JP3432248B2 - Cyclohexene derivative - Google Patents
Cyclohexene derivativeInfo
- Publication number
- JP3432248B2 JP3432248B2 JP19528993A JP19528993A JP3432248B2 JP 3432248 B2 JP3432248 B2 JP 3432248B2 JP 19528993 A JP19528993 A JP 19528993A JP 19528993 A JP19528993 A JP 19528993A JP 3432248 B2 JP3432248 B2 JP 3432248B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- compound
- toluene
- cyclohexene derivative
- crystal composition
- 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.)
- Expired - Fee Related
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- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は液晶材料として有用なシ
クロヘキセン誘導体に関し、さらに前記誘導体を含有す
る液晶組成物、および前記液晶組成物を用いた液晶表示
装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclohexene derivative useful as a liquid crystal material, a liquid crystal composition containing the derivative, and a liquid crystal display device using the liquid crystal composition.
【０００２】[0002]
【従来の技術】液晶表示装置は、時計、電卓を始めワー
プロ、テレビ等に広く利用されている。これらの液晶表
示装置のなかで特に多く使用されているのは、液晶材料
の光学的異方性および誘電異方性を利用したＴＮ型（ね
じれネマチック型）液晶表示装置である。現在液晶表示
装置に用いられる液晶材料に要求される特性としては、
液晶温度範囲が広いこと、電気光学的な応答速度が速い
こと、視角範囲が広いこと、駆動電圧が低いこと、化学
的および光学的に安定であることなどが挙げられる。2. Description of the Related Art Liquid crystal display devices are widely used in timepieces, calculators, word processors, televisions and the like. Among these liquid crystal display devices, a TN type (twisted nematic type) liquid crystal display device which utilizes the optical anisotropy and the dielectric anisotropy of the liquid crystal material is particularly often used. The characteristics required for liquid crystal materials currently used in liquid crystal display devices are:
It has a wide liquid crystal temperature range, a high electro-optical response speed, a wide viewing angle range, a low driving voltage, and a chemically and optically stable state.
【０００３】[0003]
【発明が解決しようとする課題】以上のような特性を全
て満足する単一の液晶化合物は未だ見いだされていな
い。そのためいろいろな特性をもった数種の液晶化合物
を混合したり、あるいはさらに非液晶化合物を混合した
りして実用に供しているのが現状である。A single liquid crystal compound satisfying all the above characteristics has not yet been found. Therefore, at present, several kinds of liquid crystal compounds having various characteristics are mixed, or further non-liquid crystal compounds are mixed for practical use.
【０００４】液晶表示装置の駆動電圧はしきい値電圧Ｖ
ｔｈの値に依存し、しきい値電圧Ｖｔｈは誘電異方性Δ
εの平方根に比例する。そのため誘電異方性Δεが正の
液晶材料を用いるとしきい値電圧Ｖｔｈを低い値に抑え
ることができる。そこで本発明の目的は誘電異方性Δε
が正の液晶化合物を提供することである。The driving voltage of the liquid crystal display device is the threshold voltage V
The threshold voltage Vth depends on the value of th and the dielectric anisotropy Δ
proportional to the square root of ε. Therefore, when a liquid crystal material having a positive dielectric anisotropy Δε is used, the threshold voltage Vth can be suppressed to a low value. Therefore, the object of the present invention is
Is to provide a positive liquid crystal compound.
【０００５】[0005]
【課題を解決するための手段】本発明のシクロヘキセン
誘導体は一般式（１）で表されるものである。The cyclohexene derivative of the present invention is represented by the general formula (1).
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】（ただし、Ｒ1 は炭素数１〜１０のアルキ
ル基を示し、Ｘはシアノ基またはハロゲン原子を示し、
Ｙは水素原子またはハロゲン原子を示す。）(Wherein R 1 represents an alkyl group having 1 to 10 carbon atoms, X represents a cyano group or a halogen atom,
Y represents a hydrogen atom or a halogen atom. )
【０００８】また、本発明の液晶組成物は、前記シクロ
ヘキセン誘導体を含有するものである。The liquid crystal composition of the present invention contains the above cyclohexene derivative.
