JPS63310859A - Optically active cyanobiphenyl compound - Google Patents
Optically active cyanobiphenyl compoundInfo
- Publication number
- JPS63310859A JPS63310859A JP14494887A JP14494887A JPS63310859A JP S63310859 A JPS63310859 A JP S63310859A JP 14494887 A JP14494887 A JP 14494887A JP 14494887 A JP14494887 A JP 14494887A JP S63310859 A JPS63310859 A JP S63310859A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- cyanobiphenyl
- compound
- temperature
- phase transition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 cyanobiphenyl compound Chemical class 0.000 title claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 17
- 239000012071 phase Substances 0.000 abstract description 17
- 230000007704 transition Effects 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000003098 cholesteric effect Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (+)-β-citronellol Chemical compound OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 abstract description 3
- ZRMIETZFPZGBEB-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzonitrile Chemical group C1=CC(O)=CC=C1C1=CC=C(C#N)C=C1 ZRMIETZFPZGBEB-UHFFFAOYSA-N 0.000 abstract description 3
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N Citronellol Natural products OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000006266 etherification reaction Methods 0.000 abstract description 2
- GJWSUKYXUMVMGX-UHFFFAOYSA-N (+)-(R)-citronellic acid Natural products OC(=O)CC(C)CCC=C(C)C GJWSUKYXUMVMGX-UHFFFAOYSA-N 0.000 abstract 1
- GJWSUKYXUMVMGX-SECBINFHSA-N (R)-citronellic acid Chemical compound OC(=O)C[C@H](C)CCC=C(C)C GJWSUKYXUMVMGX-SECBINFHSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DNJQGRFZQMOYGM-UHFFFAOYSA-N 4-[4-(2-methylbutyl)phenyl]benzonitrile Chemical group C1=CC(CC(C)CC)=CC=C1C1=CC=C(C#N)C=C1 DNJQGRFZQMOYGM-UHFFFAOYSA-N 0.000 description 1
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は正の誘電異方性を有する新規なシアノビフェニ
ル化合物に関し、詳しくは、（Ｒ）−シトロネロル酸の
シアノビフェニルエステルまたは（Ｒ）−シトロネロー
ルのシアノビフェニルエステルヲ提供するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cyanobiphenyl compound having positive dielectric anisotropy, and specifically provides a cyanobiphenyl ester of (R)-citronellolic acid or a cyanobiphenyl ester of (R)-citronellol. It is something to do.
正の誘電異方性を有する光学活性液晶はねじれネマチッ
ク型表示素子や、コレステリックーネマチンク相転移型
の表示素子に利用されている。これらに用いられる液晶
は、化学的及び光学的に安定であり、低温から高温まで
安定して液晶状態を示すものが望まれている。Optically active liquid crystals having positive dielectric anisotropy are used in twisted nematic type display elements and cholesteric-nematic phase transition type display elements. The liquid crystal used in these devices is desired to be chemically and optically stable and to stably exhibit a liquid crystal state from low to high temperatures.
しかしながら、このような性質を全て満足させる単一化
合物はこれまで知られておらず、このため、数種の液晶
化合物が混合物として用いられていた。However, a single compound that satisfies all of these properties has not been known so far, and for this reason several types of liquid crystal compounds have been used as a mixture.
例えば、４−ｎ−アルキルまたはアルコキシ−４°−シ
アノビフェニル化合物の混合物等が比較的広い温度範囲
で液晶相をとることが知られているが、これらの混合物
においても結晶一液晶相転移温度は一１０°Ｃ以上であ
り、満足しえるものではなかった。For example, it is known that mixtures of 4-n-alkyl or alkoxy-4°-cyanobiphenyl compounds take a liquid crystal phase over a relatively wide temperature range, but even in these mixtures, the crystal-liquid crystal phase transition temperature is The temperature was -10°C or higher, which was not satisfactory.
また、コレステリック相を与える液晶化合物として、４
−（２−メチルブチル）−４゛−シアノビフェニルが知
られているが、該化合物は液晶−等方性液体相転移温度
が約−３０°Ｃと低いために、所望の物性を得るために
は、多量を配合する必要がある欠点があった。In addition, as a liquid crystal compound that provides a cholesteric phase, 4
-(2-Methylbutyl)-4'-cyanobiphenyl is known, but since this compound has a low liquid crystal-isotropic liquid phase transition temperature of about -30°C, it is difficult to obtain the desired physical properties. However, there was a drawback that a large amount had to be added.
