JPH02101046A - Liquid crystal compound - Google Patents
Liquid crystal compoundInfo
- Publication number
- JPH02101046A JPH02101046A JP63252525A JP25252588A JPH02101046A JP H02101046 A JPH02101046 A JP H02101046A JP 63252525 A JP63252525 A JP 63252525A JP 25252588 A JP25252588 A JP 25252588A JP H02101046 A JPH02101046 A JP H02101046A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- trans
- formula
- compound
- compound shown
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 47
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 36
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 19
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 abstract description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 8
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007704 transition Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 150000003222 pyridines Chemical class 0.000 abstract description 4
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012346 acetyl chloride Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000004988 Nematic liquid crystal Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- -1 4-cyano-3fluorophenyl Chemical group 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004360 trifluorophenyl group Chemical group 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は液晶表示装置に用いられる液晶材料の成分とし
て有用な新規液晶化合物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel liquid crystal compound useful as a component of a liquid crystal material used in a liquid crystal display device.
［発明の概要］
本発明は一般式
（上式中、Ｒは炭素原子数が１〜１０の直鎖アルキル基
、Ｘ１ｔＣＮ、Ｆ又ハＣＩ２、ＹはＨ，Ｆ又はＣＩ２を
示し、シクロヘキサン環はトランス配置である。）で表
わされる新規な液晶化合物でありネマチック液晶相を示
し、ネマチック相−等方性液体転移点（Ｎ−Ｉ点）が高
くてしきい値電圧（Ｖｔｈ）が低い特徴を有する。[Summary of the Invention] The present invention is based on the general formula (in the above formula, R is a linear alkyl group having 1 to 10 carbon atoms, X1tCN, F or CI2, Y is H, F or CI2, and the cyclohexane ring is It is a novel liquid crystal compound expressed by a trans configuration (trans configuration), which exhibits a nematic liquid crystal phase, and is characterized by a high nematic phase-isotropic liquid transition point (N-I point) and a low threshold voltage (Vth). have
したがって、本発明の液晶化合物と他の液晶化合物を混
合した液晶組成物を用いることにより実用温度範囲が広
く、かつ駆動電圧が低い液晶表示装置を提供することが
できる。Therefore, by using a liquid crystal composition in which the liquid crystal compound of the present invention is mixed with another liquid crystal compound, a liquid crystal display device having a wide practical temperature range and a low driving voltage can be provided.
［従来の技術］
液晶表示装置は主にネマチック液晶相の電気光学効果を
応用したものであり、その表示方式には動的散乱型、ゲ
スト−ホスト型、ねじれネマチック型（ＴＮ型）などが
あり、ＴＮ型が最も普及している。液晶表示装置は小型
、薄型で駆動電圧が低く、消費電力が小さい、受光素子
であり長時間使用しても目が疲れない等の長所を持つた
め、従来よりウォッチ、電卓、オーディオ機器、各種計
測器等に広く利用されている。また最近ではパソコンや
ワープロのデイスプレィ、ポケットテレビ等の画素数の
非常に多い表示装置にも応用されつつあり、ＣＲＴに代
わる表示装置として注目を集めている。今後も液晶表示
装置の応用分野はさらに拡大してゆくと考えられ、これ
に伴って液晶材料に要求される特性も変化してゆくのは
当然であるが、無着色で熱、光、電気的、化学的に安定
なこと、ネマチック温度範囲ができるだけ広いこと、駆
動電圧ができるだけ低いことは基本的な特性でありあら
ゆる要求に対して必要不可欠の条件である。[Prior art] Liquid crystal display devices mainly apply the electro-optical effect of the nematic liquid crystal phase, and their display methods include dynamic scattering type, guest-host type, and twisted nematic type (TN type). , TN type is the most popular. Liquid crystal display devices have advantages such as being small and thin, have low driving voltage, low power consumption, and are light-receiving elements that do not cause eye strain even when used for long periods of time. Widely used for utensils, etc. Recently, it has also been applied to display devices with a large number of pixels, such as displays for personal computers, word processors, and pocket televisions, and is attracting attention as a display device that can replace CRTs. It is thought that the application fields of liquid crystal display devices will continue to expand in the future, and it is natural that the properties required of liquid crystal materials will change accordingly. , chemical stability, widest possible nematic temperature range, and lowest possible driving voltage are fundamental characteristics and essential conditions for all requirements.
