GB2350361A - Liquid crystalline 3,4,5-tricyanophenyl derivatives - Google Patents
Liquid crystalline 3,4,5-tricyanophenyl derivatives Download PDFInfo
- Publication number
- GB2350361A GB2350361A GB0012376A GB0012376A GB2350361A GB 2350361 A GB2350361 A GB 2350361A GB 0012376 A GB0012376 A GB 0012376A GB 0012376 A GB0012376 A GB 0012376A GB 2350361 A GB2350361 A GB 2350361A
- Authority
- GB
- United Kingdom
- Prior art keywords
- diyl
- coo
- groups
- tricyanophenyl
- atoms
- 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
- -1 3,4,5-tricyanophenyl Chemical class 0.000 title claims abstract description 95
- 239000007788 liquid Substances 0.000 title claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 66
- 239000002019 doping agent Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 24
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000013256 coordination polymer Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- POSCHTOBPNBGPH-UHFFFAOYSA-N 5-hydroxybenzene-1,2,3-tricarbonitrile Chemical compound OC1=CC(C#N)=C(C#N)C(C#N)=C1 POSCHTOBPNBGPH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 102100035861 Cytosolic 5'-nucleotidase 1A Human genes 0.000 description 4
- 101000802744 Homo sapiens Cytosolic 5'-nucleotidase 1A Proteins 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SJSRFXJWBKOROD-UHFFFAOYSA-N 1,1'-bi(cyclohexyl)-1-carboxylic acid Chemical class C1CCCCC1C1(C(=O)O)CCCCC1 SJSRFXJWBKOROD-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical class C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- OQZAQBGJENJMHT-UHFFFAOYSA-N 1,3-dibromo-5-methoxybenzene Chemical compound COC1=CC(Br)=CC(Br)=C1 OQZAQBGJENJMHT-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-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
- 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
- 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
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000004361 3,4,5-trifluorophenyl group Chemical group [H]C1=C(F)C(F)=C(F)C([H])=C1* 0.000 description 1
- PLKROHNMZPCGLD-UHFFFAOYSA-N 3-cyclohexylpyridazine Chemical class C1CCCCC1C1=CC=CN=N1 PLKROHNMZPCGLD-UHFFFAOYSA-N 0.000 description 1
- 125000001331 3-methylbutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 241001432959 Chernes Species 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 238000006751 Mitsunobu reaction Methods 0.000 description 1
- 101100521345 Mus musculus Prop1 gene Proteins 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 108700017836 Prophet of Pit-1 Proteins 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 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
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003098 cholesteric effect Effects 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
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 150000001935 cyclohexenes Chemical class 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
- 101150047356 dec-1 gene Proteins 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
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 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
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical class C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 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
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
Classifications
-
- 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
- C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
- C07C255/51—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings containing at least two cyano groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/55—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and esterified hydroxy groups bound to the carbon skeleton
-
- 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
-
- 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
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
-
- 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
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
-
- 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
- C09K19/0403—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems
- C09K2019/0407—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit the structure containing one or more specific, optionally substituted ring or ring systems containing a carbocyclic ring, e.g. dicyano-benzene, chlorofluoro-benzene or cyclohexanone
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
3,4,5-Tricyanophenyl derivatives of formula I <EMI ID=1.1 HE=30 WI=87 LX=403 LY=620 TI=CF> <PC>may be used as components in liquid crystal media and displays. These compounds exhibit very high dielectric anisotropy ( We ) and therefore can be used in small amounts as dopants to increase the value of We in liquid crystal media. In formula I: <DL TSIZE=10> <DT>R<DD>is F, Cl, CN, NCS, or a straight-chain or branched alkyl group with 1 to 25 C atoms which may be unsubstituted, mono- or polysubstituted by halogen or CN, it being also possible for one or more CH<SB>2</SB> groups to be replaced, in each case independently from one another, by -O-, -S-, -NH-, - N(CH<SB>3</SB>)-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, - CO-S-, -CH=CH-, -CH=CF-, -CF=CF- or -C I C- in such a manner that oxygen atoms are not linked directly to one another; <DT>A<SP>1</SP> and A<SP>2</SP><DD>are each independently 1,4-phenylene (wherein in addition one or more CH groups may be replaced by N),trans-1,4-cyclohexylene (in which, in addition, one or two non-adjacent CH<SB>2</SB> groups may be replaced by O and/or S), 1,4-cyclohexenylene, 1,4-bicyclo-(2,2,2)-octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydro-naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, cyclobutane-1,3-diyl, spiro[3.3]heptane-2,6-diyl or dispiro[3.1.3.1] decane-2,8-diyl, it being possible for all these groups to be unsubstituted, mono-, di-, tri- or tetrasubstituted with alkoxycarbonyl groups with 1 to 7 C atoms, wherein </DL> one or more H atoms may be substituted by F or Cl; Z<SB>1</SB> and Z<SB>2</SB> are each independently -CH<SB>2</SB>O-, -OCH<SB>2</SB>-, -COO-, - OCO-, -CH<SB>2</SB>CH<SB>2</SB>-, -(CH<SB>2</SB>)<SB>4</SB>-, -CF<SB>2</SB>CF<SB>2</SB>-, -CH=CH-, - CF=CF-, -C I C- or a single bond; and m is 0, 1 or 2.
Description
P0099212 2350361 -, 71 - 1 - 3,4,6-Tricyanophenyl Derivatives The
invention relates to 3,4,5-tricyanophenyl derivatives with a high dielectric anisotropy and to their use in liquid crystalline media and liquid crystal displays, and to liquid crystalline media and liquid crystal displays comprising such 3,4,5-tricyanophenyl derivatives.
