JPH07165635A - Difluoroethylene derivative compound and liquid crystal composition containing the compound - Google Patents
Difluoroethylene derivative compound and liquid crystal composition containing the compoundInfo
- Publication number
- JPH07165635A JPH07165635A JP5317088A JP31708893A JPH07165635A JP H07165635 A JPH07165635 A JP H07165635A JP 5317088 A JP5317088 A JP 5317088A JP 31708893 A JP31708893 A JP 31708893A JP H07165635 A JPH07165635 A JP H07165635A
- Authority
- JP
- Japan
- Prior art keywords
- group
- liquid crystal
- compound
- general formula
- alkyl group
- 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
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 74
- 150000001875 compounds Chemical class 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- -1 Difluoroethylene derivative compound Chemical class 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 12
- 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 9
- 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
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 claims 1
- KVUDKWKLRVCYAC-SSDCCQKPSA-N C1C[C@@H](CCC)CC[C@@H]1C(\F)=C(/F)C1=CC=C(F)C=C1 Chemical group C1C[C@@H](CCC)CC[C@@H]1C(\F)=C(/F)C1=CC=C(F)C=C1 KVUDKWKLRVCYAC-SSDCCQKPSA-N 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000037361 pathway Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 6
- 210000002858 crystal cell Anatomy 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VIWUJKBBJRFTMC-UHFFFAOYSA-N (1,2-difluoro-2-phenylethenyl)benzene Chemical class C=1C=CC=CC=1C(F)=C(F)C1=CC=CC=C1 VIWUJKBBJRFTMC-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- KGNQDBQYEBMPFZ-UHFFFAOYSA-N 1-fluoro-4-iodobenzene Chemical compound FC1=CC=C(I)C=C1 KGNQDBQYEBMPFZ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- CMNPITHTADJFNM-KYZUINATSA-N CCC[C@H]1CC[C@H](C(F)=C(F)F)CC1 Chemical group CCC[C@H]1CC[C@H](C(F)=C(F)F)CC1 CMNPITHTADJFNM-KYZUINATSA-N 0.000 description 2
- OHINIETVYXLTEQ-MGCOHNPYSA-N CCC[C@H]1CC[C@H](C=C(F)F)CC1 Chemical group CCC[C@H]1CC[C@H](C=C(F)F)CC1 OHINIETVYXLTEQ-MGCOHNPYSA-N 0.000 description 2
- AGBINQHSDMZNBI-MGCOHNPYSA-N CCC[C@H]1CC[C@H](CO)CC1 Chemical compound CCC[C@H]1CC[C@H](CO)CC1 AGBINQHSDMZNBI-MGCOHNPYSA-N 0.000 description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- OBJPDGTYNOUIBF-VXPUYCOJSA-N 1-[(Z)-1,2-difluoro-2-(4-propylphenyl)ethenyl]-4-propylbenzene Chemical compound C1=CC(CCC)=CC=C1C(\F)=C(\F)C1=CC=C(CCC)C=C1 OBJPDGTYNOUIBF-VXPUYCOJSA-N 0.000 description 1
- QCNUKEGGHOLBES-UHFFFAOYSA-N 4-propylcyclohexane-1-carboxylic acid Chemical compound CCCC1CCC(C(O)=O)CC1 QCNUKEGGHOLBES-UHFFFAOYSA-N 0.000 description 1
- DHYDMIPLXHLACC-BHLXARMKSA-N CCC[C@H]1CC[C@H](C(F)C(F)(F)F)CC1 Chemical compound CCC[C@H]1CC[C@H](C(F)C(F)(F)F)CC1 DHYDMIPLXHLACC-BHLXARMKSA-N 0.000 description 1
- OZKLOXFZSOVSRA-MGCOHNPYSA-N CCC[C@H]1CC[C@H](C=O)CC1 Chemical compound CCC[C@H]1CC[C@H](C=O)CC1 OZKLOXFZSOVSRA-MGCOHNPYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ジフルオロエチレン誘
導体化合物およびそれを含有する液晶組成物に関する。FIELD OF THE INVENTION The present invention relates to a difluoroethylene derivative compound and a liquid crystal composition containing the same.
【０００２】[0002]
【従来の技術】液晶表示素子は、時計、電卓をはじめ、
近年では測定器、自動車用計器、複写器、カメラ、ＯＡ
機器用表示装置、家電製品用表示装置等種々の用途に使
用され始めており、広い動作温度範囲、低動作電圧、高
速応答性、高コントラスト比、広視角、化学的安定性等
の種々の性能要求がなされている。2. Description of the Related Art Liquid crystal display devices include clocks, calculators,
In recent years, measuring instruments, automobile instruments, copying machines, cameras, OA
It has begun to be used in various applications such as device display devices and home appliance display devices, and various performance requirements such as wide operating temperature range, low operating voltage, high-speed response, high contrast ratio, wide viewing angle, chemical stability, etc. Has been done.
【０００３】しかし、現在のところ、これらの特性を単
独の材料で全て満たす材料はなく、複数の液晶、および
非液晶の材料を混合して液晶組成物として要求性能を満
たしている状態である。このため、各種特性のすべてで
はなく、一または二以上の特性に優れた液晶または非液
晶の材料開発が望まれている。However, at present, there is no material satisfying all of these characteristics with a single material, and a plurality of liquid crystal and non-liquid crystal materials are mixed to satisfy the required performance as a liquid crystal composition. For this reason, it is desired to develop a liquid crystal or non-liquid crystal material that is excellent in one or two or more of all the characteristics.
【０００４】[0004]
【発明が解決しようとする課題】液晶を用いた表示素子
分野においては、その性能向上が望まれており、低電圧
駆動、高精細表示、高コントラスト比、広視角特性、低
温応答特性、広動作温度範囲等が望まれており、これら
はいずれかを向上させると他のいずれかが犠牲になると
いう傾向がある。In the field of display devices using liquid crystals, it is desired to improve their performance, and low voltage driving, high definition display, high contrast ratio, wide viewing angle characteristics, low temperature response characteristics, wide operation are required. Temperature ranges and the like are desired, and any one of them tends to be sacrificed when the other is improved.
【０００５】特に、最近、電池駆動においては低電圧駆
動と高速応答、ＯＡ機器等においては高精細表示と高速
応答、自動車用表示等においては低温応答もしくは広動
作温度範囲で高速応答というように、その応答速度の向
上が望まれている。In particular, recently, low voltage drive and high speed response in battery drive, high definition display and high speed response in OA equipment, low temperature response in automobile display etc. or high speed response in wide operating temperature range have been made. It is desired to improve the response speed.
【０００６】このためには、いくつかの改善方法が考え
られるが、その一つとして低粘性の液晶組成物の採用が
ある。即ち、液晶組成物の粘性が低下すれば、応答速度
は向上し、低温でも実用的な速度での表示が可能にな
る。また、従来と同じ応答速度でよければ、より低電圧
で駆動できたり、より高いデューティ駆動が可能、即
ち、高精細駆動が可能になる。To solve this problem, some improvement methods can be considered. One of them is to adopt a low viscosity liquid crystal composition. That is, if the viscosity of the liquid crystal composition is reduced, the response speed is improved, and it is possible to display at a practical speed even at low temperatures. Further, if the response speed is the same as that of the conventional one, it is possible to drive with a lower voltage or drive with a higher duty, that is, high-definition drive becomes possible.
