N C(CCC)OC(CCCCCC)(OCCCCCC)OCCCCC Chemical compound C(CCC)OC(CCCCCC)(OCCCCCC)OCCCCC FLLHEJPVLSEJRX-UHFFFAOYSA-N 0.000 description 1
- GBDBODWFEXFNAF-UHFFFAOYSA-N CCC(Cl)CC([O])=O Chemical compound CCC(Cl)CC([O])=O GBDBODWFEXFNAF-UHFFFAOYSA-N 0.000 description 1
- NNWJAMJFYWIICH-UHFFFAOYSA-N CCCC(C)CC([O])=O Chemical compound CCCC(C)CC([O])=O NNWJAMJFYWIICH-UHFFFAOYSA-N 0.000 description 1
- GHWZQNVQKPKSPU-UHFFFAOYSA-N CCCCC(C)CC([O])=O Chemical compound CCCCC(C)CC([O])=O GHWZQNVQKPKSPU-UHFFFAOYSA-N 0.000 description 1
- VLVJYPJEXDLHQZ-UHFFFAOYSA-N CCCCCC(C)CC([O])=O Chemical compound CCCCCC(C)CC([O])=O VLVJYPJEXDLHQZ-UHFFFAOYSA-N 0.000 description 1
- NJBUFSIQGKKPKB-UHFFFAOYSA-N CCCCCC([O])CCC Chemical compound CCCCCC([O])CCC NJBUFSIQGKKPKB-UHFFFAOYSA-N 0.000 description 1
- GXFZXRCTBSCOLO-UHFFFAOYSA-N CCCCCCC([O])CCC Chemical compound CCCCCCC([O])CCC GXFZXRCTBSCOLO-UHFFFAOYSA-N 0.000 description 1
- ANPMIKCRCWKNIW-UHFFFAOYSA-N CCCCCCCCOC(=O)C1=CN2C=CN=C2S1 Chemical compound CCCCCCCCOC(=O)C1=CN2C=CN=C2S1 ANPMIKCRCWKNIW-UHFFFAOYSA-N 0.000 description 1
- DSXWFNQUTOOXHL-VOTSOKGWSA-N CCCCC\C=C\C[O] Chemical compound CCCCC\C=C\C[O] DSXWFNQUTOOXHL-VOTSOKGWSA-N 0.000 description 1
- XQVIFALZIOBIKP-WAYWQWQTSA-N CCCC\C=C/CC[O] Chemical compound CCCC\C=C/CC[O] XQVIFALZIOBIKP-WAYWQWQTSA-N 0.000 description 1
- GMSAHQCWPULTCV-AATRIKPKSA-N CCCC\C=C\C[O] Chemical compound CCCC\C=C\C[O] GMSAHQCWPULTCV-AATRIKPKSA-N 0.000 description 1
- BKKSKJXQHLKZJO-UHFFFAOYSA-N CCC[CH]C=O Chemical compound CCC[CH]C=O BKKSKJXQHLKZJO-UHFFFAOYSA-N 0.000 description 1
- BPNQPHJSQDBASB-PLNGDYQASA-N CCC\C=C/CC[O] Chemical compound CCC\C=C/CC[O] BPNQPHJSQDBASB-PLNGDYQASA-N 0.000 description 1
- MXMNJXSFXVVUAW-SNAWJCMRSA-N CCC\C=C\CCC[O] Chemical compound CCC\C=C\CCC[O] MXMNJXSFXVVUAW-SNAWJCMRSA-N 0.000 description 1
- ZYWNBJPKMGYJGB-SNAWJCMRSA-N CCC\C=C\C[O] Chemical compound CCC\C=C\C[O] ZYWNBJPKMGYJGB-SNAWJCMRSA-N 0.000 description 1
- NZPUTNNKVOQQNR-ARJAWSKDSA-N CC\C=C/CC[O] Chemical compound CC\C=C/CC[O] NZPUTNNKVOQQNR-ARJAWSKDSA-N 0.000 description 1
- ASOUMKUGMIXHOG-ONEGZZNKSA-N CC\C=C\CCC[O] Chemical compound CC\C=C\CCC[O] ASOUMKUGMIXHOG-ONEGZZNKSA-N 0.000 description 1
- VRGBCXQZCNPYJI-IHWYPQMZSA-N C\C=C/CC[O] Chemical compound C\C=C/CC[O] VRGBCXQZCNPYJI-IHWYPQMZSA-N 0.000 description 1
- NZXOVHWDJITLFN-NSCUHMNNSA-N C\C=C\CCC[O] Chemical compound C\C=C\CCC[O] NZXOVHWDJITLFN-NSCUHMNNSA-N 0.000 description 1
- RWPQRFXAJZYZSS-NSCUHMNNSA-N C\C=C\C[O] Chemical compound C\C=C\C[O] RWPQRFXAJZYZSS-NSCUHMNNSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical class CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- WXBWRVKWFVOPDT-UHFFFAOYSA-N [O].C(CCCCCC)C1=CC=CC=C1 Chemical compound [O].C(CCCCCC)C1=CC=CC=C1 WXBWRVKWFVOPDT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 description 1
