GB2367058A - Acetylenic biphenyl derivatives & their use as liquid crystalline components - Google Patents
Acetylenic biphenyl derivatives & their use as liquid crystalline components Download PDFInfo
- Publication number
- GB2367058A GB2367058A GB0115694A GB0115694A GB2367058A GB 2367058 A GB2367058 A GB 2367058A GB 0115694 A GB0115694 A GB 0115694A GB 0115694 A GB0115694 A GB 0115694A GB 2367058 A GB2367058 A GB 2367058A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compounds
- propynyl
- independently
- formula
- another
- 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title 1
- 239000007788 liquid Substances 0.000 title 1
- 150000000475 acetylene derivatives Chemical class 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 74
- -1 acetylene derivative ester Chemical class 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 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 6
- 239000000126 substance Substances 0.000 description 6
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 150000001502 aryl halides Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- SJSRFXJWBKOROD-UHFFFAOYSA-N 1,1'-bi(cyclohexyl)-1-carboxylic acid Chemical class C1CCCCC1C1(C(=O)O)CCCCC1 SJSRFXJWBKOROD-UHFFFAOYSA-N 0.000 description 2
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IWIOHRVOBOYWQE-UHFFFAOYSA-N (1-cyclohexylcyclohexyl)benzene Chemical class C1CCCCC1C1(C=2C=CC=CC=2)CCCCC1 IWIOHRVOBOYWQE-UHFFFAOYSA-N 0.000 description 1
- JYNLTWJPPFIEFR-UHFFFAOYSA-N 1,2-dicyclohexylcyclohexene Chemical class C1CCCCC1C1=C(C2CCCCC2)CCCC1 JYNLTWJPPFIEFR-UHFFFAOYSA-N 0.000 description 1
- 150000005481 1,2-diphenylethanes Chemical class 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- QQFSIGWYINAJOB-UHFFFAOYSA-N 1,4-dicyclohexylbenzene Chemical class C1CCCCC1C1=CC=C(C2CCCCC2)C=C1 QQFSIGWYINAJOB-UHFFFAOYSA-N 0.000 description 1
- DIHPKCMKWXFURJ-UHFFFAOYSA-N 1-(2-cyclohexylethyl)-2-phenylbenzene Chemical class C1CCCCC1CCC1=CC=CC=C1C1=CC=CC=C1 DIHPKCMKWXFURJ-UHFFFAOYSA-N 0.000 description 1
- YQSAPDQJFZPHOJ-UHFFFAOYSA-N 2-cyclohexyl-1,3-dithiane Chemical class C1CCCCC1C1SCCCS1 YQSAPDQJFZPHOJ-UHFFFAOYSA-N 0.000 description 1
- SMHSPYVJAUGNOI-UHFFFAOYSA-N 2-cyclohexyl-1,4-dioxane Chemical class C1CCCCC1C1OCCOC1 SMHSPYVJAUGNOI-UHFFFAOYSA-N 0.000 description 1
- ZKTFZNPTAJIXMK-UHFFFAOYSA-N 2-cyclohexylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1CCCCC1 ZKTFZNPTAJIXMK-UHFFFAOYSA-N 0.000 description 1
- HYYFAYFMSHAWFA-UHFFFAOYSA-N 2-cyclohexylethylbenzene Chemical class C1CCCCC1CCC1=CC=CC=C1 HYYFAYFMSHAWFA-UHFFFAOYSA-N 0.000 description 1
- IBLVSWYGUFGDMF-UHFFFAOYSA-N 2-cyclohexylethylcyclohexane Chemical class C1CCCCC1CCC1CCCCC1 IBLVSWYGUFGDMF-UHFFFAOYSA-N 0.000 description 1
- HUTHUTALXJNNRS-UHFFFAOYSA-N 2-cyclohexylpyridine Chemical class C1CCCCC1C1=CC=CC=N1 HUTHUTALXJNNRS-UHFFFAOYSA-N 0.000 description 1
- YJDDXMSIMBMMGY-UHFFFAOYSA-N 2-cyclohexylpyrimidine Chemical class C1CCCCC1C1=NC=CC=N1 YJDDXMSIMBMMGY-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- QNGKGXNZGWIDGS-UHFFFAOYSA-N 6-cyclohexyl-5-ethyl-5-phenylcyclohexa-1,3-diene Chemical class C=1C=CC=CC=1C1(CC)C=CC=CC1C1CCCCC1 QNGKGXNZGWIDGS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910018954 NaNH2 Inorganic materials 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005644 Wolff-Kishner reduction reaction Methods 0.000 description 1
- ADIAPCNCEHFEPJ-UHFFFAOYSA-N [4-(2-cyclohexylethyl)cyclohexyl]benzene Chemical class C1CCCCC1CCC(CC1)CCC1C1=CC=CC=C1 ADIAPCNCEHFEPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 description 1
- 150000001482 benzyl phenyl ethers Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000009835 boiling Methods 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical class C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical class C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical class C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-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
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- GQNMAZUQZDEAFI-UHFFFAOYSA-N lithium;1h-naphthalen-1-ide Chemical compound [Li+].[C-]1=CC=CC2=CC=CC=C21 GQNMAZUQZDEAFI-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical class C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 125000006611 nonyloxy group Chemical group 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 150000001608 tolans Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