【０００７】このような目的のため、特開平３−４１０
３７あるいは特開平３−２９４３８６に示されるような
p,p'- 二置換ジフルオロスチルベン化合物が提案されて
いる。この化合物は以下の一般式(3) で示されるような
化学構造を有している。For such a purpose, JP-A-3-410 is used.
37 or as disclosed in JP-A-3-294386.
P, p'-disubstituted difluorostilbene compounds have been proposed. This compound has a chemical structure represented by the following general formula (3).
【０００８】[0008]
【化３】 [Chemical 3]
【０００９】ただし、一般式(3) のRA、RBはn-アルキル
基、n-アルコキシ基、n-アルコキシカルボニル基を意味
する。However, R A and R B in the general formula (3) mean an n-alkyl group, an n-alkoxy group and an n-alkoxycarbonyl group.
【００１０】この一般式(3) の化合物は、低粘性でフッ
素置換されていないスチルベン化合物よりも光に対する
安定性が向上しているものであった。しかし、通常使用
されている一般の液晶化合物に比しては、光に対する安
定性がまだ劣っており、使用環境が限定されたり、紫外
線カットフィルターを併用せざるを得ないことが多かっ
た。したがって、低粘性で光に対する安定性が高い液晶
材料が望まれていた。The compound of the general formula (3) had low viscosity and improved stability to light as compared with a stilbene compound which was not substituted with fluorine. However, the stability against light is still inferior to the commonly used general liquid crystal compounds, and the use environment is limited, and it is often necessary to use an ultraviolet cut filter together. Therefore, a liquid crystal material having low viscosity and high stability to light has been desired.
【００１１】[0011]
【課題を解決するための手段】本発明は、前記課題を解
決すべく、新規な材料を提供するものであり、下記一般
式(1) で表されるジフルオロエチレン誘導体化合物を提
供するものである。The present invention provides a novel material for solving the above problems, and provides a difluoroethylene derivative compound represented by the following general formula (1). .
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】ただし、一般式(1) 中、A1、A2、A3、A4、
Y1、Y2、R1、R2、m 、n は下記のものを示す。However, in the general formula (1), A 1 , A 2 , A 3 , A 4 ,
Y 1 , Y 2 , R 1 , R 2 , m and n are as follows.
【００１４】A3は1,4-フェニレン基、A2はトランス-1,4
- シクロヘキシレン基であり、A1、A4は相互に独立して
トランス-1,4- シクロヘキシレン基、1,4-フェニレン
基、または1,4-シクロヘキセニレン基であり、これらの
環基は夫々非置換であるかあるいは置換基として１個以
上のハロゲン原子、シアノ基を有し、これらの環基中の
環を構成する１個以上の=CH-基は窒素原子に置換されて
いてもよく、また、環を構成する１個以上の -CH2-基は
酸素原子もしくは硫黄原子に置換されていてもよい。A 3 is a 1,4-phenylene group, A 2 is trans-1,4
-Is a cyclohexylene group, A 1 and A 4 are each independently a trans-1,4-cyclohexylene group, a 1,4-phenylene group, or a 1,4-cyclohexenylene group, and these rings are Each of the groups is unsubstituted or has at least one halogen atom or cyano group as a substituent, and one or more = CH-groups constituting the ring in these ring groups are substituted with a nitrogen atom. Or one or more —CH 2 — groups constituting the ring may be substituted with an oxygen atom or a sulfur atom.
【００１５】Y1、Y2は相互に独立して-COO- 、-OCO- 、
-C≡C-、-CH2CH2-、-CH=CH- 、-OCH2-、-CH2O-または単
結合を示す。Y 1 and Y 2 are independently of each other -COO-, -OCO-,
-C≡C -, - CH 2 CH 2 -, - CH = CH-, -OCH 2 -, - shows a CH 2 O- or a single bond.
【００１６】R2はフッ素原子であり、R1は炭素数 1〜10
のアルキル基、ハロゲン原子あるいはシアノ基を示し、
アルキル基の場合には、このアルキル基中の炭素−炭素
結合間あるいはこのアルキル基と環基との間の炭素−炭
素結合間に酸素原子、カルボニルオキシ基、あるいはオ
キシカルボニル基が挿入されてもよく、また、そのアル
キル基中の炭素−炭素結合の一部が三重結合あるいは二
重結合にされていてもよく、また、そのアルキル基内の
１個の-CH2- 基がカルボニル基に置換されていてもよ
く、また、そのアルキル基中の水素原子の一部もしくは
すべてがフッ素原子で置換されていてもよい。R 2 is a fluorine atom and R 1 has 1 to 10 carbon atoms.
Represents an alkyl group, a halogen atom or a cyano group of
In the case of an alkyl group, even if an oxygen atom, a carbonyloxy group or an oxycarbonyl group is inserted between carbon-carbon bonds in the alkyl group or between carbon-carbon bonds between the alkyl group and the ring group. Also, a part of the carbon-carbon bond in the alkyl group may be a triple bond or a double bond, and one -CH 2 -group in the alkyl group is substituted with a carbonyl group. In addition, some or all of the hydrogen atoms in the alkyl group may be replaced with fluorine atoms.
【００１７】m 、n は相互に独立して 0または 1を示
す。M and n each independently represent 0 or 1.
【００１８】また、本発明は、下記一般式(2) （ただ
し、一般式(2) 中A2、A3、R1およびR2については、一般
式(1) と同じものを示す）で表されるジフルオロエチレ
ン誘導体化合物を提供するものである。Further, the present invention is represented by the following general formula (2) (wherein A 2 , A 3 , R 1 and R 2 in the general formula (2) are the same as those in the general formula (1)). The present invention provides a difluoroethylene derivative compound represented.
【００１９】[0019]
【化５】 [Chemical 5]
【００２０】さらに、本発明は、一般式(1) または一般
式(2) の化合物からなる液晶化合物および一般式(1) ま
たは一般式(2) の化合物を含有する液晶組成物、さらに
は、それらの液晶化合物あるいは液晶組成物を電極付基
板間に挟持してなる液晶電気光学素子を提供するもので
ある。Furthermore, the present invention provides a liquid crystal compound comprising the compound of the general formula (1) or the general formula (2) and a liquid crystal composition containing the compound of the general formula (1) or the general formula (2). It is intended to provide a liquid crystal electro-optical element in which those liquid crystal compounds or liquid crystal compositions are sandwiched between substrates with electrodes.
【００２１】本発明の一般式(1) の化合物は、低粘性で
あり、かつ、他の液晶または非液晶との相溶性に優れ、
化学的にも安定な材料である。The compound of the general formula (1) of the present invention has low viscosity and excellent compatibility with other liquid crystals or non-liquid crystals,
It is a chemically stable material.
【００２２】さらに、本発明の化合物の一般式(1) の化
合物は、前述した一般式(3) の化合物と比較し、光に対
して安定であり耐久性が向上する、弾性係数（Ｋ33／Ｋ
11）が増加し高コントラス化する、液晶上限温度（Ｔ
C ）が上昇し液晶温度幅が増大する、粘度（η）が減少
し高速応答に有利になる等、各特性が改善された材料で
ある。Further, the compound of the general formula (1) of the compound of the present invention is more stable to light and has improved durability (K 33 ) than the compound of the general formula (3) described above. / K
11 ) increases and the contrast increases, and the maximum liquid crystal temperature (T
C ) is increased, the temperature range of the liquid crystal is increased, the viscosity (η) is decreased, which is advantageous for high-speed response.