For use in liquid crystal display applications it is often required to have available liquid crystalline compounds and media with a high positive value of the dielectric anisotropy As, which in turn requires that the material has a large molecular dipole. Until now, materials with terminal cyano groups have been used extensively for this purpose, as the cyano group is of high polarisability.
Thus, liquid crystalline compounds with a AF, of + 20 or more and having a terminal cyano group are widely known in prior art. Furthermore, liquid crystalline compounds with two cyano groups have been reported by H.A. Osman and T. Hyunh-Ba, Mol. Cryst. Liq. Cryst. 82, (1982), 331-38, S. Kelly et al., HeIv. Chim. Acta 7 (1984), 1572 ff. and 1580 ff. Osman and Hyunh-Ba, for example, describe the following compounds C51-11 I COO-&CN AE = + 14.3 CN C51-11 1 -&Coo- CN As = + 28.2 For many applications, however, liquid crystal compounds and media with still higher Ac are needed.
On the other hand, it is known that the use of compounds with cyano groups in high amounts in liquid crystal media can lead to a decrease P0099212 of the specific resistivity value and thus to a lower voltage holding ratio (VHR) in the medium. Therefore, it is desirable to reduce the amount of cyano compounds in liquid crystalline media. Therefore, materials with 3,4-difluoro- or 3,4,5-trifluorophenyl groups have been used in replacement for cyano compounds. These materials, however, usually have lower values of Ac.
Consequently, there is still a need for materials with high positive AE that can be used in liquid crystal media to increase the value of AE, without negatively affecting the other properties of the media, such as the resistivity and the liquid crystal phase range.
It was now found that the above mentioned drawbacks can be overcome by providing 3,4,5-tdcyanophenyl derivatives according to the present invention. The inventive compounds exhibit a very high value of the dielectric anisotropy. Therefore, it is possible to considerably increase the value of Ae in liquid crystal media by using the inventive compounds even in only small amounts.
One object of the present invention are 3,4,5-tricyanophenyl derivatives of formula I CN R-(A-Z)m-Al-Z' 0 CN I CN wherein R is F, Cl, CN, NCS or a straight-chain or branched alkyl group with 1 to 25 C atoms which may be unsubstituted, mono- or polysubstituted by halogen or CN, it being also possible for one or more non-adjacent CH2groups to be 35 replaced, in each case independently from one another, by -0-, -S-, -NH-, -N(CH3)-, -CO-, -COO-, -OCO-, -OCO- P0099212 0-, -S-CO-, -CO-S-, -CH=CH-, -CH=CF-, -CF=CFor C=-C- in such a manner that oxygen atoms are not linked directly to one another, A' and A 2 are each independently 1,4-phenylene, wherein in addition one or more CH groups may be replaced by N, trans1,4-cyclohexylene in which, in addition, one or two non-adjacent CH2groups may be replaced by 0 and/or S, 1,4-cyclohexenylene, 1,4-bicyclo-(2,2,2)-octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydro naphtha len e-2,6-d iyl, 1,2,3,4-tetrahydro-naphthalene 2,6-diyl, cyclobutane-1,3-diyl, spiro[3.3]heptane-2,6-diyl or dispiro[3.1.3.1] decane-2,8-diyl, it being possible for all these groups to be unsubstituted, mono-, di-, tri- or tetrasubstituted with F, Cl, CN or alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl groups with 1 to 7 C atoms, wherein one or more H atoms may be substituted by IF or Cl, Z' and Z2 are each independently -CH20-, -OCH2-, -COO-, -OCO-i -CH2CH2-, -(CH2)4-, -CF2CF2-, -CH=CH-, -CF=CF-, - C=-C- or a single bond, and M is 0, 1 or 2.
Another object of the present invention is the use of 3,4,5 tricyanophenyl derivatives of formula I in liquid crystalline media and liquid crystal displays.
Another object of the present invention is a liquid crystalline medium comprising at least two components, at least one of which is a 3,4,5 tricyanophenyl derivative of formula 1.
Yet another object of the present invention is a liquid crystal display with a liquid crystalline medium comprising at least two components, at least one of which is a 3,4,5-tricyanophenyl derivative of formula 1.
P0099212 Especially preferred are inventive 3,4,5-tricyanophenyl derivatives selected of formula [A CN R-- Z2. Z1 0 -CN IA -M CN wherein and are each independently N, 0 or --C _ 1 2 0 L' and L 2 are H or F, and m, Z1 and Z2 have the meanings given in formula I.
Further preferred are the following compounds 20 - 3,4,5-tricyanophenyl derivatives of formula 1, wherein Z1 is -COO-, - 3,4,5-tricyanophenyl derivatives of formula 1, wherein L' A' is __C - ' 2 m is 0 or 1, 30 A 2 is or and 2 L' and L 2 are H or F.
P0099212 - 3,4,5-tricyanophenyl derivatives of formula 1, wherein R is aikyi, alkoxy or alkenyl with 1 to 10 C- atoms.
Particularly preferred compounds of formula 1 are those wherein A' and A 2 are selected of 1,4-phenylene and trans-1,4-cyciohexylene, these rings being unsubstituted or substituted in 1 to 4 positions with F, Cl, CN or alky], alkoxy or alkoxycarbonyl with 1 to 4 C-atoms.
Z1 and Z2 in formula 1 preferably denote independently of one another -COO-, -OCO-, -CH2CH2-, -OCH2-, -CH20-, -CH=CH-, -C=-C- or a single bond, in particular -COO-, -OCO-, -CH2CH2-or a single bond.
A smaller group of preferred compounds of formula 1 is listed below.