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Abstract
Acetylene derivatives of the formula I <EMI ID=1.1 HE=33 WI=136 LX=332 LY=660 TI=CF> <PC>[in which <DL TSIZE=16> <DT>R<SP>1</SP>, R<SP>2</SP><DD>independently of one another are H, an alkyl radical (which is unsubstituted or at least monosubstituted by halogen) or CN, and in which, in addition, one or more CH<SB>2</SB> groups may each, independently of one another, be replaced by -O-, -C I C- or -CH=CH- in such a way that heteroatoms are not connected directly; <DT>L<SP>1</SP>, L<SP>2</SP>, L<SP>3</SP>, L<SP>4</SP>,<DD>independently of one another are H or F; <DT>L<SP>5</SP>, L<SP>6</SP><DD> <DT>Z<DD>is -C I C-, -CH<SB>2</SB>CH<SB>2</SB>- or a single bond; <DT>n, m, p<DD>independently of one another are 0 or 1, provided that n+m * 0] </DL> frequently have highly positive values of the optical anisotropy W n with moderate values of the dielectric anisotropy We and relatively low viscosity and can be used as components of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases (DAP) or electrically controlled birefringence (ECB) or the effect of dynamic scattering.
Description
Acetylene derivatives and liquid-crystalline medium
The invention relates to acetylene derivatives of the formula I
in which R', R2 independently of one another are H, an alkyl radical having 1-12 carbon atoms which is unsubstituted or at least monosubstituted by halogen or CN and in which, in addition, one or more CH2 groups may each, independently of one another, be replaced by -O-, -C#C- or -CH=CH- in such a way that heteroatoms are not connected directly,
2 3 4 L1, L2, L3, L4, independently of one another are H or F 5 6 L5 L6 Z is-C=C-,-CH2CH2-or a single bond, n, m, p independently of one another are 0 or 1, provided that n+mO.
The invention also relates to the use of the compounds of the formula I as components of liquid-crystalline media, and to liquid-crystal and electro-optical display elements which contain the liquid-crystalline media according to the invention.
The compounds of the formula I frequently have highly positive values of the optical anisotropy An with moderate values of the dielectric anisotropy As and relatively low viscosity and can be used as components of liquid-crystalline media, in particular for displays based on the principle of the twisted cell, the guest-host effect, the effect of deformation of aligned phases (DAP) or electrically controlled birefringence (ECB) or the effect of dynamic scattering.
The substances employed hitherto for this purpose all have certain disadvantages, for example inadequate stability to the action of heat, light or electric fields, or unfavourable elastic and/or dielectric properties.
The invention had the object of finding novel, stable, liquid-crystalline or mesogenic compounds of particularly high positive dielectric anisotropy and moderate to high optical anisotropy at the same time as low viscosity which are suitable as components of liquid-crystalline media, in particular for TN, TFT and
STN displays.
It has now been found that the compounds of the formula I are eminently suitable as components of liquid-crystalline media. They can be used to obtain stable liquid-crystalline media, in particular suitable for TFT or STN displays. The novel compounds are distinguished, in particular, by high thermal stability, which is advantageous for a high"holding ratio", and exhibit favourable clearing point values.
The provision of compounds of the formula I very generally considerably broadens the range of liquid-crystalline substances which are suitable, from various applicational points of view, for the preparation of liquid-crystalline mixtures.
The compounds of the formula I have a broad range of applications. Depending on the choice of substituents, these compounds can serve as base materials of which liquid-crystalline media are predominantly composed; however, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compound in order, for example, to modify the dielectric and/or optical anisotropy of a dielectric of this type and/or to optimize its threshold voltage and/or its viscosity. Addition of compounds of the formula I to liquid-crystalline dielectrics allows the An values and As values of such media to be significantly affected.