- 125000004702 alkoxy alkyl carbonyl group Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 125000005197 alkyl carbonyloxy alkyl group Chemical group 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 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
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 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
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 239000003480 eluent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 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
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229960003132 halothane Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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Abstract
通式I的化合物,具有明显地形成液晶S(近晶)相的趋势,因此,非光学活性的式I化合物除了向列相还具有倾斜近晶相,特别是Sc相。相反地,许多光学活性的式I化合物除了胆甾型相外还具有,主要在倾斜近晶手性相,特别是手性Sc相。因此,所述化合物特别适于分别用作用于制备大范围液晶混合物的组分和掺杂剂。这类具有通式I的化合物提供了用于优化和修饰液晶混合物的大范围的新的组分和混合物。
Description
本发明涉及新的咪唑并噻唑衍生物,含有这些化合物的液晶混合物和这些化合物和混合物用于光学和电光仪器的用途。
由于这些物质的光学性质受外加电压的影响,液晶特别是在电光仪器,例如显示仪中用作电介质。液晶电光设备对本领域的技术人员是熟知的。这类仪器的工作原理可基于不同的效应。因此,这些仪器具有,例如,动态散射作用单元,DAP单元(取向相变形),客/主单元,具有扭曲向列结构的TN单元,STN单元(超扭曲向列),SBE单元(超双折射效应),OMI单元(光模式干扰)或TFT单元(薄膜晶体管)。
除了上述其性质基于使用向列的或胆甾型液晶的单元类型,最近还已知基于倾斜近晶相原理,特别是手性相的显示装置。合适的倾斜近晶相是,例如,近晶C,F,G,H,I和K相,下面称为SC,SF,等。一般地优选允许特别高的响应速度的SC相。手性倾斜相一般表示为SC *,SF *,等,星号指具有手性。已知的基于手性SC *相的单元类型是,例如,SSF单元(表面稳定化的铁电),SBF单元(细间距双稳态铁电)或DHF单元(变形的螺旋铁电)。
液晶材料必须具有好的耐化学和耐热性,且对电场和磁场具有高稳定性。另外,它们应在较宽的温度范围内具有合适的过渡相,低粘度和短的响应时间。基于手性倾斜近晶相的材料还应具有足够高的自然极化,且根据单元类型的不同,具有相当小的扭曲能力(SSF单元)或尽可能高的扭曲能力(SBF和DHF单元)。为了便于在单元中取向,它们还优选在SC相上具有SA相。
合适的铁电液晶混合物优选含有至少一种光学活性掺杂剂和一种液晶材料。所述液晶材料含有至少一种非手性组分,优选多个非手性组分,它们通常应具有宽倾斜近晶相,优选SC相。光学活性的掺杂剂本身不一定是液晶,但最好具有近晶相或胆甾型相。无论如何,光学活性的掺杂剂在液晶材料中诱发倾斜近晶手性相具有合适的扭曲和足够高的自然极化。
本发明涉及下面的通式化合物其中:-m和n是0或1;-当n是0,m是1时,R1是基团R3,环状手性基团Q1或,基团R3-A3-Z3-,且当m是0,n是1时,R2是基团R4,环状手性基团Q2或,基团R4-A4-Z4-;-环A1,A2,A3,A4是反式-1,4-环己烯或1,4-亚苯基,它是未取代的,或被氟,氯,氰基或甲基单取代或二取代;-R3和R4分别是烷基或链烯基,其中一个亚甲基或两个非相邻的亚甲基任意地被-O-,-COO-和/或-OOC-替代,和/或一个或几个氢原子被氟或氯替代;-Z1,Z2,Z3和Z4,分别是单键,CH2-CH2,O-CH2,CH2-O,COO,OOC,C≡C-,(CH2)4,O(CH2)3,CH=CH-CH2O,OCH2-CH=CH,CH=CH-(CH2)2或(CH2)2-CH=CH;-且Q1和/或Q2是下列任一手性基团:
其中,R5和R6分别是烷基或链烯基,其中一个亚甲基或两个非相邻的亚甲基任意地被-O-,-COO-和/或-OOC-替代,和/或一个或几个氢原子被氟或氯替代,条件是在R5和/或R6中的氧原子不直接与Q1和Q2中的环相连。
我们惊奇地发现,全部具有咪唑并噻唑单元的式I化合物,具有明显的形成液晶相,特别是倾斜近晶相的趋势。非光学活性的式I化合物除了向列的和/或SA相一般具有倾斜近晶相,特别是SC相。许多光学活性的式I化合物除了胆甾型的和/或SA相一般具有倾斜近晶手性相,特别是SC *相。因此,这些化合物特别适于作为液晶混合物中的倾斜近晶手性相的组分或手性掺杂剂。而且,它们也适于用作向列的和胆甾型的混合物的组分或手性掺杂剂。因此,本发明提供了较大范围的新的组分和混合物,用于进一步优化和修饰液晶材料。
式I化合物具有高耐化学性,且对电场和磁场具有高稳定性。它们是无色的,容易制备,且彼此间和与已知的液晶材料之间具有足够的溶解性。
式I化合物的性质根据引入环和取代基的数目和重要性可在较大范围内变化。例如,芳香环导致光学各向异性值增高,而饱和环导致此值降低。例如,可通过再引入一个或两个环增加透明点。侧链卤素取代基对平行和垂直于纵向分子轴的介电常数有贡献,它可根据取代的类型,用于增加或降低介电各向异性。另外,可通过一个或几个环的铡链取代基,修饰中间相区,基本可抑制任何形成高有序近晶相的趋势,且通常可增加溶解性。