［発明が解決しようとする課題］
これらの特性の中で無着色で安定な液晶化合物は多数知
られているが、単一成分でネマチック温度範囲が広く、
駆動電圧が低い実用可能な液晶化合物は知られていない
。そこで、複数のネマチック液晶化合物又は非ネマチッ
ク液晶化合物を混合した液晶組成物を用いてこれらの特
性を満たしている。一般に液晶組成物は室温付近にネマ
チック相を持つ化合物とＮ−Ｉ点が１５０℃以上ある化
合物を混合して作られ、駆動電圧を下げるためにそれぞ
れ誘電率の異方性△εが正で大きな化合物を混合してい
る。しかし、従来のＮ−Ｉ点が高くて△εの大きな化合
物は弾性定数が大きいため液晶組成物に混合しても駆動
電圧が下がらない欠点を有している。[Problems to be Solved by the Invention] Among these characteristics, many uncolored and stable liquid crystal compounds are known, but they are single-component and have a wide nematic temperature range.
No practical liquid crystal compound with low driving voltage is known. Therefore, a liquid crystal composition in which a plurality of nematic liquid crystal compounds or non-nematic liquid crystal compounds are mixed is used to satisfy these characteristics. Generally, liquid crystal compositions are made by mixing a compound with a nematic phase near room temperature and a compound with an N-I point of 150°C or higher, and each has a positive and large dielectric anisotropy △ε in order to lower the driving voltage. Mixing compounds. However, conventional compounds with a high N-I point and a large Δε have a large elastic constant, so they have the disadvantage that the driving voltage cannot be lowered even if they are mixed into a liquid crystal composition.
そこで、本発明の目的は他の１種又は２種以上のネマチ
ック液晶化合物又は非液晶化合物と混合することにより
ネマチック温度範囲が広く駆動電圧の低い液晶組成物を
得ることができる新規なネマチック液晶化合物を提供す
ることである。Therefore, the object of the present invention is to provide a novel nematic liquid crystal compound that can be mixed with one or more other nematic liquid crystal compounds or non-liquid crystal compounds to obtain a liquid crystal composition with a wide nematic temperature range and a low driving voltage. The goal is to provide the following.
本発明は一般式
（上式中、Ｒは炭素原子数が１〜１０の直鎖アルキル基
、ＸはＣＮ、Ｆ又はＣβ、ＹはＨ，Ｆ又はＣＩ２を示し
、シクロヘキサン環はトランス配置である。）で表わさ
れる液晶化合物であり、次の製造方法により得ることが
できる。The present invention is based on the general formula (in the above formula, R is a linear alkyl group having 1 to 10 carbon atoms, X is CN, F or Cβ, Y is H, F or CI2, and the cyclohexane ring is in the trans configuration. ) and can be obtained by the following manufacturing method.
Ｒ−■唖咲■ 又は化合物（４）は次に方法で製造できる。R-■Musaki■ Alternatively, compound (4) can be produced by the following method.
Ｒ（侶■に◇ （２）
↓
Ｒ−■顆Ｘ妨Ｂｒ
↓
Ｒ頃へ■４ｃＮ
↓
Ｒ÷へＣ煎）ｃｏＯＨ
↓
Ｒ（ヴ■（）ｃｏＯＨ（４）
（上式中、Ｒは炭素原子数が１〜ＩＯの直鎖アルキル基
、ＸはＣＮ、Ｆ又はＣ，Ｃ１ＹはＨ，Ｆ又はＣＩ２を示
し、シクロヘキサン環はトランス配置である。）
工程１ 化合物（２）を二硫化炭素中で無水塩化アルミ
ニウムを触媒として塩化アセチルと反応させ化合物Ｂ（
３）を得る。この反応では溶媒効果が大きく塩化メチレ
ンを用いた場合にはシクロへキサン環はほとんどがシス
に転移する。R (to ■◇ (2) ↓ R-■ condyle Straight chain alkyl group having 1 to IO atoms, X is CN, F or C, C1Y is H, F or CI2, and the cyclohexane ring is in trans configuration.) Step 1 Compound (2) is dissolved in carbon disulfide. Compound B (
3) is obtained. In this reaction, the solvent effect is large and when methylene chloride is used, most of the cyclohexane rings are transferred to cis.