The meaning of the formula I covers all isotopes of the chemical elements bound in the compounds of the formula 1. In enantiomerically pure or enriched form, the compounds of the formula I are also suitable as chiral dopants and in general for producing chiral mesophases.
In the pure state, the compounds of the formula I are colourless and form liquidcrystalline mesophases in a temperature range which is favourably located for electro-optical use. They are stable chemically, thermally and to light.
The invention thus relates to the compounds of the formula I and to the use of these compounds as components of liquid-crystalline media. The invention furthermore relates to liquid-crystalline media comprising at least one compound of the formula 1, and to liquid-crystal display elements, in particular electro-optical display elements, which contain media of this type.
2 2 3 4 6 Above and below, R', R2, Z, L\ L, L3, L, L5, L6, m, n, and p are as defined above, unless expressly stated otherwise.
The following group of compounds of the sub-formulae IA to IF represents preferred embodiments of the invention:
in which R1, R2, Z, m and n are as defined above.
If R and/or R2 in the formulae above and below is an alkyl radical, this can be straight-chain or branched.
It is preferably straight-chain, has 2,3, 4,5, 6, or 7 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl or heptyl, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl or pentadecyl.
If f R1 and/or R2 is an alkyl radical in which one CH2 group has been replaced by - 0-, this can be straight-chain or branched. It is preferably straight-chain and has 1 to 10 carbon atoms. Preferably, the first CH2 group of this alkyl radical has been replaced by-0-, so that the radical R1 becomes alkoxy and is preferably methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy or nonyloxy.
Furthermore, one CH2 group elsewhere can also be replaced by-0-, so that the radical R and/or R2 is preferabiy straight-chain 2-oxapropyl (= methoxymethyl), 2- (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3-or 4-oxapentyl, 2-, 3-, 4-or 5-oxahexyl, 2-, 3-, 4-, 5-or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6-or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7-or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, 8-or 9-oxadecyl.
If R and/or R2 is an alkenyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it is in particular vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-2, -2-, -3- or -4-enyl,
hex-1-,-2-,-3-,-4-or-5-enyl, hept-1-,-2-,-3-,-4-,-5-or-6-enyl, oct-1-,-2-,-3-,-4-, - 5-,-6-or-7-eny), non-1-,-2-,-3-,-4-,-5-,-6-,-7-or-8-eny !, or dec-1-,-2-,-3-,-4-, - 5-,-6-,-7-,-8-or-9-eny).
R1 and/or R2 is particularly preferably an alkenyl radical from the following group:
If R and/or R2 is an alkenyloxy radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. It is particularly preferably a radical from the following group:
If R1and/or R2is an alkyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain. Halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent can be in any desired position, but is preferably in the o-position.
If R1 and/or R2 is an alkynyl radical, this can be straight-chain or branched. It is preferably straight-chain and has 2 to 10 carbon atoms. Accordingly, it is in particular ethynyl, prop-1-or-2-ynyl, but-1-,-2-or-3-ynyl, pent-1-,-2-,-3-or-4 ynyl, hex-1-,-2-,-3-,-4-or-5-ynyl, hept-1-,-2-,-3-,-4-,-5-or-6-ynyl, oct-1-, -2-,-
3-,-4-,-5-,-6-or-7-ynyl, non-1-,-2-,-3-,-4-,-5-,-6-,-7-or-8-ynyl, or dec-1-,-2-,3-,-4-,-5-,-6-,-7-,-8-or-9-ynyl. Compounds of the formula I containing a branched wing group R'and/or R2 may occasionally be of importance owing to better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopants if they are optically active. Smectic compounds of this type are suitable as components of ferroelectric materials.
Branched groups of this type generally contain not more than one chain branch.
Preferred branched radicals R'are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl,
3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy, 1-methylhexyloxy or 1-methylheptyloxy.
Formula I covers the racemates of these compounds and the optical antipodes, and mixtures thereof.
Of these compounds of the formula I and the sub-formulae, preference is given to those in which at least one of the radicals present therein has one of the preferred meanings indicated.
Further preferred compounds of the formula I are indicated below :
Compounds of the formula I wherein m is 0 and whose R1 group is an alkyl, oxaalkyl or alkoxy radical having 1 to 10 carbon atoms or an alkenyl radical having 2 to 10 carbon atoms.
Compounds of the formula I wherein m+n is 1.
Compounds of the formula I wherein p is 1.
Compounds of formula I in which each of the aromatic rings, independently of one another, is unsubstituted or mono-substituted by fluorine.
Compounds of the formula I in which Z is a single bond.