【０００９】更に、本発明の液晶表示装置は、前記シク
ロヘキセン誘導体を含有する液晶組成物を用いたもので
ある。Further, the liquid crystal display device of the present invention uses the liquid crystal composition containing the cyclohexene derivative.
【００１０】本発明のシクロヘキセン誘導体の製造方法
について説明する。ただしＲ1 、ＸおよびＹは特許請求
の範囲に記載されているものと同じである。The method for producing the cyclohexene derivative of the present invention will be described. However, R 1 , X and Y are the same as those described in the claims.
【００１１】本発明化合物（１）のＸがシアノ基、Ｙが
水素原子の場合の製造方法を化３を用いて説明する。ま
ず、ｐ−アルキルシクロヘキサノン（ａ）とブロモ酢酸
メチル（ｂ）を反応させ、その後、脱水反応させること
により、化合物（ｃ）を得ることができる。次にこの化
合物（ｃ）をアルカリで加水分解し、化合物（ｄ）と
し、次いで塩化チオニルにより酸クロライドである化合
物（ｅ）を得ることができる。この化合物（ｅ）をあら
かじめ調整してあるグリニア試薬（ｆ）とグリニア反応
させ、化合物（ｇ）とする。この化合物（ｇ）を還元
し、さらに脱水反応させることにより化合物（ｈ）を得
る。次にこの化合物（ｈ）をシアン化第１銅と反応さ
せ、目的のシクロヘキセン誘導体（１）が得られる。
尚、本発明化合物（１）のＸがシアノ基でない場合は、
グリニア試薬（ｆ）で化４のものを用いれば良い。The production method in the case where X of the compound (1) of the present invention is a cyano group and Y is a hydrogen atom will be described using Chemical formula 3. First, the compound (c) can be obtained by reacting the p-alkylcyclohexanone (a) with methyl bromoacetate (b) and then subjecting it to a dehydration reaction. Next, this compound (c) can be hydrolyzed with an alkali to give a compound (d), and then thionyl chloride can be used to obtain a compound (e) which is an acid chloride. The compound (e) is reacted with the previously prepared Grineer reagent (f) to give a compound (g). Compound (h) is obtained by reducing this compound (g) and further subjecting it to a dehydration reaction. Next, this compound (h) is reacted with cuprous cyanide to obtain the desired cyclohexene derivative (1).
When X of the compound (1) of the present invention is not a cyano group,
As the Grineer reagent (f), a compound of Chemical formula 4 may be used.
【００１２】[0012]
【化３】 [Chemical 3]
【００１３】[0013]
【化４】 [Chemical 4]
【００１４】本発明のシクロヘキセン誘導体は多くの液
晶化合物と混合し液晶組成物を製造することができる。
また、これらの液晶組成物を液晶表示装置に用いること
もできる。本発明の誘導体と混合可能な液晶化合物とし
てはエステル系、シクロヘキシルフェニル系、ビフェニ
ル系、ピリミジン系、ジオキサン系、トラン系などが挙
げられる。The cyclohexene derivative of the present invention can be mixed with many liquid crystal compounds to produce a liquid crystal composition.
Further, these liquid crystal compositions can also be used in a liquid crystal display device. Examples of liquid crystal compounds that can be mixed with the derivative of the present invention include ester-based, cyclohexylphenyl-based, biphenyl-based, pyrimidine-based, dioxane-based, and tolan-based compounds.
【００１５】[0015]
【実施例】次に実施例をあげ、本発明を更に具体的に説
明するが、本発明はこれら実施例により何等制約される
ものではない。EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
【００１６】（実施例１）トルエン１ｌに亜鉛１５０ｇ
と４−エチルシクロヘキサノン１２６ｇとブロモ酢酸メ
チル２００ｇを加え、９０℃で加熱攪拌させる。１時間
の反応の後、室温まで冷却し、亜鉛をろ過して取り除
き、トルエン層を取りだし、希塩酸で酸性にした後、飽
和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した後、
トルエンを留去する。この粗生成物をトルエン１ｌに溶
解させ、この溶液にｐ−トルエンスルホン酸二水和物３
０ｇを加えた後、攪拌しながら還流し、反応によって生
成する水をデカンターで除去した。この脱水反応を１時
間行った後、反応混合物を冷却した。トルエン層を飽和
炭酸ナトリウム水溶液、飽和食塩水で順次洗浄し、無水
硫酸ナトリウムで乾燥した後、トルエンを留去する。(Example 1) 150 g of zinc in 1 l of toluene
And 126 g of 4-ethylcyclohexanone and 200 g of methyl bromoacetate are added, and the mixture is heated and stirred at 90 ° C. After the reaction for 1 hour, the mixture was cooled to room temperature, zinc was removed by filtration, the toluene layer was taken out, acidified with dilute hydrochloric acid, washed with saturated brine and dried over anhydrous sodium sulfate,
Distill off the toluene. This crude product was dissolved in 1 l of toluene, and p-toluenesulfonic acid dihydrate 3 was added to this solution.