工程２ 化合物（３）を１．４−ジオキサン中で臭素、
水酸化ナトリウム、水より調整した次亜臭素酸ナトリウ
ム溶液で酸化して化合物（４）を得る。ここで使用され
る酸化剤としては次亜臭素酸ナトリウム、以外に次亜塩
酸ナトリウム、さらし粉などがある。Step 2 Compound (3) in 1,4-dioxane with bromine,
Compound (4) is obtained by oxidation with a sodium hypobromite solution prepared from sodium hydroxide and water. Oxidizing agents used here include sodium hypobromite, sodium hypochlorite, bleaching powder, and the like.
工程３ 化合物（４）と塩化チオニルを反応させて化合
物（５）を得る。Step 3 Compound (5) is obtained by reacting compound (4) with thionyl chloride.
工程４ 化合物（５）と化合物（６）を脱水ピリジン中
でエステル化させ本発明の化合物（１）を得る。Step 4 Compound (5) and compound (6) are esterified in dehydrated pyridine to obtain compound (1) of the present invention.
工程５ 化合物（２）を四塩化炭素と脱水ピリジン中で
よう素を触媒に用いて臭素と反応させ化合物（７）を得
る。ピリジンにより発生した臭化水素を捕捉することに
よりシクロヘキサン環がシスに転移するのが抑えられる
。Step 5 Compound (2) is reacted with bromine in carbon tetrachloride and dehydrated pyridine using iodine as a catalyst to obtain compound (7). By trapping the hydrogen bromide generated by pyridine, the transition of the cyclohexane ring to cis is suppressed.
工程６ 化合物（７）をＮ−メチルピロリジノン中でシ
アン化銅（１）と反応させ化合物（８）を得る。Step 6 Compound (7) is reacted with copper cyanide (1) in N-methylpyrrolidinone to obtain compound (8).
工程７ 化合物（８）をトリエチレングリコール中で水
酸化カリウムと水で加水分解して化合物（４）を得る。Step 7 Compound (8) is hydrolyzed in triethylene glycol with potassium hydroxide and water to obtain compound (4).
（実 施 例〕
以下、実施例と応用例により本発明をさらに詳しく説明
する。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples and Application Examples.
実施例１
４−［トランス−４′−Ｄランス−４″−プロピルシク
ロヘキシル）シクロヘキシル］安息香酸クロライドの製
造（工程１〜４による方法）工程ｌ 無水塩化アルミニ
ウム９．２ｇを粉細して二硫化炭素７０ｃｍ３に分散さ
せて室温で撹拌しながら塩化アセチル５．Ｏｇを滴下し
た。次に氷水冷却撹拌下にトランス−４−（トランス−
４′−プロピルシクロヘキシル）シクロヘキシルベンゼ
ン１５ｇを二硫化炭素３６ｃｍ３にとかした溶液を３０
分間で滴下し、その後氷水冷却下に１時間、さらに室温
で１時間撹拌した。反応液を濃塩酸３０ ｃｍ”と氷５
０ｇ中に注ぎ油層を分離し水で洗浄した。二硫化炭素を
蒸留して除いてから残渣をクロロホルムとアセトンの混
合溶媒から再結晶して４′ −［トランス−４″−（ト
ランス−４″′プロピルシクロヘキシル）シクロヘキシ
ル］アセトフェノン８．３ｇを得た。Example 1 Production of 4-[trans-4'-D-trans-4''-propylcyclohexyl)cyclohexyl]benzoic acid chloride (method according to steps 1 to 4) Step 1 9.2 g of anhydrous aluminum chloride was pulverized and disulfide After dispersing in 70 cm3 of carbon, 5.0 g of acetyl chloride was added dropwise with stirring at room temperature.Next, trans-4-(trans-
A solution of 15 g of 4'-propylcyclohexyl)cyclohexylbenzene dissolved in 36 cm3 of carbon disulfide was
The mixture was added dropwise over a period of minutes, and then stirred for 1 hour while cooling with ice water and then for 1 hour at room temperature. The reaction solution was mixed with 30 cm of concentrated hydrochloric acid and 5 cm of ice.
The oil layer was separated and washed with water. After removing carbon disulfide by distillation, the residue was recrystallized from a mixed solvent of chloroform and acetone to obtain 8.3 g of 4'-[trans-4''-(trans-4''-propylcyclohexyl)cyclohexyl]acetophenone. .