Compounds of formula 1, wherein at least one of the aromatic rings is monostubstituted by fluorine.
Some very particularly preferred smaller groups of compounds of the formula I are those of the sub-formulae 11 to 120 :
in which R 1 and R2 are as defined above.
Very particularly preferred compounds from this group are those of the formulae I1, I2,I7,I8 and I12.
The compounds of the formula I are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg
Thieme-Verlag, Stuttgart), to be precise, under reaction conditions which are known and suitable for said reactions.
Use can be made here of variants which are known per se, but are not mentioned here in greater detail.
The starting materials can, if desired, also be formed in situ by not isolating them from the reaction mixture, but instead immediately converting them further into the compounds of the formula 1. The compounds according to the invention can be prepared, for example, as shown in the following reaction scheme:
Scheme 1
In a further process for the preparation of compounds of the formula I in which R1 and/or R2 is alkenyl, an aryl halide is reacted with an olefin in the presence of a tertiary amine and in the presence of a palladium catalyst (R. F. Heck, Acc. Chem.
Res. 12 (1979) 146). Examples of suitable aryl halides are chlorides, bromides and iodides, in particular bromides and iodides. The tertiary amines necessary for the success of the coupling reaction, such as, for example, triethylamine, are also suitable as solvent. Examples of suitable palladium catalysts are its salts, in particular Pd (tut) acetate, wirh organophosphorus (lil) compounds, such as, for example, triarylphosphines. This process can be carried out in the presence or absence of an inert solvent at temperatures between about 0 C and 150oC, preferably between 20 C and 100oC ; suitable solvents are, for example, nitriles, such as acetonitrile, or hydrocarbons, such as benzene or toluene. The aryl halides and olefins employed as starting materials are frequently commercially available and can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.
Ethers of the formula I are obtainable by etherification of corresponding hydroxyl compounds, preferably corresponding phenols, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example into the corresponding alkali metal alkoxide or alkali metal phenoxide, by treatment with NaH, NaNH2, NaOH, KOH, Na2CO3 or K2CO3. This metal derivative can then be reacted with the appropriate alkyl halide, alkyl sulfonate or dialkyl sulfate, advantageously in an inert solvent, such as, for example, acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide, or alternatively with an excess of aqueous or aqueous-alcoholic NaOH or KOH, at temperatures between about 20'C and 100*C.
In order to prepare the laterally substituted fluorine or chlorine compounds of the formula 1, corresponding aniline derivatives can be reacted with sodium nitrite and either with tetrafluoroboric acid (in order to introduce an F atom) or with copper (l) chloride (in order to introduce a chlorine atom), to give the diazonium salts, which are then decomposed thermally at temperatures of 100-140 The organometallic compounds are prepared, for example, by metal-halogen exchange (for example in accordance with Org. React. 6, 339-366 (1951) ) between the corresponding halogen compound and an organolithium compound, such as, preferably, tert-butyllithium or lithium naphthalenide, or by reaction with magnesium turnings.
The linking of an aliphatic group R1 to an aromatic ring is preferably carried out by
Friedel-Crafts alkylation or acylation by reacting the corresponding aromatic compounds with Lewis acid catalysis. Examples of suitable Lewis acids are Suc14, ZnC12 and in particular AICb and Tic4.
In addition, the compounds of the formula I can be prepared by reducing a compound which contains one or more reducible groups and/or C-C bonds in place of H atoms, but otherwise conforms to the formula 1.
Suitable reducible groups are preferably carbonyl groups, in particular keto groups, furthermore, for example, free or esterified hydroxyl groups or aromatically bonded halogen atoms. Preferred starting materials for the reduction are compounds which conform to the formula 1, but contain a-CH=CH-group in place of a-CH2CH2-group and/or contain a-CO-group in place of a-CH2-group and/or contain a free or functionally derived (for example in the form of its p-toluenesulfonate) OH group in place of an H atom.
The reduction can be carried out, for example, by catalytic hydrogenation at temperatures between about 00 and about 2000 and at pressures between about 1 and 200 bar in an inert solvent, for example an alcohol, such as methanol, ethanol or isopropanol, an ether, such as tetrahydrofuran (THF) or dioxane, an ester, such as ethyl acetate, a carboxylic acid, such as acetic acid, or a hydrocarbon, such as cyclohexane. Suitable catalysts are advantageously noble metals, such as Pt or Pd, which may be employed in the form of oxides (for example PtO2 or PdO), on a support (for example Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form.