For reasons of simplicity, Phe in these groups is 1,4-phenylene, which can additionally be substituted by L in 2-, 3- andlor 5-position, and L is F, Cl, CN or alkyl, alkoxy or alkoxycarbonyl with 1 to 4 C atoms. Furthermore, Cyc is 1,4-cyclohexylene, Pyd is pyridine-2,5, diyi, Pyr is pyrimidine-2,5-diyi, and Dio is trans-1,3-dioxane-2,5-diyi, The groups Pyd, Pyr and Dio also include their possible position isomers. W in these formulae is 3,4,5-tricyanophenyi.
R-Phe-Z-W 11-1 R-Cyc-ZM 11-2 R-Pyd-ZM 11-3 R-Pyr-ZM 11-4 R-Dio-ZM 11-5 R-Phe-Z-Phe-ZM 12-1 R-Cyc-Z-Phe-ZM 12-2 R-Phe-Z-Cyc-ZM 12-3 R-Cyc-Z-Cyc-ZM 12-4 R-Phe-Z-Pyd-ZM 12-5 R-Pyr-Z-Phe-ZM 12-6 R-Phe-Z-Pyr-ZM 12-7 R-Phe-Z-Dio-ZM 12-8 R-Dio-Z-Dio-ZM 12-9 P0099212 R-Cyc-Z-Dio-ZM 12-10 R-Phe-Z-Phe-Z-Phe-ZM 13-1 R-Cyc-Z-Phe-Z-Phe-ZM 13-2 R-Phe-Z-Cyc-Z-Phe-ZM 13-3 R-Cyc-Z-Cyc-Z-Phe-ZM 13-4 R-Phe-Z-Phe-Z-Cyc-ZM 13-5 R-Cyc-Z-Phe-Z-Cyc-ZM 13-6 R-Phe-Z-Cyc-Z-Cyc-ZM 13-7 R-Cyc-Z-Cyc-Z-Cyc-ZM 13-8 R-Pyr-Z-Phe-Z-Phe-ZM 13-9 R-Phe-Z-Pyr-Z-Phe-ZM 13-10 R-Phe-Z-Phe-Z-Pyr-ZM 13-11 R-Pyd-Z-Phe-Z-Phe-ZM 13-12 R-Phe-Z-Pycl-Z-Phe-ZM 13-13 R-Dio-Z-Phe-Z-Phe-ZM 13-14 R-Phe-Z-Dio-Z-Phe-ZM 13-15 R-Phe-Z-Phe-Z-Dio-ZM 13-16 R-Dio-Z-Cyc-Z-Cyc-ZM 13-17 R-Cyc-Z-Dio-Z-Cyc-ZM 13-18 R-Cyc-Z-Cyc-Z-Dio-ZM 13-19 R-Dio-Z-Dio-Z-Cyc-ZM 13-20 Especially preferred are the compounds of formulae 1 1-1,11-2,12-1 to 12-4 and 13-1 to 13-8.
Z in these preferred formulae is preferably -COO-, -OCO-, -CH2CH2-, -OCH2, -CH20-, -CH=CH-, -C=-C- or a single bond, in particular COO-, -OCO-, CH2CH2-or a single bond. 30 L is preferably F, Cl, CN, N02,Cl-13, C21-15, OCH3, 0CM,COCH3, COC2H5, CF3,0CIF3,0CHIF2 or OC2F5, in particular F, Cl, CN, CH3, C21-15, OCH3,COCH3 or OCF3 most preferably F, CH3,OCH3 or COCH3. 35 P0099212 Where Phe is denoting substituted 1,4-phenylene, it is preferably mono- or disubstituted by L according to one of the preferred meanings given above. Preferably it is 2-or 3-fluoro-, 2-or 3-chloro-, 3,5-difluoro- or 3,5-dichloro-1,4-phenylene.
Especially preferred are 3,4,5-tricyanophenyl derivatives of the following formulae L I CN R 0 coo -( 0 -CN I 1-1a L2 CN 1 CN R 0 0 CN I 1-1b CN CN R COO 0 -CN I 1-2a CN CN R H 0 CN I 1-2b N CN _C N C R 0 - 0 CN I 1-4a N N 35 P0099212 CN 0 R -CO - coo -1 0 -CN 11-5a CN 5 CN 0 R-CO 0 04CN 11-5b CN wherein R has the meaning of formula 1, L' and L2are independently of each other H or F.
R in the preferred compounds described above is particularly preferably an alkyl, alkenyl or alkoxy group with 1 to 10 C atoms. Straight-chain groups are especially preferred. If R is an alkyl or alkoxy group, i.e. where one or more CH2groups 20 are replaced by -0-, this may be straight- chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyi, hepty], octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyi, decyl, undecyl, dodecy], tridecyl, 25 tetradecyl, pentadecyl, methoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example. Oxaalky], i.e. where one CH2group is replaced by -0-, is preferably straight-chain 2-oxapropyl (=methoxymethyi), 2- (=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyi), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5oxahexyl, 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 9oxadecyl, for example.
If R is an alkyl group wherein one or more CH2groups are replaced by CH=CH-, this may be straight-chain or branched. It is preferably P0099212 1 -g- straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1 -, or prop-2-enyl, but-1 -, 2- or but-3-enyl, pent-1 -, 2-, 3 or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5 or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec- 1 -, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9- enyl.
Especially preferred alkenyl groups areC2-C7-1 E-alkenyl, C4-C7-M alkenyl, C5-C7-4-alkenyl,C6-C7-5-alkenyl undC7-6-alkenyl, in particularC2-C7-1 E-alkenyl,C4-C7-M-alkenyl andC5-C7-4-alkenyl.
Examples for particularly preferred alkenyl groups are vinyl, 1 E-propenyl, 1 E-butenyl, 1 E-pentenyl, 1 E-hexenyl, 1 E-heptenyl, 3-butenyl, 3E-pentenyl, M-hexenyl, M-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-hepteny], 5-hexeny], 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.