本発明者等は、該表示素子用液晶混合物の成分として有
用な、結晶一液晶相転移温度が低（、またコレステリッ
ク相を与える場合には液晶−等方性液体相転移温度の高
い化合物を見出すべく鋭意検討を重ねた結果、次の一般
式（Ｉ）で表される新規な光学活性シアノビフェニル化
合物が結晶一液晶相転移温度が著しく低く、また該化合
物がコレステリック相を与える場合には液晶−等方性液
体相転移温度が高いので、上記目的に使用するのに極め
て好適な化合物であることを見出した。The present inventors have discovered a compound useful as a component of the liquid crystal mixture for display devices, which has a low crystal-to-liquid crystal phase transition temperature (and, in the case of providing a cholesteric phase, a high liquid crystal to isotropic liquid phase transition temperature). As a result of extensive studies, we have found that a novel optically active cyanobiphenyl compound represented by the following general formula (I) has an extremely low crystal-to-liquid crystal phase transition temperature, and when the compound provides a cholesteric phase, it has a liquid crystal-to-liquid crystal phase transition temperature. It has been found that this compound is extremely suitable for use for the above purpose because of its high isotropic liquid phase transition temperature.
（式中、Ｘは−ｃｔｈ−または−ＣＯ−を示し、木は不
斉炭素を示す。）
以下、上記要旨をもってなる本発明について更に詳細に
説明する。(In the formula, X represents -cth- or -CO-, and wood represents an asymmetric carbon.) Hereinafter, the present invention having the above-mentioned summary will be explained in more detail.
上記一般式（Ｉ）で表される化合物は、例えば、４−ヒ
ドロキシ−４′−シアノビフェニルと（Ｒ）−シトロネ
リル酸または（Ｉ？）−シトロネロールとを、周知のエ
ステル化またはエーテル化の手法を用い反応させること
により、容易に製造することができる。The compound represented by the above general formula (I) can be obtained by, for example, esterifying or etherifying 4-hydroxy-4'-cyanobiphenyl and (R)-citronellilic acid or (I?)-citronellol using a well-known esterification or etherification method. It can be easily produced by reacting with.
次に、本発明を実施例によって説明する。しかしながら
、本発明は以下の実施例によって制限を受けるものでは
ない。Next, the present invention will be explained by examples. However, the present invention is not limited by the following examples.
実施例１
（Ｒ）−シトロネリル酸０．９４ｇおよび４−ヒドロキ
シ−４°−シアノビフェニル０．９６ ｇをジクロルメ
タン１〇−に溶解し、次いでジシクロへキシルカルボジ
イミド１．１３ｇおよび４−ピロリジノピリジン０．１
ｇを加え、室温で３時間撹拌した。脱溶媒後、酢酸エチ
ルを加え、生成したジシクロヘキシル尿素をろ別し、脱
溶媒した。Example 1 0.94 g of (R)-citronellilic acid and 0.96 g of 4-hydroxy-4°-cyanobiphenyl were dissolved in 10-dichloromethane, then 1.13 g of dicyclohexylcarbodiimide and 0.0 g of 4-pyrrolidinopyridine. .1
g and stirred at room temperature for 3 hours. After removing the solvent, ethyl acetate was added, and the generated dicyclohexyl urea was filtered off and the solvent was removed.
得られた残留物を、ｎ−ヘキサン／エーテル（８／２）
を展開溶媒としてシリカゲルカラムで精製し、目的の（
Ｒ）−４−シトロネロイルオキシ−４”−シアノビフェ
ニル１．２ｇを得た。The resulting residue was diluted with n-hexane/ether (8/2).
was purified using a silica gel column as a developing solvent to obtain the desired (
1.2 g of R)-4-citronelloyloxy-4''-cyanobiphenyl was obtained.
赤外分光分析の結果、得られた生成物は次の特性吸収を
有しており、目的物であることを確認した。As a result of infrared spectroscopic analysis, the obtained product had the following characteristic absorption, and was confirmed to be the desired product.
２９５０ｃ膳−’ （ｓ）、 ２２３０ｃｍ−’
軸）、 １７５０ｃ＋ｍ−’ （ｓ）、１６００ｃｍ
−’ （ｍ）、１１８０ｃｍ−’ （ｓ）、１１２０ｃ
＋ｉ−’ （ｓ）、８３０ｃｎ＋−’ （ｓ）
また、得られた生成物の旋光度を次に示す。2950c-' (s), 2230cm-'
axis), 1750c+m-' (s), 1600cm
-' (m), 1180cm-' (s), 1120c
+i-' (s), 830cn+-' (s) Further, the optical rotation of the obtained product is shown below.
〔α） 、 ＝＋６．２６° （２５°Ｃ、Ｃ＝ ｌ
、 ＣＨＣｈ溶液）この化合物の偏光顕微鏡による相形
態観察の結果、以下の相転移を確認した。[α), = +6.26° (25°C, C = l
, CHCh solution) As a result of observing the phase morphology of this compound using a polarizing microscope, the following phase transition was confirmed.