工程２４′−［トランス−４″−（トランス４″′−プ
ロピルシクロヘキシル）シクロへキシル］アセトフェノ
ン８．３ｇを１．４−ジオキサン１２０ｃｍ３に加熱溶
解後、氷水冷却下にかきまぜて細かな結晶を析出させた
。この混合物を氷水冷却撹拌下に臭素１４６ｇと水酸化
ナトリウム９．２ｇと水５１ ｃｍ”より調整した次亜
臭素酸ナトリウム溶液を滴下した。その後、氷水冷却下
に１時間と４０℃で１時間撹拌した。次に濃塩酸３０
ｃｍ”を加え室温で３時間撹拌後、結晶を濾過し水で洗
浄してから８０℃で５時間乾燥して４−［トランス−４
′ −（トランス−４″−プロピルシクロヘキシル）シ
クロへキシル］安息香酸８．４ｇを得た。Step 24: Dissolve 8.3 g of [trans-4''-(trans-4''-propylcyclohexyl)cyclohexyl]acetophenone in 120 cm3 of 1,4-dioxane by heating, then stir while cooling with ice water to precipitate fine crystals. I let it happen. A sodium hypobromite solution prepared from 146 g of bromine, 9.2 g of sodium hydroxide, and 51 cm of water was added dropwise to this mixture while cooling with ice water and stirring. Thereafter, the mixture was stirred for 1 hour while cooling with ice water and for 1 hour at 40°C. Next, concentrated hydrochloric acid 30
After stirring at room temperature for 3 hours, the crystals were filtered, washed with water, and dried at 80°C for 5 hours to obtain 4-[trans-4
8.4 g of '-(trans-4''-propylcyclohexyl)cyclohexyl]benzoic acid was obtained.
工程３４−［トランス−４’ −（トランス−４″−プ
ロピルシクロヘキシル）シクロヘキシル］安息香酸８．
４ｇを塩化チオニル９．１ｇと共に１０時間還流した。Step 34-[trans-4'-(trans-4''-propylcyclohexyl)cyclohexyl]benzoic acid8.
4 g was refluxed with 9.1 g of thionyl chloride for 10 hours.
過剰な塩化チオニルをアスピレータ−減圧下に留去した
。残渣をヘキサンから再結し４−［トランス−４′−（
１−ランス−４″−プロピルシクロヘキシル）シクロヘ
キシル］安息香酸クロライド８１ｇを得た。Excess thionyl chloride was distilled off under aspirator vacuum. The residue was reconsolidated from hexane to form 4-[trans-4'-(
81 g of 1-lance-4''-propylcyclohexyl)cyclohexyl]benzoic acid chloride was obtained.
実施例２
４−［トランス−４’ −（１−ランス−４″−プロピ
クロヘキシル）シクロヘキシル］安息香酸クロライドの
製造（工程５〜７．３による方法）工程５４−［トラン
ス−４′ −（）−ランス４″−プロピルシクロヘキシ
ル）シクロへキシル］ベンゼン２０ｇとよう素０．４ｇ
を四塩化炭素１００ｃｍ”に溶解した。この溶液を氷水
浴で５℃以下に冷却しはげしく撹拌しながら臭素１２３
ｇを四塩化炭素１３ｃｍ”にとかした溶液をゆっくり滴
下した。滴下終了後、５℃以下で２時間と４０−５０°
Ｃで２時間攪拌した。反応液を水、１０％水酸化カリウ
ム溶液、水の順序で洗浄した。Example 2 Preparation of 4-[trans-4'-(1-trans-4''-propyclohexyl)cyclohexyl]benzoic acid chloride (method according to steps 5 to 7.3) Step 54-[trans-4'-( )-lance 4″-propylcyclohexyl)cyclohexyl]benzene 20g and iodine 0.4g
was dissolved in 100 cm of carbon tetrachloride.The solution was cooled to below 5°C in an ice-water bath, and bromine 123 was dissolved with vigorous stirring.
A solution prepared by dissolving 1.5 g of carbon tetrachloride in 13 cm of carbon tetrachloride was slowly added dropwise. After the dropwise addition was completed, the solution was heated at 40-50° for 2 hours below 5°C.
The mixture was stirred at C for 2 hours. The reaction solution was washed with water, 10% potassium hydroxide solution, and water in this order.