【００２３】特に高速ＳＴＮ用液晶材料として、一般式
(3) の化合物より優位性があり、有用である。Particularly as a liquid crystal material for high-speed STN, a general formula
It is more advantageous and useful than the compound of (3).
【００２４】本発明の化合物の具体的構造としては、以
下のような化合物がある。その代表的化合物として、環
の数が２個の化合物として以下のような化合物がある。Specific structures of the compounds of the present invention include the following compounds. As typical compounds thereof, there are the following compounds as compounds having two rings.
【００２５】[0025]
【化６】 [Chemical 6]
【００２６】一般式(4) の化合物としては、より具体的
には、以下のような化合物がある。なお、以下の説明に
おいては、一般式(4) の化合物に限らず、「-Ph-」は1,
4-フェニレン基を表し、「-Cy-」はトランス-1,4- シク
ロヘキシレン基を表し、「-Ch-」は1,4-シクロヘキセニ
レン基、好ましくは1-シクロヘキセン-1,4- イレン基を
表し、「PhF」 はモノフルオロ-1,4- フェニレン基あるい
はポリフルオロ-1,4-フェニレン基を表す。また、i は
１〜４の整数を表す。More specifically, the compound of the general formula (4) includes the following compounds. In the following description, not only the compound of the general formula (4) but also “-Ph-” is 1,
Represents a 4-phenylene group, "-Cy-" represents a trans-1,4-cyclohexylene group, "-Ch-" is a 1,4-cyclohexenylene group, preferably 1-cyclohexene-1,4- It represents an ylene group, and “PhF” represents a monofluoro-1,4-phenylene group or a polyfluoro-1,4-phenylene group. Further, i represents an integer of 1 to 4.
【００２７】[0027]
【化７】 [Chemical 7]
【００２８】また、環の数が３個の化合物として、以下
のような化合物がある。The following compounds are examples of compounds having three rings.
【００２９】[0029]
【化８】 [Chemical 8]
【００３０】一般式(5) の化合物としては、より具体的
には以下のような化合物がある。More specifically, the compound of the general formula (5) includes the following compounds.
【００３１】[0031]
【化９】 [Chemical 9]
【００３２】また、環の数が４個の化合物として、以下
のような化合物がある。Further, as a compound having four rings, there are the following compounds.
【００３３】[0033]
【化１０】 [Chemical 10]
【００３４】一般式(6) の化合物としては、より具体的
には以下のような化合物がある。More specifically, the compound of the general formula (6) includes the following compounds.
【００３５】[0035]
【化１１】 [Chemical 11]
【００３６】このほか、３環以上の化合物の場合、環と
環との間のY1、Y2を単結合以外に変更した以下のような
化合物もある。In addition, in the case of a compound having three or more rings, there are the following compounds in which Y 1 and Y 2 between the rings are changed to other than a single bond.
【００３７】[0037]
【化１２】 [Chemical 12]
【００３８】[0038]
【化１３】 [Chemical 13]
【００３９】また、A2をトランス−1,4-シクロヘキシレ
ン基の水素原子の一部をハロゲン原子もしくはシアノ基
に置換した基にしてもよい。また、A1、A3、A4の環基の
水素原子の一部をハロゲン原子もしくはシアノ基に置換
した基にしたり、環を構成する=CH-基の一部を窒素原子
に置換したり、または、環を構成する-CH2- 基の一部を
酸素原子もしくは硫黄原子に置換した例として以下のよ
うな化合物が挙げられる。Further, A 2 may be a group in which a part of hydrogen atoms of trans-1,4-cyclohexylene group is replaced with a halogen atom or a cyano group. Further, it may be a group in which a part of hydrogen atoms of the ring group of A 1 , A 3 , and A 4 is replaced with a halogen atom or a cyano group, or a part of = CH- group constituting the ring is replaced with a nitrogen atom. Alternatively, the following compounds may be mentioned as examples in which a part of the —CH 2 — group constituting the ring is replaced with an oxygen atom or a sulfur atom.
【００４０】[0040]
【化１４】 [Chemical 14]
【００４１】本発明の上記の一般式(1) の化合物は、そ
の少なくとも１種を他の液晶材料および／または非液晶
材料と混合して液晶組成物にして使用される。それによ
り、その液晶組成物を低粘性とすることができ、液晶表
示素子とした場合に高速応答が可能になる。The compound of the above general formula (1) of the present invention is used as a liquid crystal composition by mixing at least one of them with other liquid crystal material and / or non-liquid crystal material. As a result, the liquid crystal composition can have a low viscosity, and high-speed response can be achieved when the liquid crystal display device is used.
【００４２】本発明の化合物と混合させる物質として
は、例えば以下のようなものがある。なお、以下の式で
のRC、RDはアルキル基、アルコキシ基、ハロゲン原子、
シアノ基等の基を表す。また、「-NON-」 はアゾキシ基を
表す。Examples of the substance to be mixed with the compound of the present invention are as follows. In the formulas below, R C and R D are an alkyl group, an alkoxy group, a halogen atom,
Represents a group such as a cyano group. Moreover, "-NON-" represents an azoxy group.
【００４３】[0043]
【化１５】 [Chemical 15]
【００４４】[0044]
【化１６】 [Chemical 16]
【００４５】なお、これらの化合物は単なる例示にすぎ
なく、環構造もしくは末端基の水素原子をハロゲン原
子、シアノ基、メチル基等に置換してもよく、シクロヘ
キサン環、ベンゼン環の他の六員環、五員環、例えば、
ピリジン環、ジオキサン環等に置換してもよく、さらに
環と環の間の結合基を変更することも可能であり、所望
の性能に合わせて種々の材料が選択使用されればよい。These compounds are merely examples, and the hydrogen atom of the ring structure or the terminal group may be replaced with a halogen atom, a cyano group, a methyl group or the like, and other six members of the cyclohexane ring and the benzene ring. Ring, five-membered ring, for example,
It may be substituted with a pyridine ring, a dioxane ring, or the like, and the bonding group between the rings may be changed, and various materials may be selected and used according to the desired performance.
【００４６】本発明の化合物を含む液晶組成物は、液晶
セルに注入する等して、電極付の基板間に挟持され、液
晶電気光学素子を構成する。The liquid crystal composition containing the compound of the present invention is sandwiched between substrates with electrodes by injection into a liquid crystal cell or the like to form a liquid crystal electro-optical element.
【００４７】代表的な液晶セルとしては、ツイストネマ
チック（ＴＮ）型液晶電気光学素子がある。なお、ここ
で液晶電気光学素子と表現しているのは、表示用途以
外、例えば、調光窓、光シャッター、偏光交換素子等に
も使用できることを明らかにしているためである。A typical liquid crystal cell is a twisted nematic (TN) type liquid crystal electro-optical element. The expression "liquid crystal electro-optical element" is used here because it is clarified that the liquid crystal electro-optical element can be used for a light control window, an optical shutter, a polarization exchange element, etc., in addition to the display application.
【００４８】上記液晶電気光学素子は、ＴＮ方式、ゲス
ト・ホスト（ＧＨ）方式、動的散乱方式、フェーズチェ
ンジ方式、ＤＡＰ方式、二周波駆動方式、強誘電性液晶
表示方式等種々のモードで使用することができる。The liquid crystal electro-optical element is used in various modes such as a TN system, a guest-host (GH) system, a dynamic scattering system, a phase change system, a DAP system, a dual frequency drive system and a ferroelectric liquid crystal display system. can do.