Ketones can also be reduced by the methods of Clemmensen (using zinc, zinc amalgam or tin and hydrochloric acid, advantageously in aqueous-alcoholic solution or in the heterogeneous phase with water/toluene at temperatures between about 80 and 120 C) or Wolff-Kishner (using hydrazine, advantageously in the presence of alkali, such as KOH or NaOH, in a high-boiling solvent, such as diethylene glycol or triethylene glycol, at temperatures between about 100 and 2000C) to give the corresponding compounds of the formula I which contain alkyl groups and/or CH2CH2-bridges.
Furthermore, reductions using complex hydrides are possible. For example, arylsulfonyloxy groups can be removed reductively using LiAIH4, in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, advantageously in an inert solvent, such as diethyl ether or THF, at temperatures between about 0 and 1000C. Double bonds can be hydrogenated using NaBH4 or tributyltin hydride in methanol.
The starting materials are either known or can be prepared analogously to known compounds.
The liquid-crystalline media according to the invention preferably comprise from 2 to 40 components, in particular from 4 to 30 components, as further constituents besides one or more compounds according to the invention. These media very particularly preferably comprise from 7 to 25 components besides one or more compounds according to the invention. These further constituents are preferably selected from nematic or nematogenic (monotropic or isotropic) substances, in particular substances from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxylic acid or of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes, 1, 4-bis-cyclohexylbenzenes, 4,4'-biscyclohexylbiphenyls, phenyl-or cyclohexylpyrimidines, phenyl-or cyclohexylpyridines, phenyl-or cyclohexyldioxanes, phenyl-or cyclohexyl-1, 3 dithianes, 1, 2-diphenylethanes, 1, 2-dicyclohexylethanes, 1-phenyl-2cyclohexylethanes, 1-cyclohexyl-2- (4-phenylcyclohexyl) ethanes, 1-cyclohexyl-2- biphenylylethanes, 1-phenyl-2-cyclohexylphenylethanes optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acids. The 1,4phenylen groups in these compounds may also be fluorinated.
The most important compounds suitable as further constituents of media according to the invention can be characterized by the formulae 1,2, 3,4 and 5:
R'-L-E-R"1
R'-L-COO-E-R"2
R'-L-OOC-E-R"3
R'-L-CH2CH2-E-R"4 R'-L-C=C-E-R"5 In the formulae 1,2, 3,4 and 5, L and E, which may be identical or different, are in each case, independently of one another, a bivalent radical from the group formed by-Phe-, -Cyc-,-Phe-Phe-,-Phe-Cyc-,-Cyc-Cyc-,-Pyr-,-Dio-,-G-Phe-and-G-Cyc- and their mirror images, where Phe is unsubstituted or fluorine-substituted 1, 4-phenylen, Cyc is trans-1, 4-cyclohexylen or 1, 4-cyclohexylene, Pyr is pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, Dio is 1,3-dioxane-2, 5-diyl and G is 2- (trans1, 4-cyclohexyl) ethyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl or 1,3-dioxane-2, 5-diyl.
One of the radicals L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or
Phe-Cyc. The media according to the invention preferably comprise one or more components selected from the compounds of the formulae 1,2, 3, 4 and 5 in which
L and E are selected from the group consisting of Cyc, Phe and Pyr and simultaneously one or more components selected from the compounds of the formulae 1, 2,3, 4 and 5 in which one of the radicals L and E is selected from the group consisting of Cyc, Phe and Pyr and the other radical is selected from the group consisting of-Phe-Phe-, -Phe-Cyc-,-Cyc-Cyc-,-G-Phe-and-G-Cyc-, and optionally one or more components selected from the compounds of the formulae 1,2, 3,4 and 5 in which the radicals L and E are selected from the group consisting of-Phe Cyc-, -Cyc-Cyc-,-G-Phe-and-G-Cyc-.
In a smaller sub-group of the compounds of the formulae 1,2, 3,4 and 5, R' and R" are each, independently of one another, alkyl, alkenyl, alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbon atoms. This smaller sub-group is called group
A below, and the compounds are denoted by the sub-formulae 1 a, 2a, 3a, 4a and 5a. In most of these compounds, R'and R"are different from one another, one of these radicals usually being alkyl, alkenyl, alkoxy or alkoxyalkyl.