After adding 0 g, the mixture was refluxed with stirring, and water produced by the reaction was removed by a decanter. After performing this dehydration reaction for 1 hour, the reaction mixture was cooled. The toluene layer is washed successively with saturated aqueous sodium carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and toluene is distilled off.
【００１７】次にこの粗生成物をメタノール４００ｍｌ
に溶解させ、攪拌しながら水酸化ナトリウムの５０％水
溶液１２０ｍｌをゆっくり滴下する。滴下終了後６０℃
で１時間反応させ、反応終了後反応液を冷却し、四塩化
炭素で抽出する。四塩化炭素層を酸洗浄し、さらに飽和
食塩水で洗浄し、塩化カルシウムで乾燥した後、四塩化
炭素を留去する。Next, this crude product was mixed with 400 ml of methanol.
And 120 ml of a 50% aqueous solution of sodium hydroxide are slowly added dropwise while stirring. 60 ℃ after dropping
After 1 hour, the reaction solution is cooled and extracted with carbon tetrachloride. The carbon tetrachloride layer is washed with an acid, further washed with a saturated saline solution and dried with calcium chloride, and then carbon tetrachloride is distilled off.
【００１８】次にこの粗生成物を塩化チオニル４５０ｇ
の中に溶解させ、室温で２４時間攪拌させる。反応終了
後、塩化チオニルを減圧留去させ、トルエンで抽出し、
トルエン層を飽和炭酸ナトリウム水溶液、飽和食塩水で
順次洗浄し、無水硫酸ナトリウムで乾燥した後、トルエ
ンを留去する。さらに減圧蒸留して、酸クロライドを９
１ｇ得た。Next, this crude product was added to 450 g of thionyl chloride.
Dissolve in and let stir at room temperature for 24 hours. After the reaction was completed, thionyl chloride was distilled off under reduced pressure and extracted with toluene,
The toluene layer is washed successively with saturated aqueous sodium carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and toluene is distilled off. Further distill under reduced pressure to obtain acid chloride of 9
1 g was obtained.
【００１９】次にｐ−ジブロモベンゼン５４ｇを無水エ
−テル２００ｍｌに溶解させ、この溶液を金属マグネシ
ウム粉末６ｇに攪拌しながら１５〜２０℃で滴下した
後、室温で１時間反応させてｐ−ブロモフェニルマグネ
シウムブロマイドを生成させた。この生成したグリニア
試薬を先に生成させた酸クロライド３６ｇとＴＨＦ１０
０ｃｃの混合物の中へ３０℃で滴下していく。滴下終了
後、４０℃でさらに攪拌し、１時間反応させる。反応終
了後、塩酸２０ｍｌを除々に滴下した後、ジエチルエ−
テルで抽出した。抽出液を飽和食塩水で洗浄した後、無
水硫酸ナトリウムを加えて抽出液を乾燥した。これをろ
過しろ液から溶媒を減圧留去して、さらに減圧蒸留して
ケトン４０ｇを得た。Next, 54 g of p-dibromobenzene was dissolved in 200 ml of anhydrous ether, and this solution was added dropwise to 15 g of metallic magnesium powder at 15 to 20 ° C. with stirring. Phenylmagnesium bromide was produced. The produced Grineer reagent was added with 36 g of the acid chloride produced previously and 10 parts of THF.
Drop into 0 cc of mixture at 30 ° C. After completion of dropping, the mixture is further stirred at 40 ° C. and reacted for 1 hour. After the reaction was completed, 20 ml of hydrochloric acid was gradually added dropwise and then diethyl ether was added.