【００４９】以下に、液晶電気光学素子の構成および製
法の具体例を示す。プラスチック、ガラス等の基板上
に、必要に応じてSiO2、Al2O3 等のアンダーコート層や
カラーフィルター層を形成し、In2O3-SnO2（ＩＴＯ）、
SnO2等の電極を設け、パターニングした後、必要に応じ
てポリイミド、ポリアミド、SiO2、Al2O3 等のオーバー
コート層を形成し、配向処理し、これにシール材を印刷
し、電極面が相対向するように配して周辺をシールし、
シール材を硬化して空セルを形成する。Specific examples of the structure and manufacturing method of the liquid crystal electro-optical element will be described below. If necessary, an undercoat layer such as SiO 2 or Al 2 O 3 or a color filter layer may be formed on a substrate such as plastic or glass, and In 2 O 3 -SnO 2 (ITO),
After providing an electrode such as SnO 2 and patterning, if necessary, form an overcoat layer of polyimide, polyamide, SiO 2 , Al 2 O 3, etc., perform orientation treatment, print a sealing material on this, and print the electrode surface Are arranged so that they face each other, and the periphery is sealed,
The sealing material is cured to form an empty cell.
【００５０】この空セルに、本発明の化合物を含む組成
物を注入し、注入口を封止剤で封止して液晶セルを構成
する。この液晶セルに必要に応じて偏光板、カラー偏光
板、光源、カラーフィルター、半透過反射板、反射板、
導光板、紫外線カットフィルター等を積層する、文字、
図形等を印刷する、ノングレア加工する等して液晶電気
光学素子とする。A composition containing the compound of the present invention is injected into this empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. If necessary, a polarizing plate, a color polarizing plate, a light source, a color filter, a semi-transmissive reflector, a reflector,
Laminated light guide plate, UV cut filter, etc., letters,
A liquid crystal electro-optical element is obtained by printing a figure or the like or performing non-glare processing.
【００５１】なお、上述の説明は、液晶電気光学素子の
基本的な構成および製法を示したにすぎなく、例えば２
層電極を用いた基板、２層の液晶層を形成した２層液晶
セル、ＴＦＴ、ＭＩＭ等の能動素子を形成したアクティ
ブマトリクス基板を用いたアクティブマトリクス素子
等、種々の構成のものが使用できる。The above description merely shows the basic structure and manufacturing method of the liquid crystal electro-optical element.
Various structures such as a substrate using a layer electrode, a two-layer liquid crystal cell in which two liquid crystal layers are formed, an active matrix element using an active matrix substrate in which active elements such as TFT and MIM are formed can be used.
【００５２】本発明の化合物を液晶組成物に用いること
により、高デューティ駆動を行っても、高速応答が期待
できる。このため、近年注目されている高ツイスト角の
スーパーツイスト（ＳＴＮ）型液晶電気光学素子に好適
である。その他、多色性色素を用いたＧＨ型液晶表示素
子、強誘電性液晶電気光学素子等にも使用できる。By using the compound of the present invention in a liquid crystal composition, a high speed response can be expected even when high duty driving is performed. Therefore, it is suitable for a super twist (STN) type liquid crystal electro-optical element having a high twist angle, which has been receiving attention in recent years. In addition, it can also be used for a GH type liquid crystal display device using a polychromatic dye, a ferroelectric liquid crystal electro-optical device, and the like.
【００５３】本発明の一般式(1) の化合物は、例えば、
次の方法に従って製造される。The compound of the general formula (1) of the present invention is, for example,
It is manufactured according to the following method.
【００５４】[0054]
【化１７】 [Chemical 17]
【００５５】なお、上記の式中A2はトランス-1,4- シク
ロヘキシレン基であり、A3は1,4-フェニレン基であり、
A1、A4は相互に独立してトランス-1,4- シクロヘキシレ
ン基、1,4-フェニレン基、または1,4-シクロヘキセニレ
ン基であり、これらの環基は夫々非置換であるかあるい
は置換基として１個以上のハロゲン原子、シアノ基を有
し、これらの環基中の環を構成する１個以上の=CH-基は
窒素原子に置換されていてもよく、また、環を構成する
１個以上の -CH2-基は酸素原子もしくは硫黄原子に置換
されていてもよい。In the above formula, A 2 is a trans-1,4-cyclohexylene group, A 3 is a 1,4-phenylene group,
A 1 and A 4 are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, or 1,4-cyclohexenylene group, and these ring groups are each unsubstituted. Alternatively, it has one or more halogen atoms or a cyano group as a substituent, and one or more = CH- groups constituting the ring in these ring groups may be substituted with a nitrogen atom. One or more —CH 2 — groups constituting the above may be substituted with an oxygen atom or a sulfur atom.
【００５６】Y1、Y2は相互に独立して-COO- 、-OCO- 、
-C≡C-、-CH2CH2-、-CH=CH- 、-OCH2-、-CH2O-または単
結合を示す。Y 1 and Y 2 are independently of each other -COO-, -OCO-,
-C≡C -, - CH 2 CH 2 -, - CH = CH-, -OCH 2 -, - shows a CH 2 O- or a single bond.
【００５７】R2はフッ素原子であり、R1は炭素数 1〜10
のアルキル基、ハロゲン原子あるいはシアノ基を示し、
アルキル基の場合には、このアルキル基中の炭素−炭素
結合間あるいはこのアルキル基と環基との間の炭素−炭
素結合間に酸素原子、カルボニルオキシ基、あるいはオ
キシカルボニル基が挿入されてもよく、また、そのアル
キル基中の炭素−炭素結合の一部が三重結合あるいは二
重結合にされていてもよく、また、そのアルキル基内の
１個の-CH2- 基がカルボニル基に置換されていてもよ
く、また、そのアルキル基中の水素原子の一部もしくは
すべてがフッ素原子で置換されていてもよい。R 2 is a fluorine atom, and R 1 has 1 to 10 carbon atoms.
Represents an alkyl group, a halogen atom or a cyano group of
In the case of an alkyl group, even if an oxygen atom, a carbonyloxy group or an oxycarbonyl group is inserted between carbon-carbon bonds in the alkyl group or between carbon-carbon bonds between the alkyl group and the ring group. Also, a part of the carbon-carbon bond in the alkyl group may be a triple bond or a double bond, and one -CH 2 -group in the alkyl group is substituted with a carbonyl group. In addition, some or all of the hydrogen atoms in the alkyl group may be replaced with fluorine atoms.
【００５８】式(10)のカルボン酸誘導体をリチウムアル
ミニウムハイドライドによって還元して式(11)のアルコ
ール誘導体とする。次に、この化合物(11)をピリジニウ
ムクロロクロメートにて酸化して、式(12)のアルデヒド
誘導体とする。The carboxylic acid derivative of formula (10) is reduced with lithium aluminum hydride to give the alcohol derivative of formula (11). Next, the compound (11) is oxidized with pyridinium chlorochromate to give an aldehyde derivative of the formula (12).