If R is an alkyl group, wherein one CH2group is replaced by -0- and one by -CO-, these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group -CO-0- or an oxycarbonyl group -0-CO-. Preferably this group R is straight-chain and has 2 to 6 C atoms.
It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethy], 2-propionyl oxyethyi, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyi, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyi, p ropoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonyimethyi, ethoxy carbonyimethyi, propoxycarbonyimethy], butoxycarbonyimethyi, 2-(methoxycarbonyi)ethyi, 2-(ethoxycarbonyi)ethyi, 2-(propoxycarbonyl)ethy], 3-(methoxycarbonyi)propyi, 3-(ethoxycarbonyl)propyi, 4-(methoxycarbonyi)-buty].
If R is an alkyl group, wherein two or more CH2groups are replaced by -0andlor -COO-, it can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyi, 3,3-bis-carboxy- P0099212 propyl, 4,4-bis-carboxy-butyi, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy hexyi, 7,7-bis-carboxy-heptyi, 8,8-bis-carboxy-octyi, 9,9-bis-carboxy nonyi, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyf)-methyi, 2,2-bis-(methoxycarbonyi)-ethyi, 3,3-bis-(methoxycarbonyi)-propyi, 4,4-bis-(methoxycarbonyi)-butyi, 5,5-bis-(methoxycarbonyi)-pentyi, 6,6-bis-(methoxycarbonyi)-hexyi, 7,7-bis-(methoxycarbonyi)-heptyi, 8,8-bis-(methoxycarbonyi)-octyi, bis-(ethoxycarbonyi)-methyi, 2,2-bis (ethoxycarbonyl)-ethyi, 3,3-bis-(ethoxycarbonyi)-propyi, 4,4-bis (ethoxycarbonyi)-butyi, 5,5-bis-(ethoxycarbonyi)-hexyi.
If R is an alkyl or alkenyl group that is monosubstituted by CN or CF3, it is preferably straight-chain. The substitution by CN or CF3can be in any desired position.
If R is an alkyl or alkenyl group that is at least monosubstituted by halogen, it is preferably straight-chain. Halogen is preferably F or Cl, in case of multiple substitution preferably F. The resulting groups include also perfluorinated groups. In case of monosubstitution the F or Cl substituent can be in any desired position, but is preferably in co -position. Examples for especially preferred straight-chain groups with a terminal F substituent are fluormethyl, 2-fluorethyl, 3-fluorpropyl, 4-fluorbuty], 5-fluorpentyl, 6-fluorhexyl and 7-fluorheptyl. Other positions of F are, however, not excluded.
R may be an achiral or a chiral group. In case of a chiral group it is preferably selected according to the following formula Ill:
1 1 2 -X -Q -CH-Q 1 3 Q Ill wherein X' is -0-, -S-, -CO-, -COO-, -OCO-, -OCOO- or a single bond, P0099212 Q1 is an alkylene or alkylene-oxy group with 1 to 10 C atoms or a single bond, Q2 is an alkyl or alkoxy group with 1 to 10 C atoms which may be unsubstituted, mono- or polysubstituted by halogen or CN, it being also possible for one or more non-adjacent CH2groups to be replaced, in each case independently from one another, by -C=-C-, -0-, -S-, -NH-, -N(CH3)-, -CO-, -COO-i -OCO-, -OCO-0-t -S-CO- or -CO-S- in such a manner that oxygen atoms are not linked directly to one another, Q3 is halogen, a cyano group or an alkyl or alkoxy group with 1 to 4 C atoms that is different from Q2.
Preferred chiral groups R are 2-butyl (=l-methylpropyl), 2methylbutyl, 2methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2propylpentyl, 2-octyl, in particular 2-methylbutyl, 2-methylbutoxy, 2methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 2octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4methylpentyl, 4-methylhexyl, 20 2-nonyl, 2-decyl, 2-dodecyl, 6methoxyoctoxy, 6-methyloctoxy, 6methyloctanoyloxy, 5methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4methylhexanoyloxy, 2-chlorpropionyloxy, 2chloro-3-methylbutyryloxy, 2chloro-4-methylvaleryloxy, 2-chloro-3methylvaleryloxy, 2-methyl-3oxapentyl, 2-methyl-3-oxahexyl, 125 methoxypropyl-2-oxy, I-ethoxypropyl-2oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2fluorodecyloxy for example. Compounds of formula I with branched groups R can occasionally be of importance due to their better solubility in the conventional liquid 30 crystalline media. Optically active compounds of this type are in particular useful as chiral dopants. Optically active and smectic compounds of formula I are useful as components for ferroelectric media and displays. 35 Compounds of formula I with SA- phases are particularly suitable e.g. for thermal adressed displays.
P0099212 In addition, chiral compounds of the formula I containing an achiral branched group R may occasionally be of importance, for example, due to a reduction in the tendency towards crystallization. Branched groups of this type generally do not contain more than one chain branch. Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), isopropoxy, 2-methyl propoxy and 3-methylbutoxy.
The inventive compounds of formula I can be synthesized according to or in analogy to methods known per se and described in the literature (for example in standard works of organic chemistry, 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 also be made here of variants which are known per se, but are not described here in greater detail. Some specific methods of preparation can be taken from the examples.
In particular, inventive compounds of formula I wherein Z' is an ester group can be prepared according to or in analogy to reaction scheme 1 from 3,4,5-tricyanophenol and the known acid derivatives of formula la.
The following reaction schemes and synthesis routes in the following are exemplarily described for inventive compounds wherein X is CN.
Scheme 1 CN R-(A2-Z2)m-A-CO-U' + HO-1 0 -CN Ia CN P0099212 CN R-(A 2_Z2),jAl-COO- 0 -CN la CN wherein U' is Cl, Br or OH and R, A', A 2, Z2 and m have the meaning of formula 1.