It was extracted with tell. The extract was washed with saturated brine, anhydrous sodium sulfate was added, and the extract was dried. This was filtered, the solvent was distilled off from the filtrate under reduced pressure, and further distilled under reduced pressure to obtain 40 g of ketone.
【００２０】次にこのケトン４０ｇにＴＨＦ２００ｃｃ
を加え、２０℃で水素化リチウムアルミニウム３ｇを加
え、そのままの温度で３時間攪拌し、反応させる。反応
終了後、酢酸エチル８ｃｃを加え、希塩酸で酸性にし、
トルエンで抽出をする。トルエン層を飽和炭酸ナトリウ
ム水溶液、飽和食塩水で順次洗浄し、無水硫酸ナトリウ
ムで乾燥した後、トルエンを留去する。この粗生成物を
トルエン２００ｃｃに溶解させ、この溶液に硫酸水素カ
リウム６ｇを加えた後、攪拌しながら還流し、反応によ
って生成する水をデカンターで除去した。この脱水反応
を１時間行った後、反応混合物を冷却した。トルエン層
を飽和炭酸ナトリウム水溶液、飽和食塩水で順次洗浄
し、無水硫酸ナトリウムで乾燥した後、トルエンを留去
する。さらに減圧蒸留し、エチレン化合物１５ｇを得
た。Next, 40 g of this ketone was added to 200 cc of THF.
Then, 3 g of lithium aluminum hydride is added at 20 ° C., and the mixture is stirred at the same temperature for 3 hours to react. After completion of the reaction, add 8 cc of ethyl acetate, acidify with dilute hydrochloric acid,
Extract with toluene. The toluene layer is washed successively with saturated aqueous sodium carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and toluene is distilled off. The crude product was dissolved in 200 cc of toluene, 6 g of potassium hydrogen sulfate was added to this solution, and the mixture was refluxed with stirring, and water produced by the reaction was removed by a decanter. After performing this dehydration reaction for 1 hour, the reaction mixture was cooled. The toluene layer is washed successively with saturated aqueous sodium carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and toluene is distilled off. Further, it was distilled under reduced pressure to obtain 15 g of an ethylene compound.
【００２１】次にこの化合物をＮ−メチルピロリドン５
０ｍｌに溶解させ、シアン化第１銅７ｇを加えて２時間
還流する。その後約２０ｍｌのＮ−メチルピロリドンを
留去させ、次いで塩化第２鉄水を加え６０℃で攪拌し、
トルエン抽出し酸洗浄し、さらに飽和食塩水で洗浄し、
無水硫酸ナトリウムで乾燥した後、トルエンを留去し、
シリカゲルカラムにて精製し、さらにアセトンから再結
晶し、化５記載の化合物（２）である１−（４−エチル
シクロヘキセニル）−２−（４−シアノフェニル）−エ
チレン５ｇを得た。このものはネマチック液晶で、Ｃ−
Ｎ点５２℃、Ｎ−Ｉ点７３．３℃であった。また、この
ものの誘電異方性Δεの値は＋１４であった。この化合
物（２）の赤外吸収スペクトルを図１に示す。Next, this compound was added to N-methylpyrrolidone 5
Dissolve in 0 ml, add 7 g of cuprous cyanide and reflux for 2 hours. Thereafter, about 20 ml of N-methylpyrrolidone was distilled off, ferric chloride water was added, and the mixture was stirred at 60 ° C.,
Extracted with toluene, washed with acid, washed with saturated saline,
After drying over anhydrous sodium sulfate, the toluene was distilled off,
The product was purified by a silica gel column and further recrystallized from acetone to obtain 5 g of 1- (4-ethylcyclohexenyl) -2- (4-cyanophenyl) -ethylene which is the compound (2) described in Chemical formula 5. This is a nematic liquid crystal, C-
The N point was 52 ° C and the NI point was 73.3 ° C. The value of the dielectric anisotropy Δε of this product was +14. The infrared absorption spectrum of this compound (2) is shown in FIG.