【００５９】そして、得られた化合物(12)をジブロモジ
フルオロメタンおよびトリスジメチルアミノホスフィン
と反応させて、一般式(13)の1,1-ジフルオロエチレン化
合物とする。次いで、三フッ化コバルトによってフッ素
化して、式(14)の1,1,1,2-テトラフルオロエタン化合物
とし、これをt-ブチルリチウムにて脱ＨＦして式(15)の
トリフルオロエチレン化合物とする。最後に式(16)のリ
チウム化合物と反応させることによって、一般式(1) の
ジフルオロ化合物を得ることができる。Then, the obtained compound (12) is reacted with dibromodifluoromethane and trisdimethylaminophosphine to give a 1,1-difluoroethylene compound of the general formula (13). Then, it is fluorinated with cobalt trifluoride to give a 1,1,1,2-tetrafluoroethane compound of formula (14), which is de-HFed with t-butyllithium to give trifluoroethylene of formula (15). It is a compound. Finally, by reacting with the lithium compound of formula (16), the difluoro compound of general formula (1) can be obtained.
【００６０】また、一般式(1) の化合物のR1にアシル基
を導入する方法は、R1が水素原子である一般式(1) の化
合物とアシルハライドとのフリーデル・クラフツ反応を
用いればよい。また、シアノ基を導入する方法は、R1が
臭素原子またはヨウ素原子である一般式(1) の化合物を
CuCNと反応させればよい。また、一般式(1) の化合物の
Y1にビニリデン基（-C＝C-）を導入する方法は、R1が塩
素原子または臭素原子またはヨウ素原子である一般式
(1) の化合物とアルケニルグリニア化合物とのカップリ
ング反応を用いればよい。また、一般式(1) の化合物の
Y1にエチリニデン基（-C≡C-）を導入する方法は、R1が
臭素原子またはヨウ素原子である一般式(1) の化合物と
アルキニルリチウム化合物とのカップリング反応を用い
ればよい。The method of introducing an acyl group into R 1 of the compound of general formula (1) uses the Friedel-Crafts reaction between the compound of general formula (1) in which R 1 is a hydrogen atom and an acyl halide. Good. Further, the method of introducing a cyano group is carried out by using a compound of the general formula (1) in which R 1 is a bromine atom or an iodine atom.
It can be reacted with CuCN. In addition, the compound of the general formula (1)
The vinylidene group (-C = C-) is introduced into Y 1 by a general formula in which R 1 is a chlorine atom, a bromine atom or an iodine atom.
The coupling reaction between the compound (1) and the alkenyl grinder compound may be used. In addition, the compound of the general formula (1)
A method of introducing an ethylidene group (—C≡C—) into Y 1 may be a coupling reaction between a compound of the general formula (1) in which R 1 is a bromine atom or an iodine atom and an alkynyllithium compound.
【００６１】[0061]
［実施例１］ ＜第１ステップ＞１リットルの四ツ口フラスコにリチウ
ムアルミニウムハイドライド(LiAiH4)を22.3g(0.588mo
l) およびテトラヒドロフラン(THF) を 300ml入れ、0
℃に冷却した。ここにトランス-4-n- プロピルシクロヘ
キサンカルボン酸 100g(0.588mol)をＴＨＦ300ml に溶
解した溶液を、撹拌しながら10℃以下にて２時間かけて
滴下した。さらに室温で１２時間撹拌後、20% 硫酸水溶
液を200ml 加え、エーテルで抽出し、水洗、乾燥後、溶
媒を留去し、さらに減圧蒸留(88 ℃/4mmHg) によって、
トランス-4-n- プロピルシクロヘキサンメタノール（n-
C3H7-Cy-CH2OH ）を89.3g （収率97% ）得た。[Example 1] <First step> 22.3 g (0.588 mo) of lithium aluminum hydride (LiAiH 4 ) was added to a 1-liter four-necked flask.
l) and tetrahydrofuran (THF) 300 ml, 0
Cooled to ° C. A solution of 100 g (0.588 mol) of trans-4-n-propylcyclohexanecarboxylic acid dissolved in 300 ml of THF was added dropwise with stirring at 10 ° C. or lower over 2 hours. After stirring at room temperature for 12 hours, 200 ml of 20% sulfuric acid aqueous solution was added, extracted with ether, washed with water, dried, evaporated to remove the solvent, and further distilled under reduced pressure (88 ° C / 4mmHg).
Trans-4-n-propylcyclohexanemethanol (n-
The C 3 H 7 -Cy-CH 2 OH) to give 89.3 g (97% yield).
【００６２】＜第２ステップ＞次に、２リットルの四ツ
口フラスコにピリジニウムクロロクロメート(PCC) を37
0.2g(1.717mol)、酢酸ナトリウムを23.5g(0.286mol) お
よび塩化メチレン1.2リットルを仕込み、室温下で、先
に得られたトランス-4-n- プロピルシクロヘキサンメタ
ノール89.3g(0.572mol) の塩化メチレン溶液を滴下し
た。室温で１時間撹拌後、エーテルを１リットル加え、
さらに無水MgSO4 を添加し、タール状物質を濾別した。
濾液を減圧濃縮後、再びエーテルを200ml 加えて、ター
ル状物質を濾別した。濾液を減圧濃縮後、シリカゲルカ
ラムクロマトグラフィーにて精製し、さらに得られた粗
液を減圧蒸留して(64 ℃/3mmHg) 、トランス-4-n- プロ
ピルシクロヘキサンアルデヒド（n-C3H7-Cy-CHO ）を5
6.0g （収率64% ）得た。<Second Step> Next, 37 g of pyridinium chlorochromate (PCC) was placed in a 2-liter four-necked flask.
0.2 g (1.717 mol), sodium acetate 23.5 g (0.286 mol) and methylene chloride 1.2 liter were charged, and at room temperature, trans-4-n-propylcyclohexanemethanol (89.3 g, 0.572 mol) was chlorinated. The methylene solution was added dropwise. After stirring for 1 hour at room temperature, add 1 liter of ether,
Further anhydrous MgSO 4 was added, and the tar-like substance was filtered off.
The filtrate was concentrated under reduced pressure, 200 ml of ether was added again, and the tar-like substance was filtered off. The filtrate after concentrated under reduced pressure, and purified by silica gel column chromatography, the further resulting crude liquid was distilled under reduced pressure (64 ℃ / 3mmHg), trans -4-n-propyl cyclohexane aldehyde (nC 3 H 7 -Cy- CHO) 5
6.0 g (yield 64%) was obtained.
【００６３】＜第３ステップ＞冷却管およびガス吹き込
み管付きの１リットル四ッ口フラスコに、CaH2にて脱水
したトリグライムを400ml 入れ、0 ℃に冷却し、ジブロ
モジフルオロメタン(CF2Br2 ) を101g(0.481mol)吹き込
んだ。次いで、0 ℃にて、トリスジメチルアミノホスフ
ィン(Me2N)3P 156.7g(0.961mol) および200ml のトリグ
ライム溶液を15分かけて滴下した。滴下後、室温で15分
撹拌後、先に得られたトランス-4-n- プロピルシクロヘ
キサンアルデヒド37.0g(0.24mol)および100ml のトリグ
ライム溶液を、室温下、15分かけて滴下し、さらに85℃
にて2 時間反応させた。<Third Step> 400 ml of triglyme dehydrated with CaH 2 was placed in a 1-liter four-necked flask equipped with a cooling tube and a gas blowing tube, cooled to 0 ° C., and dibromodifluoromethane (CF 2 Br 2 ) was added. Was blown in at 101 g (0.481 mol). Then, at 0 ° C., 156.7 g (0.961 mol) of trisdimethylaminophosphine (Me 2 N) 3 P and 200 ml of a triglyme solution were added dropwise over 15 minutes. After dropping, stir for 15 minutes at room temperature, then add 37.0 g (0.24 mol) of trans-4-n-propylcyclohexanaldehyde and 100 ml of triglyme solution obtained above at room temperature over 15 minutes, and then add 85 ° C.