四塩化炭素を留去してから残渣をクロロホルムとアセト
ンの混合溶媒から再結晶して、４−［トランスー４′−
（１−ランス−４″−プロピルシクロヘキシル）シクロ
へキシル］ブロモベンゼンｌ。After carbon tetrachloride was distilled off, the residue was recrystallized from a mixed solvent of chloroform and acetone to obtain 4-[trans-4'-
(1-lance-4″-propylcyclohexyl)cyclohexyl]bromobenzene l.
ｇを得た。I got g.
工程６４−［トランス−４′−（１−ランス−４−一プ
ロビルシクロヘキシル）シクロヘキシル］ブロモベンゼ
ン１０ｇとシアン化銅（Ｉ）３．８ｇとＮ−メチルピロ
リジノン５５ｃｍ３を４時間還流した。反応物を５０℃
まで冷却し、ＦｅＣｌ２．−６８２０２２ｇと濃塩酸５
ｃｍ”と水３３ｃｎ１３から調整した溶液を加え５０℃
で１時間放置した。析出した結晶を濾過し、水で洗浄し
た。結晶をアセトンとメタノールの混合溶媒から再結晶
して、４−［トランス−４′−（１−ランス−４“−プ
ロビルシクロヘキシル）シクロヘキシル］ベンゾニトリ
ル７．７ｇを得た。Step 64-10 g of [trans-4'-(1-trans-4-1propylcyclohexyl)cyclohexyl]bromobenzene, 3.8 g of copper(I) cyanide, and 55 cm3 of N-methylpyrrolidinone were refluxed for 4 hours. Reactant at 50℃
Cool to FeCl2. -682022g and concentrated hydrochloric acid 5
Add a solution prepared from 33 cm” and 33 cm of water and heat at 50°C.
I left it for 1 hour. The precipitated crystals were filtered and washed with water. The crystals were recrystallized from a mixed solvent of acetone and methanol to obtain 7.7 g of 4-[trans-4'-(1-trans-4"-probylcyclohexyl)cyclohexyl]benzonitrile.
工程７４−［トランス−４′ −（トランス−４″−プ
ロピルシクロヘキシル）シクロへキシル］ベンゾニトリ
ル７．７ｇと水酸化カリウム７．６ｇと水４ ｃｍ３
とエチレングリコール２３０ｃｍ”を１５時間撹拌しな
がら還流した。反応物を冷却後、濃塩酸２０ｃｍ”を加
えて５時間撹拌した。結晶を濾過し水で洗浄してから乾
燥して４−［トランス−４′−（１−ランス−４″−プ
ロピルシクロヘキシル）シクロヘキシル］安息香酸７５
ｇを得た。Step 74 - [trans-4'-(trans-4''-propylcyclohexyl)cyclohexyl] 7.7 g of benzonitrile, 7.6 g of potassium hydroxide, and 4 cm3 of water
and 230 cm" of ethylene glycol were refluxed with stirring for 15 hours. After cooling the reaction mixture, 20 cm" of concentrated hydrochloric acid was added and stirred for 5 hours. The crystals were filtered, washed with water, and dried to give 4-[trans-4'-(1-trans-4''-propylcyclohexyl)cyclohexyl]benzoic acid 75
I got g.
工程８ 工程３と同様にして４−［トランス−４’ −
（トランス−４″−プロピルシクロヘキシル）シクロヘ
キシル］安息香酸クロライド７１ｇを得た。Step 8 In the same manner as Step 3, 4-[trans-4'-
71 g of (trans-4''-propylcyclohexyl)cyclohexyl]benzoic acid chloride was obtained.
実施例３４−フルオロフェノル ４’ −［トランス−
４″＝（トランス−４″′−プロピルシクロヘキシル）
シクロヘキシル］ベンゾエートの製造方法。Example 34-Fluorophenol 4'-[trans-
4″=(trans-4″’-propylcyclohexyl)
Method for producing [cyclohexyl]benzoate.