【００２２】[0022]
【化５】 [Chemical 5]
【００２３】（実施例２）化６で表される化合物のみか
らなる液晶組成物の特性はＮ−Ｉ点５２．１℃、Δｎ
０．１２０、粘度２２．９ｃＰ、Ｖth１．４５Ｖであっ
た。この液晶組成物９０重量部に、本発明化合物１−
（４−エチルシクロヘキセニル）−２−（４−シアノフ
ェニル）−エチレン１０重量部を加えた液晶組成物のＮ
−Ｉ点は５３．４℃、Δｎ０．１３２で粘度は２７．８
ｃＰであり、Ｖthは１．２７Ｖと低くなった。なお、し
きい値電圧Ｖthはこの液晶組成物をセル厚９μｍのＴＮ
型液晶表示装置に搭載した際の値である。(Example 2) The characteristics of the liquid crystal composition consisting only of the compound represented by Chemical formula 6 are as follows: NI point 52.1 ° C., Δn
It had a viscosity of 0.120, a viscosity of 22.9 cP and a Vth of 1.45V. To 90 parts by weight of this liquid crystal composition, the compound of the present invention 1-
N of a liquid crystal composition containing 10 parts by weight of (4-ethylcyclohexenyl) -2- (4-cyanophenyl) -ethylene
-I point is 53.4 ° C, Δn is 0.132, and viscosity is 27.8.
It was cP and Vth was lowered to 1.27V. The threshold voltage Vth is determined by using this liquid crystal composition as
This is the value when mounted on a liquid crystal display device.
【００２４】[0024]
【化６】 [Chemical 6]
【００２５】[0025]
【発明の効果】本発明のシクロヘキセン誘導体は、誘電
異方性Δεが正を示す。そのため本発明の化合物を含有
する液晶組成物は液晶材料として優れた特性を有し、ま
たその液晶組成物を用いた液晶表示装置は良好な表示特
性を有する。さらに本発明誘導体は種々の化合物との相
互溶解性が大きく、液晶組成物の構成成分として多くの
液晶材料と組み合わせて使用することができ、液晶組成
物の特性改良に有用なものである。The cyclohexene derivative of the present invention has a positive dielectric anisotropy Δε. Therefore, a liquid crystal composition containing the compound of the present invention has excellent properties as a liquid crystal material, and a liquid crystal display device using the liquid crystal composition has good display properties. Further, the derivative of the present invention has a large mutual solubility with various compounds and can be used in combination with many liquid crystal materials as a constituent component of a liquid crystal composition, and is useful for improving the characteristics of the liquid crystal composition.
【図１】本発明化合物の一つである１−（４−エチルシ
クロヘキセニル）−２−（４−シアノフェニル）−エチ
レンの赤外吸収スペクトルを表す図である。FIG. 1 is a diagram showing an infrared absorption spectrum of 1- (4-ethylcyclohexenyl) -2- (4-cyanophenyl) -ethylene which is one of the compounds of the present invention.
Claims (3)
誘導体。 【化１】 （ただし、Ｒ1 は炭素数１〜１０のアルキル基を示し、
Ｘはシアノ基またはハロゲン原子を示し、Ｙは水素原子
またはハロゲン原子を示す。）1. A cyclohexene derivative represented by the general formula (1). [Chemical 1] (However, R 1 represents an alkyl group having 1 to 10 carbon atoms,
X represents a cyano group or a halogen atom, and Y represents a hydrogen atom or a halogen atom. )
含有する液晶組成物。2. A liquid crystal composition containing the cyclohexene derivative according to claim 1.
含有する液晶組成物を用いた液晶表示装置。3. A liquid crystal display device using the liquid crystal composition containing the cyclohexene derivative according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19528993A JP3432248B2 (en) | 1993-07-13 | 1993-07-13 | Cyclohexene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19528993A JP3432248B2 (en) | 1993-07-13 | 1993-07-13 | Cyclohexene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0725794A JPH0725794A (en) | 1995-01-27 |
| JP3432248B2 true JP3432248B2 (en) | 2003-08-04 |
Family
ID=16338679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19528993A Expired - Fee Related JP3432248B2 (en) | 1993-07-13 | 1993-07-13 | Cyclohexene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3432248B2 (en) |
-
1993
- 1993-07-13 JP JP19528993A patent/JP3432248B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725794A (en) | 1995-01-27 |
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