Was reacted for 2 hours.
【００６４】0 ℃に冷却後、水300ml を加え、n-ヘキサ
ンで抽出し、水洗、乾燥後、溶媒を留去し、得られた粗
液をシリカゲルカラムクロマトグラフィーにて精製し、
さらに得られた粗液を減圧蒸留(78 ℃/20mmHg)して、2-
（トランス-4-n- プロピルシクロヘキシル）-1,1- ジフ
ルオロエチレン（n-C3H7-Cy-CH=CF2）を28.6g （収率63
％）得た。After cooling to 0 ° C., 300 ml of water was added, the mixture was extracted with n-hexane, washed with water and dried, the solvent was distilled off, and the obtained crude liquid was purified by silica gel column chromatography.
Furthermore, the crude liquid obtained was distilled under reduced pressure (78 ° C / 20 mmHg) to give 2-
28.6 g of (trans-4-n-propylcyclohexyl) -1,1-difluoroethylene (nC 3 H 7 -Cy-CH = CF 2 ) (yield 63
%)Obtained.
【００６５】＜第４ステップ＞２リットルのオートクレ
ーブに先に得られた2-（トランス-4-n- プロピルシクロ
ヘキシル）-1,1- ジフルオロエチレンを28.6g(0.152mo
l) 、三フッ化コバルトを123.4g(1.06mol) 、水1ml お
よびFC-113(CCl2FCClF2)を1000ml仕込み、100 ℃にて3
時間反応させた。冷却後、無機塩を濾別し、有機層を10
％NaHCO3水溶液で洗浄し、さらに水洗後、溶媒を留去
し、得られた粗液をシリカゲルカラムクロマトグラフィ
ーにて精製して、2-（トランス-4-n- プロピルシクロヘ
キシル）-1,1,1,2- テトラフルオロエタン（n-C3H7-Cy-
CHFCF3）の粗液を15.5g （純度86％）得た。<Fourth Step> 28.6 g (0.152 mol) of 2- (trans-4-n-propylcyclohexyl) -1,1-difluoroethylene obtained above was placed in a 2 liter autoclave.
l), 123.4 g (1.06 mol) of cobalt trifluoride, 1 ml of water and 1000 ml of FC-113 (CCl 2 FCClF 2 ) were charged, and 3
Reacted for hours. After cooling, the inorganic salt was filtered off and the organic layer was washed with 10
% NaHCO 3 aqueous solution, further washed with water, the solvent was distilled off, and the resulting crude liquid was purified by silica gel column chromatography to give 2- (trans-4-n-propylcyclohexyl) -1,1. , 1,2-Tetrafluoroethane (nC 3 H 7 -Cy-
15.5 g (purity 86%) of a crude liquid of CHFCF 3 ) was obtained.
【００６６】＜第５ステップ＞1 リットル四ツ口フラス
コに、先に得られた2-（トランス-4-n- プロピルシクロ
ヘキシル）-1,1,1,2- テトラフルオロエタンの粗液15.5
g と乾燥ＴＨＦ 200mlを仕込み、-78 ℃に冷却した。次
いで、t-BuLiのn-ペンタン溶液(1.6mol/リットル) を4
4.2ml(0.07mol) 、30分かけて滴下した。さらに、-78
℃にて2 時間反応させた後、室温まで昇温し、1N塩酸を
500ml 加え、有機層を分離した。水層をn-ヘキサンで抽
出後、有機層と合わせて水洗、乾燥後、溶媒を留去し、
得られた粗液をシリカゲルカラムクロマトグラフィーに
て精製して、2-（トランス-4-n- プロピルシクロヘキシ
ル）-1,1,2- トリフルオロエチレン（n-C3H7-Cy-CF=C
F2）を7.53g （収率62％）得た。<Fifth Step> In a 1-liter four-necked flask, a crude liquid of the previously obtained 2- (trans-4-n-propylcyclohexyl) -1,1,1,2-tetrafluoroethane (15.5) was added.
g and 200 ml of dry THF were charged, and the mixture was cooled to -78 ° C. Then, t-BuLi in n-pentane (1.6 mol / liter) was added to
4.2 ml (0.07 mol) was added dropwise over 30 minutes. In addition, -78
After reacting at ℃ for 2 hours, warm to room temperature and add 1N hydrochloric acid.
500 ml was added and the organic layer was separated. After the aqueous layer was extracted with n-hexane, the organic layer was washed with water and dried, and then the solvent was distilled off.
The resulting crude liquid was purified by silica gel column chromatography to give 2- (trans-4-n-propylcyclohexyl) -1,1,2-trifluoroethylene (nC 3 H 7 -Cy-CF = C
F 2) to give 7.53 g (62% yield).
【００６７】＜第６ステップ＞300ml の四ツ口フラスコ
に4-フルオロヨードベンゼン5.59g(25.2mmol) および乾
燥エーテルを30mlを仕込み、-78 ℃に冷却した。次い
で、n-BuLiのn-ヘキサン溶液(1.63mol/ リットル) を17
ml(27.8mmol)、15分かけて滴下した。さらに、-78 ℃に
て1 時間撹拌後、テトラメチレンジアミン(TMEDA) を3.
8ml(25.5mmol) を加え、さらに先に得られた2-（トラン
ス-4-n- プロピルシクロヘキシル）-1,1,2- トリフルオ
ロエチレン1.3g(6.31mmmol) および乾燥ＴＨＦ 60ml の
混合溶液を30分かけて滴下した。さらに同温度で 2時間
反応させた後、室温まで昇温し、1N塩酸を500ml 加え、
有機層を分離した。水層をn-ヘキサンで抽出後、有機層
と合わせて水洗、乾燥後、溶媒を留去し、得られた粗液
をシリカゲルカラムクロマトグラフィーにて精製し、さ
らに得られた固体をメタノールより再結晶して、(E)-1-
（4-フルオロフェニル）-2- （トランス-4-n- プロピル
シクロヘキシル）-1,2- ジフルオロエチレン（n-C3H7-C
y-CF=CF-Ph-F）を0.71g （収率40％）得た。<Sixth Step> A 300 ml four-necked flask was charged with 5.59 g (25.2 mmol) of 4-fluoroiodobenzene and 30 ml of dry ether and cooled to -78.degree. Then, add n-BuLi in n-hexane (1.63 mol / liter) to
ml (27.8 mmol) was added dropwise over 15 minutes. After stirring at -78 ° C for 1 hour, add tetramethylenediamine (TMEDA) to 3.
8 ml (25.5 mmol) was added, and a mixed solution of 1.3 g (6.31 mmol) of 2- (trans-4-n-propylcyclohexyl) -1,1,2-trifluoroethylene obtained above and 60 ml of dry THF was added. It dripped over 30 minutes. After reacting at the same temperature for 2 hours, the temperature was raised to room temperature and 500 ml of 1N hydrochloric acid was added.
The organic layer was separated. The aqueous layer was extracted with n-hexane, and the organic layer was washed with water and dried, the solvent was distilled off, the crude liquid obtained was purified by silica gel column chromatography, and the obtained solid was re-purified from methanol. Crystallize and (E) -1-
(4-Fluorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene (nC 3 H 7 -C
0.71 g (yield 40%) of y-CF = CF-Ph-F) was obtained.
【００６８】[0068]
【化１８】 [Chemical 18]
【００６９】本化合物の分析結果を表１に示す。The analysis results of this compound are shown in Table 1.