因此本发明的化合物可进一步优化液晶混合物,且可在较大范围内修饰这些混合物的电光性质。
本说明书中的定义解释如下:
“烷基或链烯基,其中一个亚甲基或两个非相邻的亚甲基任意地被-O-,-COO-和/或-OOC-替代,和/或一个或几个氢原子被氟或氯替代”包括直链和支链(任意手性的)基团,如烷基,1-链烯基,2-链烯基,3-链烯基,4-链烯基,链烯基具有末端双键,烷氧基,链烯基氧,烷氧烷基,链烯基氧烷基,烷氧链烯基,烷基羰基氧,烷基羰基氧烷基,烷氧羰基烷基,烷氧烷基羰基氧,氟代烷基,二氟代烷基,三氟代烷基,氯代烷基,氰基烷基,甲基烷基,氟代烷氧基,氟代烷基羰氧,甲基烷氧,甲基烷氧羰基等等。优选的基团的例子包括甲基,乙基,丙基,丁基,戊基,己基,庚基,辛基,壬基,癸基,十一烷基,十二烷基,1-甲基丙基,1-甲基庚基,2-甲基庚基,(Z)-2-戊烯基,(Z)-2-己烯基,(Z)-2-庚烯基,(Z)-2-辛烯基,(Z)-2-壬烯基,(E)-3-戊烯基,(E)-3-己烯基,(E)-3-庚烯基,(E)-3-辛烯基,(E)-3-壬烯基,(Z)-4-己烯基,(Z)-4-庚烯基,(Z)-4-辛烯基,(Z)-4-壬烯基;链烯基具有末端双键,如3-丁烯基,4-戊烯基,5-己烯基,6-庚烯基,7-辛烯基,8-壬烯基;甲氧基,乙氧基,丙氧基,丁氧基,戊氧基,己氧基,庚氧基,辛氧基,壬氧基,1-甲基丙氧基,1-甲基庚氧基,(E)-2-丙烯基氧,(E)-2-丁烯基氧,(E)-2-戊烯基氧,(E)-2-己烯基氧,(E)-2-庚烯基氧,(E)-2-辛烯基氧,(Z)-3-戊烯基氧,(Z)-3-己烯基氧,(Z)-3-庚烯基氧,(Z)-3-辛烯基氧,(Z)-3-壬烯基氧,(E)-4-己烯基氧,(E)-4-庚烯基氧,(E)-4-辛烯基氧,(E)-4-壬烯基氧;甲氧乙基,甲氧丙基,甲氧丁基,甲氧戊基,甲氧己基,甲氧庚基,乙氧甲基,丙氧甲基,丁氧甲基,戊氧甲基,己氧甲基,乙氧乙基,丙氧乙基,丁氧乙基,戊氧乙基,己氧乙基,庚氧乙基,乙氧丙基,丙氧丙基,丁氧丙基,戊氧丙基;2-氟丙氧,2-氟戊氧,2-氟辛氧,2-氯己氧,2-氯辛氧,丁基羰氧,戊基羰氧,己基羰氧,庚基羰氧,2-氟丁基羰氧,2-氟戊基羰氧,2-氟己基羰氧,2-氟庚基羰氧,2-氯丁基羰氧,2-氯戊基羰氧,2-氯己基羰氧,2-氯庚基羰氧,2-甲基戊基羰氧,2-甲基己基羰氧,2-甲基庚基羰氧,2-甲基戊基氧羰基,2-甲基己基氧羰基,2-甲基庚基氧羰基,乙氧羰基甲氧,丙氧羰基甲氧,丁氧羰基甲氧,戊氧羰基甲氧,己氧羰基甲氧等等。
特别优选的式I化合物是那些其中R3至R6基团具有3-12个碳原子的。它们可以是直链或支链。基团R3和R4优选是直链的。但是,也优选那些R3和R4基团因为分支和/或因为存在氟或氯取代基导致手性侧链和导致化合物I具有光学活性的化合物。优选的手性基团R3和R4是1-甲基烷基,1-甲基烷氧基,1-甲基烷氧羰基,2-氟烷氧基,2-氯烷氧基,2-氟烷酰氧和2-氯烷酰氧。基团R5和R6优选是直链的。
Z1优选是单键,-CH2CH2-,-OCH2-或-OOC-,Z2优选是单键,-CH2CH2-,-CH2O-或-COO-,Z3和Z4优选是单键,-CH2CH2-,-CH2O-,-OCH2-,-COO-,或-OOC-。
环A1至A4优选为1,4-亚苯基,被氟单或双取代的1,4-亚苯基,和/或亚环己基。优选的氟取代的环是2-氟-1,4-亚苯基,3-氟-1,4-亚苯基和2,3-二氟-1,4-亚苯基。一般地,特别优选那些环A1或A2中至少一个是1,4-亚苯基,2-氟-1,4-亚苯基,3-氟-1,4-亚苯基或2,3-二氟-1,4-亚苯基的式I化合物。
优选在一个或两个对映体形式的式I化合物中存在手性环Q1和Q2。在存在Q1和/或Q2的式I化合物中,优选那些其中Q1和/或Q2导致了光学活性的式I化合物。环Q1和Q2可相同或不同,但优选相同。优选的其中存在Q1和/或Q2的式I化合物是那些其中Q1和/或Q2具有式i和/或ii结构的化合物。
其中Q1和Q2以及R3和R4定义如上,Z12,Z13,Z21,Z31,Z32,Z41和Z42是单键和/或CH2CH2,Z21还可以是CH2O,Z12和Z31还可以是OCH2,Z41还可以是CH2O或OCH2,Z32还可以是CH2O或COO且Z42还可以是OCH2或OOC,且取代基X1至X4是氢或氟。优选地,在每种情况下,取代基X1至X4中不多于一个或两个不是氢,且优选基团Z12至Z42中不多于一个不是单键。
在式IA至IP的化合物中,特别优选那些,除了咪唑并噻唑单元和任意存在的手性环Q1和/或Q2外只再具有一个环的化合物。它们是式IA,IF和IJ至IO的化合物。
可按照下列反应流程制备通式I的咪唑并噻唑。
首先使通式II的醛与磺酰氯和硫脲反应制备通式III的氨基噻唑。此反应在文献中有类似例子的描述,例如在Helv.Chim.Acta 38,1291(1955)中。然后,按照J.Chem.Soc.P.I,1989,643,中的类似方法,使式III的氨基噻唑与通式V的溴乙酰衍生物反应制备通式VI的亚铵盐(immoniumsalt),此化合物不需纯化通过在合适的溶剂,例如,乙醇中加热环化制备式I化合物。式V的溴乙酰化合物可通过,例如使用溴化铜(II),α-溴化通式IV的相应的未溴化的乙酰衍生物容易地制备。该反应在有机化学杂志29,3459(1964)中有类似例子的描述。
如果在基团R1A1Z1和/或R2A2Z2中存在酯基,优选直到咪唑并噻唑单元形成后再进行酯化。而且,如果在基团R1A1Z1和/或R2A2Z2中存在醚基,根据需要优选咪唑并噻唑单元形成后再进行醚化。
用于合成式I化合物的起始物是已知化合物或已知化合物的类似物或可从已知化合物经几步反应制备的。许多起始物是商业上可获得的。因此,例如,醛可从合适的腈通过用DIBAH还原制备,如果需要,可通过均裂反应予以扩大,制备式II的醛。在例如,EP-A-0122389中有这些腈,醛和均裂反应的描述。式IV的甲基羰基化合物对本领域的技术人员一般是已知的。因此,例如,合适的甲基酮可从相应的腈通过与甲基锂或甲基镁卤化物反应,或通过Friedel-Crafts酰化反应从芳族化合物容易地获得。合适的腈在液晶文献中有大量描述。