Thus, from the acids of formula W (U' = OH), it is easily possible according to known methods to prepare the corresponding acid halogenides (U' = Cl, Br), which are reacted with 3,4,5 tricyanophenol in the presence of a base to form the ester compounds of formula la. Alternatively, it is possible to react the acids of formula la directly with 3,4,5-tricyanophenol to the ester compounds of formula la in the presence of a dehydrating agent, like e.g. dicyclohexylcarbodiimid.
Inventive compounds of formula 1 wherein Z' is an ether group can be prepared according to or in analogy to reaction scheme 2 from 3,4,5 tricyanophenol and the known functional alkanes of formula lb.
Scheme 2 CN R-(A 2_Z2)m-AI---CH2-U 2 + HO-( 0 -CN 1b CN CN R-(A2_Z2)m-Al-CH20---10 -CN lb CN wherein U2 is Cl, Br, 1, OH,OS02, CH3, p-toluenesulfonyl, 6S02CH3 or 0S02C4F9, and R, A', A2, Z2 and m have the meaning of formula 1.
P0099212 The functional alkanes of formula lb can be obtained e.g. by reduction of the acids of formula la (T = OH) with complex Al hydrides, giving the corresponding alcohol of formula lb (U2 = OH).
The alcohol can then be further reacted either directly via Mitsunobu reaction or after transformation of the OH group into another leaving group U2 (e.g. Cl, Br, 1, OSO2OCF3) e.g. by the method of B. Jursic, Tetrahedron 44, 6677 (1980).
3,4,5-Tricyanophenol can be synthesized according to or in analogy to reaction scheme 3 or 4, starting from either 3,5-bromophenol or 3,5-dibromoanisole and followed by cyanation and, in case of scheme 4, by demethylation, as described e.g. by M. Kohn and G.
Soltesz, Monatsh. Chern 46, 245 (1925).
Scheme 3 Br Br CN HO-(0 HO-(0 -Br HO- 0 -CN Br Br CN Scheme 4 Br r CH30-CO CH3 0-(0 Br Br CN Br CN CH30- 0 -CN 3w HO---1 0 CN CN CN P0099212 The inventive compounds of formula 1 are particularly useful as components in liquid crystalline media.
Liquid crystalline media according to the invention preferably comprise 2 to 40, especially preferably 4 to 30 components as further constituents in addition to one or more inventive compounds. Very preferably these media comprise 2 to 25, preferably 3 to 15 compounds, at least one of which is a compound of formula 1. The further constituents are preferably low molecular weight liquid crystalline compounds selected from nematic or nematogenic substances, for example from the known classes of the azoxy benzenes, benzylidene-anilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl esters of cyclohehexane carboxylic acid, phenyl or cyclohexyi esters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters of cyclohexylcyclohexane carboxylic acid, cyclohexylphenyl esters of benzoic acid, of cyclohexane carboxylic acid and of cyclohexylcyclohexane carboxylic acid, phenylcyclo hexanes, cyclohexylbiphenyls, phenylcyclohexylcyclohexanes, cyclo hexylcyclohexanes, cyclohexylcyclohexenes, cyclohexylcyclohexy] cyclohexenes, 1,4-bis-cyclohexyibenzenes, 4,4'-bis-cyclohexyibi phenyls, phenyl- or cyclohexylpyrimidines, phenyl- or cyclohexyl pyridines, phenylor cyclohexylpyridazines, phenyl- or cyclohexyl dioxanes, phenyl- or cyclohexyi-1,3-dithianes, 1,2-di-phenylethanes, 1,2-dicyclohexylethanes, 1-phenyi-2-cyclohexylethanes, 1-cyclohexyi 2-(4-phenylcyclohexyi)ethanes, 1-cyclohexyf-2-biphenylethanes, 1 phenyi-2-cyclohexyi-phenylethanes, optionally halogenated stilbenes, benzyl phenyl ether, tolanes, substituted cinnamic acids and further classes of nematic or nematogenic substances. The 1,4-phenylene groups in these compounds may also be laterally mono- or difluorinated.
The preferred liquid crystalline media are based on the achiral compounds of this type.
P0099212 The most important compounds suitbale as components of the inventive liquid crystalline media can be characterized by the following formulae 1 to 6 R'-L-E-R" 1 R-L-COO-E-W 2 R'-L-OOC-E-R" 3 R'-L-CH2CH2-E-R" 4 R'-L-C=-C-E-R" 5 R-L-CH=CH-E-R" 6 wherein 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-phenylene, Cyc is trans 1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr is pyrimidine-2,5-diyi or pyridine-2,5-diyi, Dio is 1,3-dioxane-2,5-diyi and G is 2-(trans-1,4 cyclohexyl)ethyl, pyrimidine-2,5-diyi, pyridine-2,5-diyl or 1,3-dioxane 2,5-diyi.
In the case of compounds of formula 6, the rings L and E directly linked to the CH=CH group are preferably each Cyc.
One of the radicals L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. The inventive media preferably comprise one or more components selected from the compounds of formulae 1 to 5 in which L and E are selected from the group consisting of Cyc, Phe and Pyr, and simultaneously one or more 30 components selected from the compounds of formulae 1 to 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- und -G-Cyc-, and optionally one or more components selected from the compounds 35 of formulae 1 to 5 in which the radicals L and E are selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and - G-Cyc-.
P0099212 In a smaller subgroup of compounds of formulae 1, 2, 3, 4, 5 and 6 R' and W, in each case independently of one another, denote alkyl, alkeny], alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 C atoms. In the following this smaller subgroup is called group A, and the compounds forming this subgroup are labelled with the subformulae l a, 2a, 3a, 4a, 5a and 6a. In most of these compounds R' and W' are different, and one of these radicals is usually alky], alkenyi, alkoxy or alkoxyalkyl.