工程４４−フルオロフェノール０．３４ｇを脱水ピリジ
ン６ ｃｍ”に溶解し、氷水冷却下振りまぜなから４−
［トランス−４′−（１−ランス−４″−プロビルシク
ロヘキシル）シクロヘキシル］安息香酸クロライドｌ
ｏｇを少しずつ加えた。その後、氷水冷却下で１時間、
さらに室温で２４時間放置した。反応物を濃塩酸２０ｃ
ｍ３と氷３０ｇ中に注ぎ析出した結晶を濾過し水洗した
。結晶をクロロホルムとアセトンの混合溶媒から再結晶
してチーフルオロフェニル ４′ −［トランス−４″
−（トランス−４″′−プロピルシクロヘキシル）シク
ロヘキシル］ベンゾエート０．５ｇを得た。この化合物
の相転移温度は次のとうりであった。Step 44 - Dissolve 0.34 g of fluorophenol in 6 cm" of dehydrated pyridine and stir while cooling with ice water.
[trans-4'-(1-trans-4''-propylcyclohexyl)cyclohexyl]benzoic acid chloride l
og was added little by little. Then cooled in ice water for 1 hour.
Furthermore, it was left to stand at room temperature for 24 hours. The reaction product was added with 20 c of concentrated hydrochloric acid.
The precipitated crystals were filtered and washed with water. The crystals were recrystallized from a mixed solvent of chloroform and acetone to obtain trifluorophenyl 4'-[trans-4''
0.5 g of -(trans-4'''-propylcyclohexyl)cyclohexyl]benzoate was obtained. The phase transition temperature of this compound was as follows.
Ｃ，Ｈ，（）へ■（）ｃ００％Ｆ
（ここで、Ｃは固体、ＳはスメクチックＳ相、Ｎはネマ
チック相、■は等方性液体を示す。以下同様。）
実施例４〜６
実施例３と同様な製造方法により次の化合物を得た。こ
れらの化合物の相転移温度を並記した。To C, H, ()■ ()c00%F (Here, C is a solid, S is a smectic S phase, N is a nematic phase, and ■ is an isotropic liquid. The same applies hereinafter.) Examples 4 to 6 The following compound was obtained by the same manufacturing method as in Example 3. The phase transition temperatures of these compounds are also listed.
４−シアノ−３フルオロフエニル ４′−［トランス−
４″−（トランス−４″′−プロピルシクロヘキシル）
シクロヘキシル］ベンゾエート１０８°０ ３５２℃
Ｃ□→Ｎ□→Ｉ
４−シアノ−３−クロロフェニル ４′−［トランス−
４″−（トランス−４″′−プロピルシクロヘキシル）
シクロヘキシル］ベンゾエート１２６℃ １３２°Ｃ３
１６℃
Ｃ□→Ｓ□−Ｎ□→■
４−シアノフェニル ４′−［１−ランス−４″−（ト
ランス−４″′−プロピルシクロヘキシル ）シクロヘ
キシル］ベンゾエート
Ｃ，Ｈ，−Ｑ図気妹ｃ ｏ ｏ （）ＣＮ１４５℃ 〉
３５０℃
Ｃ−−Ｎ□→Ｉ
応用例１
市販の液晶組成物ＺＬＩ−１５６５（メルり社製）９０
重量％に４−シアノ−４″−ペンチルレターフェニル１
０重量％を混合した液晶組成物を作りＮ−Ｉ点を測定し
たところ１０１ ’Ｃであつた。また、この液晶組成物
を厚さ８．０μｍのＴＮ型セルに封入して、そのしきい
値電圧を測定したところ２．４Ｖであった。同様にして
、ＺＬＩ−１５６５を９０重量％に実施例３の化合物１
０重量％を混合して作った液晶組成物のＮ−Ｉ点は１０
９°Ｃ１しきい値電圧は２．４Ｖあった。4-cyano-3fluorophenyl 4'-[trans-
4″-(trans-4″′-propylcyclohexyl)
cyclohexyl]benzoate 108°0 352°C C□→N□→I 4-cyano-3-chlorophenyl 4'-[trans-
4″-(trans-4″′-propylcyclohexyl)
cyclohexyl] benzoate 126°C 132°C3
16℃ C□→S□-N□→■ 4-Cyanophenyl 4'-[1-lance-4"-(trans-4"'-propylcyclohexyl)cyclohexyl]benzoate C, H, -Q o o ()CN145℃ 〉
350°C C--N□→I Application example 1 Commercially available liquid crystal composition ZLI-1565 (manufactured by Merli Co., Ltd.) 90
4-cyano-4″-pentylletterphenyl 1% by weight
A liquid crystal composition containing 0% by weight was prepared and the N-I point was measured and found to be 101'C. Further, this liquid crystal composition was sealed in a TN type cell having a thickness of 8.0 μm, and its threshold voltage was measured and found to be 2.4V. Similarly, compound 1 of Example 3 was added to 90% by weight of ZLI-1565.