式I的化合物可彼此间和/或与其它的液晶组分以混合物的形式使用。因此,本发明还涉及具有至少两个组分的液晶混合物,其中至少一个组分是式I化合物。第二个组分和任选其它组分还可以是通式I化合物或其它合适的液晶组分。式I的化合物优选用作混合物的组分,它具有胆甾型和/或倾斜近晶相,例如手性SC相。式I的化合物可用作非手性组分和/或手性掺杂剂。
根据本发明,除了式I化合物,在混合物中可使用的合适的液晶组分对本领域的技术人员来说是大量已知的。例如从D.Demus等.,FlüssigeKristalle in Tabellen[在表中的液晶],VEB Deutscher Verlag furGrundstoffindustrie,Leipzig,I和II卷,或从Landolt-Brnstein,液晶,卷IV7a-d中可知,且它们中许多是商业上可得的。
根据本发明的式I化合物由于在其它液晶材料中具有很好的溶解性,且由于它们彼此间可很好的混溶,因此,式I化合物在本发明的混合物中的比例可相对高一些,可以是,例如,0.1-50%重量比。如果式I的非手性化合物用作组分,一般地其比例是约1-40%重量比,优选3-30%重量比。手性掺杂剂的比例基本上取决于混合物的扭曲能力,自然极化和所需的间距。因此,一种或多种使用的式I手性掺杂剂可根据应用在较大范围内变化,可以是,例如,约0.1-40%重量比。用于具有倾斜近晶相的液晶显示设备,式I的光学活性掺杂剂一般使用约1-30%重量比,优选约3-25%重量比。
本发明的混合物,除了含有一种或几种式I化合物外,至少还含有另外一种选自下列通式化合物的化合物 其中p是0或1;q和r是1或2,q+r=2或3;s是0,1或2;R7和R8分别是烷基,链烯基,烷氧基,链烯基氧,烷氧烷基,烷氧烷氧基,烷酰氧,链烯酰氧,烷氧羰基,链烯氧羰基;R9和R12分别是烷基或链烯基;R10和R11分别是烷基,链烯基,烷氧基和/或链烯氧;Z5,Z6和Z7分别是单键,CH2-CH2或CH2O,且Z6还可以是OCH2,COO或OOC;E和F分别是亚苯基-1,4-二基或反式-环己烯-1,4-二基;X1和X2分别是氢或氟;(R*)和(S*)指相对应构型。
式XIII到XVII的化合物是光学活性的掺杂剂,根据所需效果的不同,可在混合物中除了一种或几种式I化合物外,以一种或两种对映体的形式存在。
取代基R7至R12,优选每个取代基的碳原子数不超过18;特别优选约5-12个碳原子;取代基R7至R12可以是直链或支链的,但优选直链的。
可用已知方法制备液晶混合物和电光设备。
下面将进一步举例说明本发明的式I化合物和本发明类型的液晶混合物的制备。式I化合物的光学对映体具有相同的相转化温度和诱导相同的自然极化和扭曲绝对值,但具有相反的标志(sign)。表示相转化特征的缩写符号具有如下含义:
C 晶体
S 近晶相
SA,SB,SC,等近晶相A,B,C,等
SC *,SF *,等 手性近晶相C,F,等
N 向列型
N* 胆甾型
I 各向同性
实施例1
a)向32.1g细磨过的溴化铜(II)中加入50ml乙酸乙酯并回流30分钟。向沸腾的反应混合物中滴加入8.3g对羟基苯乙酮在50ml氯仿中的热的溶液,并连续回流5小时。将冷却的混合物过滤,剩余物用乙酸乙酯充分洗涤,滤液与活性炭一起稍加回流,然后冷却并过滤。减压蒸除大部分溶剂,并抽滤出所形成的结晶,在强减压下干燥。得到8.1g2-溴-1-(4-羟基苯基)乙酮(ethanone),为淡棕色结晶,熔点为122-124℃。
b)保持反应温度在25-28℃的条件下向21.3g壬醛(nonanal)中滴加入20g磺酰氯。在室温搅拌反应溶液16小时。然后加入11.4g硫脲并在约90℃回流3小时。向沸腾的反应溶液中滴加入200ml水,并再在90℃保持反应混合物1小时。将反应混合物热过滤,冷却并用醚萃取,分出水相用2N氢氧化钠调至pH为10。此相用醚萃取,醚相用硫酸钠干燥,蒸除醚,剩余固体用环己烷重结晶。得到8g2-氨基-5-庚基噻唑,为无色薄片,熔点为75-76℃。
c)在室温,向7.4g2-氨基-5-庚基噻唑在30ml无水丙酮中的溶液中滴加入7.3g2-溴-1-(4-羟基苯基)乙酮在30ml无水丙酮中的溶液。反应混合物在室温搅拌16小时,然后减压蒸除溶剂。向剩余物中加入300ml二氯甲烷和300ml1M碳酸氢钠溶液的两相混合物,并在室温充分搅拌混合物20分钟。抽滤所沉淀的固体,减压干燥,然后直接在100ml乙醇中回流24小时。然后冷却,减压蒸除溶剂,剩余物溶于乙酸乙酯,混合物用硅胶过滤。蒸发滤液,固体剩余物用乙酸乙酯/环己烷重结晶。得到2.6g2-庚基-6-(4-羟基苯基)咪唑并[2,1-b]噻唑,为微黄色结晶,熔点122℃。
可用类似方法得到下列化合物:-2-戊基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑,m.p.(C/SA):89.7℃,c.p.(SA/I):127.4℃;-2-己基-6-(4-辛基苯基)咪唑并[2,1-b]噻唑;-2-己基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑,m.p.(C/SC):84.1℃,SF/SC:80.8℃,SC/SA:96.2℃,c.p.(SA/I):124.7℃;-2-己基-6-(4-癸基苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-(4-庚基苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-(4-辛基苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑,m.p.(C/SC):86.8℃,SC/SA:112.7℃,c.p.