【００７０】実施例１と同様にして、以下の化合物を得
ることができる。The following compounds can be obtained in the same manner as in Example 1.
【００７１】[0071]
【化１９】 [Chemical 19]
【００７２】［実施例２］実施例１の第６ステップにお
いて、4-フルオロヨードベンゼンのかわりに4-フルオロ
-4'-ヨードビフェニルを7.51g(25.2mmol) 用いる以外は
実施例１と同様に反応を行い、(E)-1-（4-（4-フルオロ
フェニル）フェニル）-2- （トランス-4-n- プロピルシ
クロヘキシル）-1,2- ジフルオロエチレン（n-C3H7-Cy-
CF=CF-Ph--Ph-F ）を0.68g （収率30％）得た。[Example 2] In the sixth step of Example 1, 4-fluoro-iodobenzene was used in place of 4-fluoro
Reaction was carried out in the same manner as in Example 1 except that 7.51 g (25.2 mmol) of -4'-iodobiphenyl was used, and (E) -1- (4- (4-fluorophenyl) phenyl) -2- (trans-4 -n-Propylcyclohexyl) -1,2-difluoroethylene (nC 3 H 7 -Cy-
CF = CF-Ph--Ph-F) was obtained at 0.68 g (yield 30%).
【００７３】[0073]
【化２０】 [Chemical 20]
【００７４】本化合物の分析結果を表２に示す。The analysis results of this compound are shown in Table 2.
【００７５】実施例２と同様にして、以下の化合物を得
ることができる。The following compounds can be obtained in the same manner as in Example 2.
【００７６】[0076]
【化２１】 [Chemical 21]
【００７７】［実施例３］メルク社製液晶組成物「ZLI-
1565」80wt％に、実施例１の化合物 (E)-1- （4-フルオ
ロフェニル）-2- （トランス-4-n- プロピルシクロヘキ
シル）-1,2- ジフルオロエチレンを20wt％加えて液晶組
成物とした。本液晶組成物の液晶物性を表３に示す。表
３より明らかなように、本発明化合物は低粘性であり、
高速ＳＴＮ用液晶材料として有用である。[Example 3] Liquid crystal composition "ZLI-" manufactured by Merck & Co., Inc.
1565 "to 80 wt%, 20 wt% of the compound (E) -1- (4-fluorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2-difluoroethylene of Example 1 was added to the liquid crystal composition. It was a thing. Table 3 shows the liquid crystal properties of the present liquid crystal composition. As is clear from Table 3, the compound of the present invention has low viscosity,
It is useful as a liquid crystal material for high-speed STN.
【００７８】［実施例４および比較例１〜２］メルク社
製液晶組成物「ZLI-1565」80wt％に、本発明の実施例１
の化合物を20wt％加えて液晶組成物（実施例４）とし
た。比較例として、メルク社製液晶組成物「ZLI-1565」
のみの液晶組成物（比較例１）およびメルク社製液晶組
成物「ZLI-1565」80wt％にトランス-4,4'-ビス-(n-プロ
ピル) ジフルオロスチルベンを20wt％加えた液晶組成物
（比較例２）を作成した。これらを偏光板付きの液晶セ
ルに封入して、ＳＴＮ型液晶表示素子を作成した。[Example 4 and Comparative Examples 1 and 2] 80 wt% of the liquid crystal composition "ZLI-1565" manufactured by Merck was added to Example 1 of the present invention.
A liquid crystal composition (Example 4) was obtained by adding 20% by weight of the compound (1). As a comparative example, a liquid crystal composition "ZLI-1565" manufactured by Merck & Co., Inc.
Liquid crystal composition of Comparative Example 1 (Comparative Example 1) and liquid crystal composition of 20% by weight of trans-4,4′-bis- (n-propyl) difluorostilbene added to 80% by weight of liquid crystal composition “ZLI-1565” manufactured by Merck Ltd. ( Comparative example 2) was prepared. These were enclosed in a liquid crystal cell with a polarizing plate to prepare an STN type liquid crystal display element.
【００７９】この実施例４および比較例２の液晶表示素
子の素子の表示特性はほぼ同程度であり、比較例１の素
子に比べて高速応答が得られた。次いで、実施例４およ
び比較例２の液晶表示素子を紫外線カーボンアークラン
プで 500時間照射した。照射後、各素子内の液晶組成物
を分析した。The display characteristics of the elements of the liquid crystal display elements of Example 4 and Comparative Example 2 were substantially the same, and a higher speed response than that of the element of Comparative Example 1 was obtained. Then, the liquid crystal display elements of Example 4 and Comparative Example 2 were irradiated with an ultraviolet carbon arc lamp for 500 hours. After irradiation, the liquid crystal composition in each device was analyzed.
【００８０】その結果、実施例４の液晶組成物の場合に
は、0.3%の(Z)-1-（4-フルオロフェニル）-2- （トラン
ス-4-n- プロピルシクロヘキシル）-1,2- ジフルオロエ
チレンが生成した。一方、比較例２の液晶組成物の場合
には、6.3%の(Z)-4,4'- ビス-(n-プロピル) ジフルオロ
スチルベンの生成が確認された。As a result, in the case of the liquid crystal composition of Example 4, 0.3% (Z) -1- (4-fluorophenyl) -2- (trans-4-n-propylcyclohexyl) -1,2 -Difluoroethylene was produced. On the other hand, in the case of the liquid crystal composition of Comparative Example 2, it was confirmed that 6.3% of (Z) -4,4′-bis- (n-propyl) difluorostilbene was produced.
【００８１】[0081]
【表１】 [Table 1]
【００８２】[0082]
【表２】 [Table 2]
【００８３】[0083]
【表３】 [Table 3]
【００８４】[0084]
【発明の効果】本発明の一般式(1) R1-(A1)m-Y1-A2-CF=CF-A3-Y2-(A4)n-R2 （A1〜A4、R1、R2、Y1、Y2、m 、n については前記の意
味を持つ）で示される化合物は、粘性が低く、液晶組成
物として用いることにより、少量の添加でも応答速度が
向上するものであり、低電圧駆動、高デューティ駆動、
広温度域動作等が可能になる。The general formula (1) R 1- (A 1 ) m -Y 1 -A 2 -CF = CF-A 3 -Y 2- (A 4 ) n -R 2 (A 1 ~ The compounds represented by A 4 , R 1 , R 2 , Y 1 , Y 2 , m, and n have the above-mentioned meanings) and have a low viscosity. Is improved, low voltage drive, high duty drive,
Wide temperature range operation is possible.
【００８５】また、ジフルオロスチルベンタイプの液晶
よりも、紫外光に対して安定であり耐久性が向上する、
弾性係数（Ｋ33／Ｋ11）が増加し高コントラス化する、
液晶上限温度（ＴC ）が上昇し液晶温度幅が増大する、
粘度（η）が減少し高速応答に有利になる等、各特性が
改善された材料である。Further, compared with the difluorostilbene type liquid crystal, it is more stable to ultraviolet light and has improved durability.
The elastic modulus (K 33 / K 11 ) increases and the contrast becomes high,
Liquid crystal upper limit temperature (T C) is a liquid crystal temperature range is increased to rise,
It is a material with improved properties such as reduced viscosity (η), which is advantageous for high-speed response.