In another smaller subgroup of compounds of formulae 1, 2, 3, 4, 5 and 6, which is called group B, W' is -F, -C], -NCS or -(O)iCH3-(k+i) FkClbwith i being 0 or 1 and k+l being 1, 2 or 3; the compounds wherein W' has this meaning are labelled with the subformuiae 1 b, 2b, 3b, 4b, 5b and 6b. Especially preferred are compounds of subformulae 1 b, 2b, 3b, 4b, 5b and 6b wherein W' is -F, -C], -NCS, -CF3, -OCHF2or -OCF3.
In the compounds of subformulae 1 b, 2b, 3b, 4b, 5b and 6b R' is as defined given for the compounds of the subformulae l a-6a, and is preferably alkyl, alkenyl, alkoxy or aikoxyalky].
In a further smaller subgroup of compounds of formulae 1, 2, 3, 4, 5 and 6 W is -CN; this subgroup in the following is called group C and the compounds of this subgroup are labelled with the subformulae lc, 2c, 3c, 4c, 5c and 6 c. In the compounds of the subformulae 1 c, 2c, 3c, 4c, 5c and 6c R' is as defined for the compounds of the subformulae l a-6a, and is preferably alkyl, alkoxy or alkenyl.
Apart of the preferred compounds of groups A, B and C, other compounds of formulae 1, 2, 3, 4, 5 and 6 having other variants of the proposed substituents are also customary. Many of these compounds or mixtures thereof are commercially available. All these compounds can be prepared according to or in analogy to methods known per se and described in the literature (for example in standard works of organic chemistry, such as Houben-Weyl, Methoden der P0099212 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 also be made here of variants which are known per se, but are not described here in greater detail.
The inventive media in addition to compounds of formula I 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 inventive media 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 % with the sum of the proportions by weight of the compounds from group A and/or group B and/or group C present in the inventive media being preferably 5 % to 90 %, in particular 20 % to 90 %.
The inventive media preferably comprise 1 to 40 %, in particular 5 to 30 % of inventive compounds of formula 1. Further preferred are media comprising more than 40 %, in particular 45 to 90 % of compounds of formula 1. The media preferably comprise 1 to 5, in particular 1, 2 or 3 or compounds of formula I. 25 The preparation of the media that can be used according to the invention is carried out by conventional methods. Usually the desired amount of the components used in lower proportion is dissolved in the components forming the main part of the medium, preferably at 30 elevated temperatures. It is also possible to mix solutions of the components in an organic solvent, like e.g. aceton, chloroform or methanol, and to remove the solvent after mixing, e.g. by distillation. The liquid crystal media can also comprise other additives that are 35 known to the expert and are described in the literature (for example in standard works, such as H.Kelker/R. Hatz, Handbook of Liquid P0099212 Crystals, Verlag Chemie, Weinheim 1980). For example, it is possible to add 0- 15 % of pleochroic dyes, substances to modify the dielectric anisotropy, viscosity and/or the orientation of the nematic phases, or chiral dopants.
The inventive compounds can be used in liquid crystal media and liquid crystal displays, such as STN, TN, AMD-TN, temperature compensation, guest-host, phase change or surface stabilized or polymer stabilized cholesteric texture (SSCT, PSCT) displays. They are in particular useful as high A& dopants in liquid crystal media and displays of the above mentioned types.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever.
In the foregoing and in the following examples, unless otherwise indicated, all temperatures are set forth uncorrected in degrees Celsius and all parts and percentages are by weight.
The following abbreviations are used to illustrate the liquid crystalline phase behaviour of the compounds: K = crystalline; N = nematic; S = smectic; I = isotropic. The numbers between these symbols indicate the phase transition temperatures in degree Celsius. Furthermore, An is the birefringence at 589 nm and 20 "C and Ae is the dielectric anisotropy at 20 "C.
P0099212 Example 1
Compound (1) can be prepared according to scheme 1 above CN C3H7 -)- COO 0 -CN M (1) and has the following properties: AF, + 82, An = 0.201.
Example 2
Compound (2) can be prepared in analogy to example 1 Chl c 3 H 7 CH20 - 0 -CN CN (2) and has the following properties: AF. + 47, An = 0. 125. 25 Example 3 Compound (3) can be prepared in analogy to example 1 CN 30 C3 H7 -& CH 2 CF12---(O-CN W (3) P0099212 Examples 4 to 39 Analoguously to example 1 compounds (4) to(39) can be prepared.
Table 1
CN C3H7 z 0 -CN CN No. R z AE An 4 CH3 coo C2Hs coo 1 n-C31-17 coo +82 0.201 6 n-C4H9 coo 7 n-C51-111 coo 8 CH30 coo 9 C21-1,5 0 coo n-C31-170 coo 11 n-C4H90 coo 12 C H2CH coo 13 E-CH3-C H2'C H COO 14 C H2:"-CH-0 coo C H2=CH-CH20 COO 16 CH3 C H20 17 C2Hs CH20 2 n-C31-17 C H20 +47 0.125 18 n-C41-19 C H20 19 n-C51-111 C H20 P0099212 Table 1 (continued) _No. R Z1 AF, An CH30 CH20 21 C2H50 CH20 22 n-C31-170 CH20 23 n-C41-190 CH20 24 C1-12"=CH CH20 E-CH3-CH=CH CH20 26 CH2:-'Cl-1-0 CH20 27 C1-12=CH-CH20 CH20 28 CH3 CH2CH2 29 C2H5 CH2CH2 3 n-C31-17 CH2CH2 30 n-C4H9 CH2CH2 31n-C51-111 CH2CH2 32 CH30 CH2CH2 33 C2H50 CH2CH2 34 n-C31-170 CH2CH2 35 n-C4H90 CH2CH2 36 CH2=CH CH2CH2 37 E-CH3-CH=CH CH2CH2 38 C1-12=CH-0 CH2CH2 39 CH2=CH-CH20 CH2CH2 Remark: values extrapolated at 20T from 10 % solutoin in ZLI-4792.