(SA/I):129℃;-2-庚基-6-(4-癸基苯基)咪唑并[2,1-b]噻唑;-2-辛基-6-(4-庚基苯基)咪唑并[2,1-b]噻唑;-2-辛基-6-(4-辛基苯基)咪唑并[2,1-b]噻唑;-2-辛基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑;-2-辛基-6-(4-癸基苯基)咪唑并[2,1-b]噻唑;-2-壬基-6-(4-庚基苯基)咪唑并[2,1-b]噻唑;-2-壬基-6-(4-辛基苯基)咪唑并[2,1-b]噻唑;-2-壬基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑;-2-壬基-6-(4-癸基苯基)咪唑并[2,1-b]噻唑;-2-癸基-6-(4-庚基苯基)咪唑并[2,1-b]噻唑;-2-癸基-6-(4-辛基苯基)咪唑并[2,1-b]噻唑;-2-癸基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-(2-氟-4-壬基苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-(3-氟-4-壬基苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-(2,3-二氟-4-壬基苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-[2-(4-壬基苯基)乙基]咪唑并[2,1-b]噻唑;-2-庚基-6-(反式-4-庚基环己基)咪唑并[2,1-b]噻唑,m.p.(C/SA):71℃,S1/SA:61.8℃,c.p.(SA/I):71.7℃;-2-庚基-6-[2-(反式-4-壬基环己基)乙基]咪唑并[2,1-b]噻唑;-2-庚基-6-(4’-壬基联苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-(2’,3’-二氟-4’-壬基联苯基)咪唑并[2,1-b]噻唑;-2-庚基-6-[4-(反式-4-壬基环己基)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-{4-[2-(反式-4-辛基环己基)乙基]苯基}咪唑并[2,1-b]噻唑;-2-(4-庚基苯基)-6-庚基咪唑并[2,1-b]噻唑;-2-(4-庚基苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-(4-庚基苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-(4-庚基苯基)-6-癸基咪唑并[2,1-b]噻唑;-2-(4-辛基苯基)-6-庚基咪唑并[2,1-b]噻唑;-2-(4-辛基苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-(4-辛基苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-(4-辛基苯基)-6-癸基咪唑并[2,1-b]噻唑;-2-(4-壬基苯基)-6-庚基咪唑并[2,1-b]噻唑;-2-(4-壬基苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-(4-壬基苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-(4-癸基苯基)-6-庚基咪唑并[2,1-b]噻唑;-2-(4-癸基苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-(2-氟-4-庚基苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-(3-氟-4-庚基苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-(2,3-二氟-4-庚基苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-[2-(4-庚基苯基)乙基]-6-壬基咪唑并[2,1-b]噻唑;-2-(反式-4-庚基环己基)-6-壬基咪唑并[2,1-b]噻唑;-2-[2-(反式-4-庚基环己基)乙基]-6-庚基咪唑并[2,1-b]噻唑;-2-(4’庚基联苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-(2’,3’-二氟-4’-庚基联苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-[4-(4-反式-庚基环己基)苯基]-2-壬基咪唑并[2,1-b]噻唑;-2-{4-[2-(反式-4-庚基环己基)乙基]苯基}-6-辛基咪唑并[2,1-b]噻唑;-2-(4-壬基苯基)-6-(4-庚基苯基)咪唑并[2,1-b]噻唑;-2-(2,3-二氟-4-壬基苯基)-6-(4-庚基苯基)咪唑并[2,1-b]噻唑;-2-(4-壬基苯基)-6-(2,3-二氟-4-庚基苯基)咪唑并[2,1-b]噻唑。
实施例2
将0.314g2-庚基-6-(4-羟基苯基)咪唑并[2,1-b]噻唑(制备类似实施例1),0.11g氢氧化钾和0.29g溴代辛烷在15ml乙醇/水(2∶1)中的混合物回流16小时。然后将反应混合物冷却,用醚萃取,有机相用硫酸钠干燥,过滤并蒸发。剩余物用绝对乙醇重结晶。得到0.348g2-庚基-6-(4-辛基氧苯基)咪唑并[2,1-b]噻唑,为无色结晶,m.p.(C/S1):61℃,S1/S2:113℃,S2/S3:115.3℃,S3/SC:121.7℃,c.p.(SC/I):148.9℃。
可用类似方法得到下列化合物:-2-庚基-6-(4-庚基氧苯基)咪唑并[2,1-b]噻唑;-(R)-2-庚基-6-[4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-(S)-2-庚基-6-[4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-[4-((E)-2-辛烯氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-[4-((Z)-3-辛烯氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-[4-((E)-4-辛烯氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-[4-(7-辛烯氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-(4-壬基氧苯基)咪唑并[2,1-b]噻唑;-2-己基-6-(4-辛基氧苯基)咪唑并[2,1-b]噻唑;-(R)-2-己基-6-[4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-2-己基-6-(4-壬基氧苯基)咪唑并[2,1-b]噻唑;-2-辛基-6-(4-庚基氧苯基)咪唑并[2,1-b]噻唑;-2-辛基-6-(4-辛基氧苯基)咪唑并[2,1-b]噻唑;m.p.