The N-I point of the liquid crystal composition prepared by mixing 0% by weight is 10.
The 9°C1 threshold voltage was 2.4V.
応用例２
応用例１と同様ニシテ、ＺＬＩ−１５６５を９０重量％
と実施例４の化合物をｌＯ重量％混合して作った液晶組
成物のＮ−Ｉ点は１１３°Ｃ５しきい値電圧は１．８Ｖ
であった。Application example 2 Same as application example 1, 90% by weight of Nishite and ZLI-1565
The N-I point of the liquid crystal composition prepared by mixing 10% by weight of the compound of Example 4 and the compound of Example 4 was 113°C5, and the threshold voltage was 1.8V.
Met.
応用例３
応用例１と同様＋、ｍして、ＺＬＩ−１５６５を９０重
量％と実施例５の化合物を１０重量％混合して作った液
晶組成物のＮ−Ｉ点は１１０°Ｃ１しきい値電圧は１．
９Ｖであった。Application Example 3 As in Application Example 1, the N-I point of a liquid crystal composition prepared by mixing 90% by weight of ZLI-1565 and 10% by weight of the compound of Example 5 was 110°C1 threshold. The value voltage is 1.
It was 9V.
応用例４
応用例１と同様にして、ＺＬＩ−１５６５を９０重量％
と実施例６の化合物を１０重量％混合して作った液晶組
成物のＮ−Ｉ点は１１５°Ｃ１しきい値電圧は２．２ｖ
であった。Application example 4 Same as application example 1, 90% by weight of ZLI-1565
The N-I point of the liquid crystal composition prepared by mixing 10% by weight of the compound of Example 6 and the compound of Example 6 is 115°C1, and the threshold voltage is 2.2V.
Met.
応用例１〜４の結果を第１表にまとめて示した。The results of Application Examples 1 to 4 are summarized in Table 1.
第１表
［発明の効果］
以上述べたように本発明の液晶化合物は非常に高いＮ−
Ｉ点を持つことがわかった。また本発明の液晶化合物と
他の液晶組成物を混合することにより実用温度範囲が広
く、かつ駆動電圧の低い液晶組成物が得られることが確
認できた。Table 1 [Effects of the Invention] As stated above, the liquid crystal compound of the present invention has a very high N-
It turns out that it has an I point. Furthermore, it was confirmed that by mixing the liquid crystal compound of the present invention with another liquid crystal composition, a liquid crystal composition having a wide practical temperature range and a low driving voltage could be obtained.
以上 出願人 セイコーエプソン株式会社that's all Applicant: Seiko Epson Corporation
Claims (1)
、ＸはＣＮ、Ｆ又はＣｌ、ＹはＨ、Ｆ又はＣｌを示し、
シクロヘキサン環はトランス配置である。）で表わされ
る液晶化合物。[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the above formula, R is a straight chain alkyl group having 1 to 10 carbon atoms, X is CN, F or Cl, Y represents H, F or Cl,
The cyclohexane ring is in the trans configuration. ) is a liquid crystal compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252525A JPH02101046A (en) | 1988-10-06 | 1988-10-06 | Liquid crystal compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252525A JPH02101046A (en) | 1988-10-06 | 1988-10-06 | Liquid crystal compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02101046A true JPH02101046A (en) | 1990-04-12 |
Family
ID=17238583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63252525A Pending JPH02101046A (en) | 1988-10-06 | 1988-10-06 | Liquid crystal compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02101046A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824543A (en) * | 2017-11-23 | 2019-05-31 | 江苏和成显示科技有限公司 | A kind of compound and its liquid-crystal composition and application |
-
1988
- 1988-10-06 JP JP63252525A patent/JPH02101046A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824543A (en) * | 2017-11-23 | 2019-05-31 | 江苏和成显示科技有限公司 | A kind of compound and its liquid-crystal composition and application |
| CN109824543B (en) * | 2017-11-23 | 2022-02-22 | 江苏和成显示科技有限公司 | Compound, liquid crystal composition and application thereof |
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