P0099212 Examples 40 to 78 Analoguously to example 1 compounds (40) to(78) can be prepared.
Table 2
CN c 3 H7 -C)- z 0 -CN CN No. R z AE An 40 CH3 coo 41 C2H5 coo 42 n-C3H7 coo 43 n-C4Hg coo 44 n-C51-111 coo 45 CH30 coo 46 C21-1,50 coo 47 n-C3H70 coo 48 n-C4H90 coo 49 CH2CH coo 50 E-CH3-CH2:" "CH COO 51 C1-12--:C1-1-0 coo 52 CH2:--CH-CH20 coo 53 CH3 CH20 54 C21-1s CH20 P0099212 Table 2 (continued) No. R zI AE An n-C31-17 CH20 56 n-C41-19 CH20 57 n-C5H11 CH20 58 CH30 CH20 59 C2H50 CH20 n-C3H70 CH20 61 n-C41-190 CH20 62 CH2"CH CH20 63 E-CH3-CH=CH CH20 64 C1,12=CH-0 CH20 CH2=CH-CH20 CH20 66 CH3 CH2CH2 67 C2H5 CH2CH2 68 n-C3H7 CH2CH2 69 n-C4H9 CH2CH2 n-C51-111 CH2CH2 71 CH30 CH2CH2 72 C2H50 CH2CH2 73 n-C31-170 CH2CH2 74 n-C41-190 CH2CH2 C1-12=CH CH2CH2 76 E-CH3-CH=CH CH2CH2 77 CH2=CH-0 CH2CH2 78 C1-12=CH-CH20 CH2CH2 Remark: values extrapolated at 200 C from 10% solution in ZLI-4792.
P0099212 Examples 79 to 117 Analoguously to example 1 compounds (79) to(l 17) can be prepared.
Table 3
CN c 3 H 7_ A 2 Z 2 A' -COO 0 -CIM CN No. R A 2Z2Al- AE An 79 CH3 cc C2H5 cc 81 n-C3117 cc 82 n-C4119 cc 83 n-C51111 cc 84 CH30 cc C2H50 cc 86 n-C31---170cc 87 n-C41---190cc 88 CH2 "CH cc 89 E-CH3-CH2:_-CH CC CH2=CH-O cc 91 CH2=CH-CH20 cc 92 CH3 CP 93 C2H5 CP 94 n-C31---17CP n-C4H9 CP 96 n-C51---111CP 97 CH30 CP 98 C2H50 CP 99 n-C31---170CP P0099212 Table 3 (continued) No. R A 2 fA' Arc An 100 n-C41-19 CP 101 CH2CH CP 102 E-CH3-CH=CH CP 103 CH2=CH-0 CP 104 CH2=CH-CH20 CP 105 CH3 pp 106 C2Hs pp 107 n-C3H7 pp 108 n-C4H9 pp 109 n-C51-111 pp 110 CH30 pp ill C2H50 pp 112 n-C3H70 pp 113 n-C4H90 pp 114 CH2=CH pp 115 E-CH3-CH=CH pp 116 CH2=CH-0 pp 117 C1-12=CH-CH20 pp Remarks: values extrapolated at 2TC from 10 % solutoin in ZLI-4792.
cc --c CP -0- 0 pp 0 --CO)- P0099212
Claims (10)
1 A 3,4,5-Tricyanophenyl derivative of formula I CN R-(A 2 -Z 2)m-A 1 -Z 1 0 CN CN wherein R is F, Cl, CN, NCS or a straight-chain or branched alkyl group with 1 to 25 C atoms which may be 15 unsubstituted, mono- or polysubstituted by halogen or CN, it being also possible for one or more nonadjacent CH2groups to be replaced, in each case independently from one another, by -0-, -S-, -NH-, N(CH3)-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, 20 CO-S-, - CH=CH-, -CH=CF-, -CF=CF- or -C=-C- in such a manner that oxygen atoms are not linked directly to one another, A' and A2 are each independently 1,4-phenylene, wherein in addition one or more CH groups may be replaced by N, trans- 1,4- cyclohexylene in which, in addition, one or two non-adjacent CH2 groups may be replaced by 0 and/or S, 1,4-cyclohexenylene, 1,4-bicyclo-(2,2, 2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diYl,
30 decahydro- naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, cyclobutane- 1,3-diyl, spiro[3.3]heptane-2,6-diyl or dispiro[3.1.3. I] decane2,8-diyl, it being possible for all these groups to be unsubstituted, mono-, di-, tri- or tetrasubstituted with 35 F, Cl, CN or alkyl, alkoxy, alkylcarbonyl or ' P0099212 alkoxycarbonyl groups with 1 to 7 C atoms, wherein one or more H atoms may be substituted by F or Cl, Z1 and Z2 are each independently -CH20-, -OCH2-, -COO-, OCO-, -CH2CH2-, -(CH2)4-, -CIF2CF2-, -CH=CH-, CF=CF-, -C=-C- or a single bond, and m is 0, 1 or 2.
2. A 3,4,5-Thcyanophenyl derivative. according to claim 1, selected of formula IA CN R- -(: - Z2K - Z 1 - 0 -CN IA CN wherein and are each independently L1 N 4 - ' or -:0)--.
- 'm 2 2 ' -(N) 0 L' and L 2 are H or F, and m, Z1 and Z2 have the meanings given in formula 1.