(C/S1):65℃,S1/S2:85℃,S2/S3:107℃,S3/SC:107℃,c.p.(SC/I):149℃;-(S)-2-辛基-6-[4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-2-辛基-6-(4-壬基氧苯基)咪唑并[2,1-b]噻唑;m.p.(C/S1):68℃,S1/S2:99.5℃,S2/S3:120℃,S3/SC:124.5℃,c.p.(SC/I):151.5℃;-2-壬基-6-(4-庚基氧苯基)咪唑并[2,1-b]噻唑;-2-壬基-6-(4-辛基氧苯基)咪唑并[2,1-b]噻唑;-(S)-2-壬基-6-[4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-(2-氟-4-辛基氧苯基)咪唑并[2,1-b]噻唑;-(S)-2-辛基-6-[2-氟-4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-(3-氟-4-辛基氧苯基)咪唑并[2,1-b]噻唑;-(S)-2-辛基-6-[3-氟-4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-(2,3-二氟-4-辛基氧苯基)咪唑并[2,1-b]噻唑;-(S)-2-辛基-6-[2,3-二氟-4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-[2-(4-辛基氧苯基)乙基]咪唑并[2,1-b]噻唑;-2-壬基-6-[(4-庚基苯氧)甲基]咪唑并[2,1-b]噻唑;-2-辛基-6-(4’-辛基氧联苯基)咪唑并[2,1-b]噻唑;-2-辛基-6-(2’,3’-二氟-4’-辛基氧联苯基)咪唑并[2,1-b]噻唑;-(S)-2-辛基-6-[2’,3’-二氟-4’-(2-辛基氧)联苯基]咪唑并[2,1-b]噻唑;-2-庚基-6-{4-[(反式-4-辛基环己基)甲氧]苯基}咪唑并[2,1-b]噻唑;-2-(4-庚基氧苯基)-6-庚基咪唑并[2,1-b]噻唑;-2-(4-庚基氧苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-(4-庚基氧苯基)-6-壬基咪唑并[2,1-b]噻唑;-2-(4-庚基氧苯基)-6-癸基咪唑并[2,1-b]噻唑;-2-(4-辛基氧苯基)-6-庚基咪唑并[2,1-b]噻唑;-2-(4-辛基氧苯基)-6-辛基咪唑并[2,1-b]噻唑;-(S)-2-[4-(2-辛基氧)苯基]-6-辛基咪唑并[2,1-b]噻唑;-2-[4-((E)-2-辛烯氧)苯基]-6-庚基咪唑并[2,1-b]噻唑;-2-[4-((Z)-3-辛烯氧)苯基]-6-庚基咪唑并[2,1-b]噻唑;-2-[4-((E)-4-辛烯氧)苯基]-6-庚基咪唑并[2,1-b]噻唑;-2-(4-壬基氧苯基)-6-庚基咪唑并[2,1-b]噻唑;-2-(4-壬基氧苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-(2-氟-4-辛基氧苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-(3-氟-4-辛基氧苯基)-6-辛基咪唑并[2,1-b]噻唑;-(S)-2-[3-氟-4-(2-辛基氧)苯基]-6-辛基咪唑并[2,1-b]噻唑;-2-(2,3-二氟-4-辛基氧苯基苯基)-6-辛基咪唑并[2,1-b]噻唑;-2-[2-(4-庚基苯基)乙基]-6-壬基咪唑并[2,1-b]噻唑;-2-(反式-4-庚基环己基)-6-壬基咪唑并[2,1-b]噻唑;-2-[2-(反式-4-庚基环己基)乙基]-6-庚基咪唑并[2,1-b]噻唑;-2-(4’-庚基联苯基基)-6-壬基咪唑并[2,1-b]噻唑;-2-(2’,3’-二氟-4’-庚基联苯基基)-6-壬基咪唑并[2,1-b]噻唑;-2-{4-[(反式-4-辛基环己基)甲氧]苯基}-2-庚基咪唑并[2,1-b]噻唑;-2-(4-辛基苯基)-6-(4-辛基氧苯基)咪唑并[2,1-b]噻唑;-2-(4-辛基氧苯基)-6-(4-辛基苯基)咪唑并[2,1-b]噻唑;-2-(2,3-二氟-4-辛基氧苯基)-6-(4-辛基苯基)咪唑并[2,1-b]噻唑;-2-(4-辛基氧苯基)-6-(2,3-二氟-4-辛基苯基)咪唑并[2,1-b]噻唑;-2-(4-辛基氧苯基)-6-(2,3-二氟-4-辛基氧苯基)咪唑并[2,1-b]噻唑;-2-(2,3-二氟-4-辛基氧苯基)-6-(4-辛基氧苯基)咪唑并[2,1-b]噻唑;-(S,S)-2-[4-(2-辛基氧)苯基]-6-[4-(2-辛基氧)苯基]咪唑并[2,1-b]噻唑。
实施例3
a)将按照实施例1类似方法从α-溴代丙酮酸乙酯制备的2g2-庚基咪唑并[2,1-b]噻唑-6-羧酸乙酯在50ml1N的甲醇KOH(methano1ic KOH)中的混合物在室温保存过夜,然后用1N硫酸酸化,用200ml水稀释然后用醚萃取。醚相用硫酸钠干燥,过滤,蒸发。得到2-庚基咪唑并[2,1-b]噻唑-6-羧酸。
b)在搅拌下,在10分钟内,向1.3g2-庚基咪唑并[2,1-b]噻唑-6-羧酸,1g4-辛基氧苯酚和0.1g4-(二甲基氨基)吡啶在25ml二氯甲烷的溶液中分批加入1.2gN,N’-二环己基碳化二亚胺。将混合物在室温搅拌过夜,然后过滤。滤液用二氯甲烷稀释,用两份50ml饱和碳酸钠溶液洗涤,然后用水洗涤,无水硫酸镁干燥并过滤,蒸发滤液。剩余物用乙酸乙酯/环己烷重结晶,得到4-辛基氧苯基2-庚基咪唑并[2,1-b]噻唑-6-羧酸酯,m.p.(C/SA):112.6℃,c.p.(SA/I):151.4℃。