【００８６】特に高速ＳＴＮ用液晶材料として、ジフル
オロスチルベンタイプの液晶より優位性があり、有用で
ある。Particularly, as a liquid crystal material for high-speed STN, it is superior to difluorostilbene type liquid crystal and useful.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｋ 19/20 19/30 9279−4Ｈ Ｇ０２Ｆ 1/13 ５００ (72)発明者 高 英昌 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 (72)発明者 尾池 啓子 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C09K 19/20 19/30 9279-4H G02F 1/13 500 (72) Inventor Hidemasa Taka Kanagawa Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Center 1150, Hazawa-ku, Tokyo (72) Inventor Keiko Oike 1150, Hazawa-machi Kanagawa-ku Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Center
Claims (5)
レン誘導体化合物。 【化１】 R1-(A1)m-Y1-A2-CF=CF-A3-Y2-(A4)n-R2 (1) ただし、一般式 (1)中、A1、A2、A3、A4、Y1、Y2、R1、
R2、m 、n は下記のものを示す。A3は1,4-フェニレン
基、A2はトランス-1,4- シクロヘキシレン基であり、
A1、A4は相互に独立してトランス-1,4- シクロヘキシレ
ン基、1,4-フェニレン基、または1,4-シクロヘキセニレ
ン基であり、これらの環基は夫々非置換であるかあるい
は置換基として１個以上のハロゲン原子、シアノ基を有
し、これらの環基中の環を構成する１個以上の=CH-基は
窒素原子に置換されていてもよく、また、環を構成する
１個以上の -CH2-基は酸素原子もしくは硫黄原子に置換
されていてもよい。Y1、Y2は相互に独立して-COO- 、-O
CO- 、-C≡C-、-CH2CH2-、-CH=CH- 、-OCH2-、-CH2O-ま
たは単結合を示す。R2はフッ素原子であり、R1は、炭素
数 1〜10のアルキル基、ハロゲン原子あるいはシアノ基
を示し、アルキル基の場合には、このアルキル基中の炭
素−炭素結合間あるいはこのアルキル基と環基との間の
炭素−炭素結合間に酸素原子、カルボニルオキシ基、あ
るいはオキシカルボニル基が挿入されてもよく、また、
そのアルキル基中の炭素−炭素結合の一部が三重結合あ
るいは二重結合にされていてもよく、また、そのアルキ
ル基内の１個の-CH2- 基がカルボニル基に置換されてい
てもよく、また、そのアルキル基中の水素原子の一部も
しくはすべてがフッ素原子で置換されていてもよい。m
、n は相互に独立して 0または 1を示す。1. A difluoroethylene derivative compound represented by the following general formula (1). Embedded image R 1- (A 1 ) m -Y 1 -A 2 -CF = CF-A 3 -Y 2- (A 4 ) n -R 2 (1) However, in the general formula (1), A 1 , A 2 , A 3 , A 4 , Y 1 , Y 2 , R 1 ,
R 2 , m and n are as follows. A 3 is a 1,4-phenylene group, A 2 is a trans-1,4-cyclohexylene group,
A 1 and A 4 are each independently a trans-1,4-cyclohexylene group, 1,4-phenylene group, or 1,4-cyclohexenylene group, and these ring groups are each unsubstituted. Alternatively, it has one or more halogen atoms or a cyano group as a substituent, and one or more = CH- groups constituting the ring in these ring groups may be substituted with a nitrogen atom. One or more —CH 2 — groups constituting the above may be substituted with an oxygen atom or a sulfur atom. Y 1 and Y 2 are independent of each other -COO-, -O
CO-, -C≡C -, - CH 2 CH 2 -, - CH = CH-, -OCH 2 -, - shows a CH 2 O- or a single bond. R 2 is a fluorine atom, R 1 represents an alkyl group having 1 to 10 carbon atoms, a halogen atom or a cyano group, and in the case of an alkyl group, carbon-carbon bond in this alkyl group or this alkyl group An oxygen atom, a carbonyloxy group, or an oxycarbonyl group may be inserted between the carbon-carbon bond between the ring group and the ring group, and,
A part of the carbon-carbon bond in the alkyl group may be a triple bond or a double bond, and one —CH 2 — group in the alkyl group may be substituted with a carbonyl group. Of course, some or all of the hydrogen atoms in the alkyl group may be replaced by fluorine atoms. m
, N independently of each other represent 0 or 1.
A2、A3、R1およびR2については、一般式 (1)と同じもの
を示す）で表される請求項１のジフルオロエチレン誘導
体化合物。 【化２】R1-A2-CF=CF-A3-R2 (2)2. The following general formula (2) (wherein the general formula (2)
The difluoroethylene derivative compound according to claim 1, which is represented by general formula (1) for A 2 , A 3 , R 1 and R 2 . [Chemical formula 2] R 1 -A 2 -CF = CF-A 3 -R 2 (2)
導体から選ばれる液晶性を有する化合物。3. A compound having liquid crystallinity selected from the difluoroethylene derivative according to claim 1.
導体化合物を少なくとも１種含有する液晶組成物。4. A liquid crystal composition containing at least one difluoroethylene derivative compound according to claim 1.
液晶組成物を電極付基板間に挟持してなる液晶電気光学
素子。5. A liquid crystal electro-optical element comprising a liquid crystal compound according to claim 3 or a liquid crystal composition according to claim 4 sandwiched between substrates with electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31708893A JP3541410B2 (en) | 1993-12-16 | 1993-12-16 | Difluoroethylene derivative compound, liquid crystal composition containing the same, and liquid crystal electro-optical element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31708893A JP3541410B2 (en) | 1993-12-16 | 1993-12-16 | Difluoroethylene derivative compound, liquid crystal composition containing the same, and liquid crystal electro-optical element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07165635A true JPH07165635A (en) | 1995-06-27 |
| JP3541410B2 JP3541410B2 (en) | 2004-07-14 |
Family
ID=18084301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31708893A Expired - Fee Related JP3541410B2 (en) | 1993-12-16 | 1993-12-16 | Difluoroethylene derivative compound, liquid crystal composition containing the same, and liquid crystal electro-optical element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3541410B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011083677A1 (en) * | 2010-01-06 | 2011-07-14 | Jnc株式会社 | Liquid crystal compound, liquid crystal composition and liquid crystal display element |
| CN103131426A (en) * | 2011-11-25 | 2013-06-05 | 达兴材料股份有限公司 | Liquid crystal compound and liquid crystal medium |
| CN103146393A (en) * | 2013-02-01 | 2013-06-12 | 西安近代化学研究所 | 3,4,5-trifluoro-biphenyl liquid crystal compound with ethylene |
-
1993
- 1993-12-16 JP JP31708893A patent/JP3541410B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011083677A1 (en) * | 2010-01-06 | 2011-07-14 | Jnc株式会社 | Liquid crystal compound, liquid crystal composition and liquid crystal display element |
| US8940185B2 (en) | 2010-01-06 | 2015-01-27 | Jnc Corporation | Liquid crystal compound, liquid crystal composition and liquid crystal display device |
| JP5880832B2 (en) * | 2010-01-06 | 2016-03-09 | Jnc株式会社 | Liquid crystal compound, liquid crystal composition, and liquid crystal display device |
| CN103131426A (en) * | 2011-11-25 | 2013-06-05 | 达兴材料股份有限公司 | Liquid crystal compound and liquid crystal medium |
| CN103146393A (en) * | 2013-02-01 | 2013-06-12 | 西安近代化学研究所 | 3,4,5-trifluoro-biphenyl liquid crystal compound with ethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3541410B2 (en) | 2004-07-14 |
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