In another smaller sub-group of the compounds of the formulae 1,2, 3,4 and 5, which is called group B, R"is-F,-Cl,-NCS or- (O), CH3- (k+!) FkCII, where i is 0 or 1, and k and I are 1,2 or 3; the compounds in which R"has this meaning are denoted by the sub-formulae 1 b, 2b, 3b, 4b and 5b. Particular preference is given to those compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b in which R"is-F,-Cl,-NCS,
- CF3.-OCHF2or-OCF3. In the compounds of the sub-formulae 1 b, 2b, 3b, 4b and 5b, R'is as defined for the compounds of the sub-formulae 1a-5a and is preferably alkyl, alkenyl, alkoxy or alkoxyalkyl.
In a further smaller sub-group of the compounds of the formulae 1,2, 3,4 and 5, R" is-CN; this sub-group is called group C below, and the compounds of this sub-group are correspondingly described by sub-formulae 1c, 2c, 3c, 4c and 5c. In the compounds of the sub-formulae 1 c, 2c, 3c, 4c and 5c, R'is as defined for the compounds of the sub-formulae 1a-5a and is preferably alkyl, alkoxy or alkenyl.
In addition to the preferred compounds of groups A, B and C, other compounds of the formulae 1,2, 3,4 and 5 having other variants of the proposed substituents are also customary. All these substances can be obtained by methods which are known from the literature or analogously thereto.
Besides compounds of the formula I according to the invention, the media according to the invention preferably comprise one or more compounds selected from group A and/or group B and/or group C. The proportions by weight of the compounds from these groups in the media according to the invention are preferably:
Group A: 0 to 90%, preferably 20 to 90%, in particular 30 to 90%
Group B: 0 to 80%, preferably 10 to 80%, in particular 10 to 65%
Group C: 0 to 80%, preferably 5 to 80%, in particular 5 to 50%, the sum of the proportions by weight of the group A and/or B and/or C compounds present in the particular media according to the invention preferably being 5%-90% and in particular from 10% to 90%.
The media according to the invention preferably comprise from 1 to 40%, particularly preferably from 5 to 30%, of the compounds according to the invention. Further preferred media are those which comprise more than 40%, in particular from 45 to 90%, of compounds according to the invention. The media preferably comprise three, four or five compounds according to the invention.
The media according to the invention are prepared in a manner which is customary per se. In general, the components are dissolved in one another, advantageously at elevated temperature. By means of suitable additives, the liquid-crystalline phases can be modified in accordance with the invention in such a manner that they can be used in all types of liquid-crystal display elements which have been disclosed hitherto. Additives of this type are known to those skilled in the art and are described in detail in the literature (H. Kelker/R. Hatz, Handbook of Liquid Crystals, Verlag
Chemie, Weinheim, 1980). For example, pleochroic dyes can be added for the production of coloured guest-host systems, or substances can be added to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases.
The examples below are intended to illustrate the invention without representing a limitation. Above and below, percentages are percent by weight. All temperatures are given in degrees Celsius. m. p. denotes melting point, cl. p. = clearing point, Tg = glass transition temperature. Furthermore, C = crystalline state, N = nematic phase, Sm = smectic phase and I = isotropic phase. The numbers between these symbols indicate the conversion temperatures. An denotes the optical anisotropy (589 nm, 200C) and As the dielectric anisotropy (1 kHz, 20 C). The An and As values of the compounds according to the invention were obtained by extrapolation from liquidcrystalline mixtures consisting of 10% of the particular compound according to the invention and 90% of the commercially available liquid crystal ZLI 4792 (Merck,
Darmstadt).
The viscosity (mm2/sec) was determined at 20oC.
"Conventional work-up"means that water is added if necessary, the mixture is extracted with methylene chloride, diethyl ether or toluene, the phases are separated, the organic phase is dried and evaporated, and the product is purified by distillation under reduced pressure or crystallization and/or chromatography.
The following abbreviations are used:
THF tetrahydrofuran
KOtBu potassium tert-butoxide
RT room temperature
MTB ether methyl tert-butyl ether
Example 1
A mixture of 2. 0 g of 4"-Bromo-2', 2"-difluoro-4-pentyl-[1, 1' ; 4', terphenyl 1, 5. 0 g of pentyne, 0. 020 g of bis (triphenylphosphine)-palladium ( !))-chloride, 0. 054 g of copper (l) iodide and 50 ml of triethylamine was stirred overnight at 40 OC (reflux of pentyne). The mixture was allowed to cool and was subsequently subjected to conventional work-up, giving 2', 2"-Difluoro-4-pentyl-4"-pent-1-ynyl- [1, 1', 4', 1"]terphenyI2 (K67 N 124 I, ## = 1. 9, An = 0.3138).