可用类似方法得到下列化合物:-4-(2-辛基氧)苯基(S)-2-庚基咪唑并[2,1-b]噻唑-6-羧酸酯;-4-辛基苯基2-庚基咪唑并[2,1-b]噻唑-6-羧酸酯;-2-(4-辛基苯基)咪唑并[2,1-b]噻唑-6-羧酸辛酯;-2-(4-辛基氧苯基)咪唑并[2,1-b]噻唑-6-羧酸辛酯;-(S)-2-(4-辛基氧苯基)咪唑并[2,1-b]噻唑-6-羧酸2-辛基酯;-2-[4-((S)-2-辛基氧)苯基]咪唑并[2,1-b]噻唑-6-羧酸(S)-2-辛基酯;-2-[4-((S)-2-辛基氧)苯基]咪唑并[2,1-b]噻唑-6-羧酸(R)-2-辛基酯;-4-(2-庚基咪唑并[2,1-b]噻唑-6-基)苯甲酸辛酯,m.p.(C/S1):61.8℃,S1/SA:97℃,c.p.(SA/I):129℃;-(S)-4-(2-辛基咪唑并[2,1-b]噻唑-6-基)苯甲酸2-辛酯;-4-(6-庚基咪唑并[2,1-b]噻唑-2-基)苯甲酸辛酯;-(R)-4-(6-庚基咪唑并[2,1-b]噻唑-2-基)苯甲酸辛酯,m.p.(C/I):112.4℃;-(S)-4-(6-辛基咪唑并[2,1-b]噻唑-2-基)苯甲酸2-辛酯;-(S,S)-2-[4-(2-辛基氧羰基)苯基]咪唑并[2,1-b]噻唑-6-基羧酸2-辛酯;-(S,S)-6-[4-(2-辛基氧羰基)苯基]咪唑并[2,1-b]噻唑-2-基羧酸2-辛酯,m.p.(C/N*):62.7℃,c.p.(N*/I):66.2℃;-4-(2-庚基咪唑并[2,1-b]噻唑-6-基)苯基壬烷羧酸酯,m.p.(C/SC):92.7℃,SC/SA:119℃,c.p.(SA/I):147℃;-4-(2-辛基咪唑并[2,1-b]噻唑-6-基)苯基辛烷羧酸酯;-4-(2-壬基咪唑并[2,1-b]噻唑-6-基)苯基辛烷羧酸酯;-4-(2-辛基咪唑并[2,1-b]噻唑-6-基)苯基壬烷羧酸酯;-2,3-二氟-4-(2-庚基咪唑并[2,1-b]噻唑-6-基)苯基癸烷羧酸酯,m.p.(C/N):85.1℃,N/SC:90.2℃,c.p.(SC/I):96.6℃;-4-(2-辛基咪唑并[2,1-b]噻唑-6-基)苯基反式-4-庚基环己烷羧酸酯;-4-[2-(4-辛基苯基)咪唑并[2,1-b]噻唑-6-基)苯基壬烷羧酸酯;-4-(2-辛基咪唑并[2,1-b]噻唑-6-基)苯基(R)-2-氟己烷羧酸酯;-2,3-二氟-4-(2-辛基咪唑并[2,1-b]噻唑-6-基)苯基(R)-2-氟己烷羧酸酯,m.p.(C/SA):88.3℃,c.p.(SA/I):91.8℃;-4-[2-辛基咪唑并[2,1-b]噻唑-6-基)苯基(R)-2-氯己烷羧酸酯;-4-(6-壬基咪唑并[2,1-b]噻唑-2-基)苯基庚烷羧酸酯;-4-(6-辛基咪唑并[2,1-b]噻唑-2-基)苯基辛烷羧酸酯;-4-(6-庚基咪唑并[2,1-b]噻唑-2-基)苯基壬烷羧酸酯;-4-(6-壬基咪唑并[2,1-b]噻唑-2-基)苯基(R)-2-氟己烷羧酸酯;-4-(6-辛基咪唑并[2,1-b]噻唑-2-基)苯基(R)-2-氯己烷羧酸酯;-4-(6-辛基咪唑并[2,1-b]噻唑-2-基)苯基反式-4-庚基环己烷羧酸酯;-4-[6-(4-辛基苯基)咪唑并[2,1-b]噻唑-2-基]苯基壬烷羧酸酯。
实施例4
无水条件下将0.08g4-(2-羧基咪唑并[2,1-b]噻唑-6-基)苯甲醛,0.133g(2R,3S)-2-辛基-1,3-丁二醇(制备参见EP-A-0 457 105),15ml甲苯和3滴2N硫酸的混合物回流2小时。然后,冷却,加入1ml三乙胺,用醚和饱和碳酸氢钠溶液进行分配。用硫酸镁干燥有机溶液,过滤,蒸发至干,剩余物用硅胶色谱纯化,使用甲苯/乙酸乙酯(10∶1)为洗脱剂。然后用乙酸乙酯/己烷(1∶3)结晶,得到0.079g2-((2R,3S,5R)-4-甲基-5-辛基-1,3-二噁烷-2-基)-6-[4-((2R,3S,5R)-4-甲基-5-辛基-1,3-二噁烷-2-基)苯基]咪唑并[2,1-b]噻唑,m.p.(C/SA):179℃,c.p.(SA/I):191.2℃。
可用类似方法得到下列化合物:-2-((2R,3R,5S)-4-甲基-5-辛基-1,3-二噁烷-2-基)-6-[4-((2S,3R,5S)-4-甲基-5-辛基-1,3-二噁烷-2-基)苯基]咪唑并[2,1-b]噻唑;-2-((2R,3S,5R)-4-甲基-5-己基-1,3-二噁烷-2-基)-6-[4-((2R,3S,5R)-4-甲基-5-己基-1,3-二噁烷-2-基)苯基]咪唑并[2,1-b]噻唑;-2-((2R,3S,5R)-4-甲基-5-癸基-1,3-二噁烷-2-基)-6-[4-((2R,3S,5R)-4-甲基-5-癸基-1,3-二噁烷-2-基)苯基]咪唑并[2,1-b]噻唑;-2-((4R,5R)-4,5-二甲氧羰基-1,3-二噁烷基)-6-[4-((4R,5R)-4,5-二甲氧羰基-1,3-二噁烷基)]咪唑并[2,1-b]噻唑;-2-((4S,5S)-4,5-二甲氧羰基-1,3-二噁烷基)-6-[4-((4S,5S)-4,5-二甲氧羰基-1,3-二噁烷基)]咪唑并[2,1-b]噻唑;-2-((4R,5R)-4,5-二乙氧羰基-1,3-二噁烷基)-6-[4-((4R,5R)-4,5-二乙氧羰基-1,3-二噁烷基)]咪唑并[2,1-b]噻唑;
实施例5
为了研究式I化合物在混合物中的性质,制备了试验混合物。为了此目的,将待测定式I组分与基质混合物(BM)混合。为了进行对比,制备了对比混合物,其中一个组分作为对比组分与基质混合物BM混合。测定这些混合物的相序列和自然极化(PS在nC/cm2)以及切换时间和切换角。测定条件如下:在8.5μ单元厚度和δ电压为10Hz和5V/μ的条件下测定PS;在10V/μ方波电压(峰/峰)条件下测定切换时间作为到Imax的时间,且在2μ单元厚度和电压为25V的条件下测定切换角。所有测量都保持在25℃进行。基质混合物(BM)16.6%重量比的反式-4-[4-(2,3-二氟-4-辛基氧苯甲酰氧)苯基]环己基(R)-2-氟己酸酯;23.8%重量比的2-(4-己基氧苯基)-5-壬基嘧啶;23.4%重量比的2-(4-壬基氧苯基)-5-壬基嘧啶;11.8%重量比的2-(4-壬基氧苯基)-5-辛基嘧啶;12.1%重量比的2-(4-庚基氧苯基)-5-庚基嘧啶;12.3%重量比的2-(4-癸基氧苯基)-5-辛基嘧啶;相序列[℃]:I-74.6-N*-67.7-SA-60.6-SC *--7.6C对比混合物15.0%重量比的2-(4-壬基氧苯基)-5-壬基嘧啶;85.0%重量比的BM;相序列[℃]:I-71.0-N*-66.0-SA-60.0-SC *-;PS:16.0nC/cm2,切换时间:120μs,切换角:50.2°。