3. A 3,4,5-Tricyanophenyl derivative according to claim 1 or 2, wherein Z1 is -COO-.
4. A 3,4,5-Thcyanophenyl derivative according to at least one of claims 1 to 3, wherein A' is 2 P0099212 m is 0 or 1, L' A 2 is or and L' and L 2 are H or F.
5. A 3,4,5-Tricyanophenyl derivative according to at least one of claims 1 to 4, wherein R is alkyl, alkoxy or alkenyl with 1 to 10 C10 atoms.
6. A 3,4,5-Tricyanophenyl derivative substantially as hereinbefore described in the foregoing examples. 15
7. Use of a 3,4,5-tricyanophenyl derivative according to at least one of claims 1 to 6 in a liquid crystalline media or liquid crystal display.
8. A liquid crystalline medium or liquid crystal display comprising a 3,4,5-tricyanophenyl derivative as claimed in any one of claims 1 to 20 6.
9. A liquid crystalline medium comprising at least two components, at least one of which is a 3,4,5-tricyanophenyl derivative according to at least one of claims 1 to 6. 25
10. A liquid crystal display with a liquid crystalline medium comprising at least two components, at least one of which is a 3,4,5tricyanophenyl derivative according to at least one of claims 1-6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP99110066 | 1999-05-22 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0012376D0 GB0012376D0 (en) | 2000-07-12 |
| GB2350361A true GB2350361A (en) | 2000-11-29 |
| GB2350361B GB2350361B (en) | 2003-12-03 |
Family
ID=8238230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0012376A Expired - Fee Related GB2350361B (en) | 1999-05-22 | 2000-05-22 | 3,4,5-tricyanophenyl derivatives |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2350361B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026991A1 (en) * | 2002-08-20 | 2004-04-01 | Merck Patent Gmbh | Liquid crystalline medium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5661344A (en) * | 1979-10-24 | 1981-05-26 | Chisso Corp | 4-substituted benzoic acid 3',5'-dicyanophenyl esters |
| JPS62111984A (en) * | 1985-11-12 | 1987-05-22 | Nippon Telegr & Teleph Corp <Ntt> | Alkylcyanophthalocyanines |
-
2000
- 2000-05-22 GB GB0012376A patent/GB2350361B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5661344A (en) * | 1979-10-24 | 1981-05-26 | Chisso Corp | 4-substituted benzoic acid 3',5'-dicyanophenyl esters |
| JPS62111984A (en) * | 1985-11-12 | 1987-05-22 | Nippon Telegr & Teleph Corp <Ntt> | Alkylcyanophthalocyanines |
Non-Patent Citations (2)
| Title |
|---|
| Chemical Abstracts, abstr no 109:47364 & JP 62 111 984 A 22.05.1987 * |
| WPI Abstract Accession No 1981-50766D/28 & JP 56 061 344 A 26.05.1981 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004026991A1 (en) * | 2002-08-20 | 2004-04-01 | Merck Patent Gmbh | Liquid crystalline medium |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0012376D0 (en) | 2000-07-12 |
| GB2350361B (en) | 2003-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100437234B1 (en) | Electro-optic liquid crystal display | |
| EP1054001B1 (en) | Isothiocyanate tolanes and liquid crystal mixtures containing them | |
| KR101512525B1 (en) | Pyridine compounds for liquid-crystalline mixtures | |
| EP2714843B2 (en) | Liquid crystal medium and liquid crystal display device | |
| US7442475B2 (en) | Cyanopyridone derivatives as liquid crystals | |
| EP2904068B1 (en) | Liquid crystal medium and liquid crystal display | |
| EP2708587B1 (en) | Liquid crystal medium and liquid crystal display | |
| EP2986688B1 (en) | Mesogenic compound, liquid crystal medium and liquid crystal display | |
| WO2006061094A1 (en) | Liquid crystal compounds, liquid crystal medium and liquid crystal display | |
| EP2032552B1 (en) | Mesogenic compounds, liquid crystal medium and liquid crystal display | |
| WO2006079406A1 (en) | Mesogenic compounds, liquid crystal medium and liquid crystal display | |
| DE19959721A1 (en) | New vinyl-substituted mesogenic compounds, useful as components of liquid crystal compositions, provide good low temperature properties | |
| GB2388600A (en) | Polymerisable mesogenic or liquid crystalline compounds comprising a cinnamic acid residue and an acetylene group | |
| KR20050088092A (en) | Cyclobutane derivatives | |
| TWI390022B (en) | Liquid crystal compounds, liquid crystal medium and liquid crystal display | |
| US6080452A (en) | Electro-optical liquid-crystal display | |
| KR20060135001A (en) | Liquid crystal compounds, liquid crystal media and liquid crystal displays | |
| EP1776438B1 (en) | Liquid crystal compounds, liquid crystal medium and liquid crystal display | |
| EP1739151B1 (en) | Mesogenic compounds, liquid crystal medium and liquid display | |
| GB2350361A (en) | Liquid crystalline 3,4,5-tricyanophenyl derivatives | |
| DE19525314A1 (en) | Stable liq. crystalline or mesogenic di:oxanyl di:oxane(s) and intermediates - are prepd. by reducing di:oxanyl acetal(s), di:ester(s) or di:nitrile(s) to di:ol(s) and condensing with aldehyde or acetal, useful in liq. crystalline medium e.g. for LCD | |
| EP1447435B1 (en) | 1,4-Di-(trans-4-Cyclohexyl)benzene derivatives and their use in liquid crystal media and liquid crystal devices | |
| EP1816180B1 (en) | Mesogenic compounds, liquid crystal medium, and liquid crystal display | |
| EP1690915B1 (en) | Mesogenic compounds, liquid crystal medium and liquid crystal display | |
| EP1690916B1 (en) | Mesogenic compounds, liquid crystal medium and liquid crystal display |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20110522 |