The following examples can be prepared analogously :
Examples 2-24
R3-0-Z R4 (2) n-propyl F 1-propynyl zu (3) n-propyl-0--1-pentynyl (4) n-pentyl 4 propynyl F (5) 1-propynyl-1-propynyl - 0- (6) 1-pentynyl-1-pentynyl - 0- (7) n-propyl -CH2CH2-1-propynyl (8) n-pentyl -CH2CH2-1-propynyl --D (9) 1-propynyl -CH2CH2-1-propynyl -D (10) 1-pentynyl ',-C*C-1-pentynyl (11) n-propyl-0--1-propynyl (12) n-propyl 1-pentynyl (K 73 N 131 I, Ag = 2. 3, An = 0. 3192) (13) n-pentyl-0--1-propynyl
(14) 1-propynyl-0--1-propynyl (15) 1-pentynyl-0--1-pentynyl (16) n-propyl-CH2CH2-1-propynyl (17) n-pentyl-CH2CH2-1-propynyl (18) 1-propynyl-0--CH2CH2-1-propynyl (19) 1-pentynyl-C=-C-1-pentynyl (20) n-propyl--1-propynyl (21) n-propyl--1-pentynyl (22) n-pentyl--1-propynyl (23) 1-propynyl--1-propynyl (24) 1-pentynyl--1-pentynyl Examples 25-46
R3 {+ Z R4 (25) n-propyl \-1-propynyl F (26) n-propyl \,-1-pentynyl (27) n-pentyl \-1-propynyl F (28) 1-propynyl)-1-pentynyl F (29) n-propyl -CH2CH2-1-propynyl
(30) n-pentyl \-CH2CH2-1-propynyl (31) 1-propynyl ! --D (32) 1-pentynyl F-C=C-1-pentynyl - 0 (33) n-propyl-0--1-propynyl (34) n-propyl-0--1-pentynyl (35) n-pentyl-0--1-propynyl (36) 1-propynyl-0--1-propynyl (37) 1-pentynyl-0--1-pentynyl (38) n-propyl-AA-.-CH2CH2-1-propynyl (39) n-pentyl-CH2CH2-1-propynyl (40) 1-propynyl-CH2CH2-1-propynyl (41) 1-pentynyl-0--C=C-1-pentynyl (42) n-propyl--1-propynyl (43) n-propyl--1-pentynyl (44) n-pentyl--1-propynyl (45) 1-propynyl--1-propynyl (46) 1-pentynyl--1-pentynyl
Examples 47-69
R3-0-Z R4 (47) n-propyl F 1-propynyl - 0- (48) n-propyl \-1-pentynyl - 0- (49) n-pentyl \-1-propynyl - 0- (50) 1-propyny ! \-1-propynyt - 0- (51) 1-pentynyl F 1-pentynyl - 0- (52) n-propyl F-CH2CH2-1-propynyl - \. ) (53) n-pentyl F-CH2CH2-1-propynyl - 0 (54) 1-propynyl F-CH2CH2-1-propynyl - zu (55) 1-pentynyl 1-pentynyl - 0 (56) n-propyl 1-propynyl (57) n-propyl-0--1-pentynyl (58) n-pentyl-0--1-propynyl (59) 1-propynyl-0--1-propynyl (60) 1-pentynyl-0--1-pentynyl
(61) n-propyl-Y\--CH2CH2-1-propynyl (62) n-pentyl-0--CH2CH2-1-propynyl (63) 1-propynyl-0--CH2CH2-1-propynyl (64) 1-pentynyl-o\-C=C-1-pentynyl (65) n-propyl--1-propynyl (66) n-propyl--1-pentynyl (67) n-pentyl--1-propynyl (68) 1-propynyl--1-propynyl (69) 1-pentynyl--1-pentynyl
Claims (13)
1. An acetylene derivative of the formula I :
in which R1, R2 independently of one another are H, an alkyl radical having 1-12 carbon atoms which is unsubstituted or at least monosubstituted by halogen or CN and in which, in addition, one or more CH2 groups may each, independently of one another, be replaced by-0-,-CC or-CH=CH-in such a way that heteroatoms are not
connected directly, 2 3 L1, L2, L3, independently of one another are H or F L4, L5 L6 Z is-C=C-or a single bond, n, m, p independently of one another are 0 or 1, provided that n + m # 0.
2. An acetylene derivative ester as claimed in claim 1, wherein m is 0 and R1 is an alkyl, oxaalkyl or alkoxy radical having 1 to 10 carbon atoms or an alkenyl radical having 2 to 10 carbon atoms.