试验混合物115.0%重量比的2-庚基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑;85.0%重量比的BM;相序列[℃]:I-76.7-N*-74.5-SA-61.7-SC *-;PS:17.7nC/cm2,切换时间:100μs,切换角:40°。试验混合物215.0%重量比的2-己基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑;85.0%重量比的BM;相序列[℃]:I-74.4-N*-71.4-SA-60.3-SC *-;PS:16.8nC/cm2,切换时间:132μs,切换角:52.1°。试验混合物315.0%重量比的2-戊基-6-(4-壬基苯基)咪唑并[2,1-b]噻唑;85.0%重量比的BM;相序列[℃]:I-76.1-N*-73.0-SA-59.9-SC *-;PS:16.1nC/cm2,切换时间:132μs,切换角:51.3°。试验混合物415.0%重量比的2-庚基-6-(4-辛基氧苯基)咪唑并[2,1-b]噻唑;85.0%重量比的BM;相序列[℃]:I-80.9-N*-75.3-SA-70.6-SC *-;PS:20.1nC/cm2,切换时间:150μs,切换角:60.3°。试验混合物515.0%重量比的4-(2-庚基咪唑并[2,1-b]噻唑-6-基)苯基壬烷羧酸酯;85.0%重量比的BM;相序列[℃]:I-78.7-N*-73.6-SA-68.2-SC *-;PS:20.5nC/cm2,切换时间:140μs,切换角:56.2°。试验混合物615.0%重量比的4-辛基氧苯基2-庚基咪唑并[2,1-b]噻唑-6-羧酸酯;85.0%重量比的BM;相序列[℃]:I-78.2-N*-71.5-SA-61.3-SC *-;PS:16.3nC/cm2。
Claims (11)
1、下列通式的咪唑并噻唑衍生物其中符号m,n,R1和R2具有如下含义:m和n为0或1,R1 当n是0,m是1时,R1是基团R3或Q1或,基团R3-A3-Z3-,R2 当m是0,n是1时,R2是基团R4或Q2或,基团R4-A4-Z4-,且彼此独立,-R3和R4分别是烷基或链烯基,其中一个亚甲基或多个非相邻的亚甲基任意地被-O-,-COO-或-OOC-替代,和/或一个或几个氢原子被氟或氯替代,-Q1和Q2是下列任一手性基团:其中,R5和R6分别是烷基或链烯基,其中一个亚甲基或多个非相邻的亚甲基可被-O-,-COO-或-OOC-替代,和/或一个或几个氢原子可被氟或氯替代,条件是氧原子不直接与Q1或Q2中的环相连,-A1,A2,A3,A4是反式-1,4-亚环己基或1,4-亚苯基,它是未取代的,或被氟,氯,氰基或甲基单取代或二取代,且-Z1,Z2,Z3和Z4,分别是单键,-CH2-CH2-,-O-CH2-,-CH2-O-,-COO-,-OOC-,-C≡C-,-(CH2)4-,-O(CH2)3-,-CH=CH-CH2O-,-OCH2-CH=CH-,-CH=CH-(CH2)2-或-(CH2)2-CH=CH-。
2、权利要求1的咪唑并噻唑衍生物,是非光学活性的且形成倾斜近晶相。
3、权利要求1的咪唑并噻唑衍生物,是光学活性的。
4、权利要求1-3的任一咪唑并噻唑衍生物,其中R3,R4,R5和R6是具有3-12个碳原子的直链或支链基团。
5、权利要求1-4的任一咪唑并噻唑衍生物,其中A1和/或A2中是1,4-亚苯基,2-氟-1,4-亚苯基,3-氟-1,4-亚苯基或2,3-二氟-1,4-亚苯基。
6、权利要求1-5的任一咪唑并噻唑衍生物,其中Q1和/或Q2是式i和/或ii基团。
7、具有至少两个组分的液晶混合物,含有至少一种式I的咪唑并噻唑衍生物。
8、权利要求7的液晶混合物,含有至少一种光学活性掺杂剂和具有至少一种非手性组分的液晶材料,其中从手性式I的咪唑并噻唑衍生物形成一种或几种掺杂剂和/或从非手性式I的咪唑并噻唑衍生物形成一种或几种组分。
10、含有至少一种式I的咪唑并噻唑衍生物的光学或电光设备。
11、含有权利要求7,8和9任一液晶混合物的光学或电光设备。
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EP1306419A1 (en) * | 2001-10-23 | 2003-05-02 | Clariant International Ltd. | Active matrix liquid crystal device and smectic liquid crystal mixture |
DE10222166A1 (de) * | 2002-05-20 | 2003-12-11 | Fraunhofer Ges Forschung | Chirale Verbindungen und deren Verwendung |
CN101193899A (zh) * | 2005-06-09 | 2008-06-04 | 默克专利股份有限公司 | 噻吩并(3,4-d)噻唑的单体、低聚物和聚合物 |
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DE3342631A1 (de) * | 1983-11-25 | 1985-06-05 | Merck Patent Gmbh, 6100 Darmstadt | Thienothiophenderivate |
DE3734332A1 (de) * | 1986-10-25 | 1988-07-28 | Merck Patent Gmbh | Heterocyclische fluessigkristallverbindungen |
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HK1001619A1 (en) | 1998-07-03 |
JPH1095785A (ja) | 1998-04-14 |
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DE59707350D1 (de) | 2002-07-04 |
US5851425A (en) | 1998-12-22 |
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