3. An acetylene derivative as claimed in claim 1 or claim 2, wherein m + n is 1.
4. An acetylene derivative as claimed in any of claims 1 to 3, wherein pis 1.
5. An acetylene derivative as claimed in any of claims 1 to 3, wherein each of the aromatic rings independently of one another, is unsubstituted or mono-substituted by fluorine.
6. An acetylene derivative as claimed in any of the preceding claims, wherein at least one of the aromatic rings is mono-substituted by fluorine.
7. An acetylene derivative as claimed in any of the preceding claims, in which Z is a single bond.
8. An acetylene derivative of the formulae IA to IF:
1 2 in which R, R2, Z m and n are as defined in claim 1.
9. An acetylene derivative substantially as hereinbefore described in the foregoing examples.
10. Use of a compound of the formula I as claimed in any of claims 1 to 9 as components of liquid-crystalline media.
11. A liquid-crystalline medium having at least two liquid-crystalline components, wherein it comprises at least one compound of the formula 1.
12. A liquid-crystal display element, wherein it contains a liquidcrystalline medium as claimed in claim 11.
13. An electro-optical display element, wherein it contains, as dielectric, a liquid-crystalline medium as claimed in claim 11.
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| Application Number | Priority Date | Filing Date | Title |
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| EP00114151 | 2000-07-12 |
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| GB2367058B GB2367058B (en) | 2004-07-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1346995A1 (en) * | 2002-03-15 | 2003-09-24 | MERCK PATENT GmbH | Process for the preparation of ring compounds |
| WO2005007775A1 (en) * | 2003-07-11 | 2005-01-27 | Merck Patent Gmbh | Liquid-crystal medium containing monofluoroterphenyl compounds |
| CN107109221A (en) * | 2014-12-19 | 2017-08-29 | 默克专利股份有限公司 | Double mesomorphic compounds and mesogenic media |
| CN107636114A (en) * | 2015-07-02 | 2018-01-26 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
| CN113604227A (en) * | 2021-08-06 | 2021-11-05 | 南昌虚拟现实研究院股份有限公司 | Liquid crystal medium, preparation method thereof and liquid crystal lens |
Families Citing this family (1)
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| CN113773226B (en) * | 2021-08-06 | 2023-12-08 | 南昌虚拟现实研究院股份有限公司 | Process for producing cyanopropyne derivative, liquid crystal medium and liquid crystal lens |
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| EP2332944A3 (en) * | 2002-03-15 | 2011-11-16 | Merck Patent GmbH | Process for the preparation of ring compounds |
| US8124817B2 (en) | 2002-03-15 | 2012-02-28 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| US7183447B2 (en) | 2002-03-15 | 2007-02-27 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| US8350100B2 (en) | 2002-03-15 | 2013-01-08 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| US7411100B2 (en) | 2002-03-15 | 2008-08-12 | Merck Gmbh | Process for the preparation of ring compounds |
| EP2103589A1 (en) * | 2002-03-15 | 2009-09-23 | Merck Patent GmbH | Polypenylenes as liquid crystals |
| US7842845B2 (en) | 2002-03-15 | 2010-11-30 | Merck Gmbh | Process for the preparation of ring compounds |
| US7786332B2 (en) | 2002-03-15 | 2010-08-31 | Merck Patent Gmbh | Process for the preparation of ring compounds |
| EP1346995A1 (en) * | 2002-03-15 | 2003-09-24 | MERCK PATENT GmbH | Process for the preparation of ring compounds |
| WO2005007775A1 (en) * | 2003-07-11 | 2005-01-27 | Merck Patent Gmbh | Liquid-crystal medium containing monofluoroterphenyl compounds |
| US7390538B2 (en) | 2003-07-11 | 2008-06-24 | Merck Patent Gmbh | Liquid-crystal medium containing monofluoroterphenyl compounds |
| CN107109221A (en) * | 2014-12-19 | 2017-08-29 | 默克专利股份有限公司 | Double mesomorphic compounds and mesogenic media |
| JP2018501248A (en) * | 2014-12-19 | 2018-01-18 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Bimesogenic compounds and mesogenic media |
| CN107109221B (en) * | 2014-12-19 | 2021-03-12 | 默克专利股份有限公司 | Bimesogenic compounds and mesogenic media |
| CN107636114A (en) * | 2015-07-02 | 2018-01-26 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
| CN113604227A (en) * | 2021-08-06 | 2021-11-05 | 南昌虚拟现实研究院股份有限公司 | Liquid crystal medium, preparation method thereof and liquid crystal lens |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0115694D0 (en) | 2001-08-22 |
| GB2367058B (en) | 2004-07-14 |
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