実施例２
（Ｒ）−４−シトロネリルオキシ）−４゛−シアノビフ
ェニルの製造
４−ヒドロキシ−４゛−シアノビフェニル１．００ ｇ
、水酸化カリウム０．２４ ｇ及びジオキサン１０ｄ
をとり、撹拌した後、ここに、（Ｒ）−シトロネロール
のｐ−トルエンスルホン酸エステル１．６ｇを加え、還
流下に１０時間撹拌した。脱溶媒後、ジエチルエーテル
を加え、５％塩酸で中和し、水洗、乾燥後脱溶媒した。Example 2 Production of (R)-4-citronellyloxy)-4′-cyanobiphenyl 1.00 g of 4-hydroxy-4′-cyanobiphenyl
, 0.24 g of potassium hydroxide and 10 d of dioxane
After stirring, 1.6 g of p-toluenesulfonic acid ester of (R)-citronellol was added thereto, and the mixture was stirred under reflux for 10 hours. After removing the solvent, diethyl ether was added, neutralized with 5% hydrochloric acid, washed with water, dried, and then the solvent was removed.
得られた残留物を、ｎ−ヘキサン／エーテル（９／１）
を展開溶媒としてシリカゲルカラムで精製し、目的の（
Ｒ）−４−シトロネリルオキシー４′〜シアノビフヱニ
ル１．４ｇを得た。The resulting residue was diluted with n-hexane/ether (9/1).
was purified using a silica gel column as a developing solvent to obtain the desired (
1.4 g of R)-4-citronellyloxy-4'-cyanobiphenyl was obtained.
赤外分光分析の結果、得られた生成物は次の特性吸収を
有しており、目的物であることを確認した。As a result of infrared spectroscopic analysis, the obtained product had the following characteristic absorption, and was confirmed to be the desired product.
３０５０ｃｍ−’ （ｗ）、２９５０ｃｎ＋−’ （ｓ
）、２２３０ｃｍ−’ （ｓ）、１６００ｃｍ−’ （
ｓ）、１４９５ｃｍ−’ （ｓ）、１２９０ｃｍ−’
（ｍ）、１２５０ｃ＋ｍ−’ （ｓ）、１１８０ｃｍ−
’ （ｍ）、８２０ｃｍ−’ （ｓ）また、得られた生
成物の旋光度を次に示す。3050cm-' (w), 2950cn+-' (s
), 2230cm-' (s), 1600cm-' (
s), 1495cm-' (s), 1290cm-'
(m), 1250c+m-' (s), 1180cm-
' (m), 820 cm-' (s) Also, the optical rotation of the obtained product is shown below.
〔α〕ゎ＝ ＋３．８６’ （２５°Ｃ，Ｃ・１、Ｃ
ＨＣｌ３溶液）この化合物の偏光顕微鏡による相形態観
察の結果、以下の相転移を確認した。[α]ゎ= +3.86' (25°C, C・1, C
HCl3 solution) As a result of observing the phase morphology of this compound using a polarizing microscope, the following phase transition was confirmed.
以上の実施例の結果から、本発明のシアノビフェニル化
合物は、結晶一液晶相転移温度が一１５°Ｃ以下と極め
て低いので、相転移温度の低い液晶混合物を得るのに適
していることが明らかである。From the results of the above examples, it is clear that the cyanobiphenyl compound of the present invention has an extremely low crystal-liquid crystal phase transition temperature of 115°C or less, and is therefore suitable for obtaining a liquid crystal mixture with a low phase transition temperature. It is.
Claims (1)
ル化合物。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｘは−ＣＨ＿２−または−ＣＯ−を示し、＊は
不斉炭素を示す。）[Claims] An optically active cyanobiphenyl compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents -CH_2- or -CO-, and * represents an asymmetric carbon.)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14494887A JPH0791258B2 (en) | 1987-06-10 | 1987-06-10 | Optically active cyanobiphenyl compound |
| US07/177,979 US4956488A (en) | 1987-04-13 | 1988-04-05 | Optically active cyanobiphenyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14494887A JPH0791258B2 (en) | 1987-06-10 | 1987-06-10 | Optically active cyanobiphenyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63310859A true JPS63310859A (en) | 1988-12-19 |
| JPH0791258B2 JPH0791258B2 (en) | 1995-10-04 |
Family
ID=15373910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14494887A Expired - Lifetime JPH0791258B2 (en) | 1987-04-13 | 1987-06-10 | Optically active cyanobiphenyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791258B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02231460A (en) * | 1989-03-03 | 1990-09-13 | Adeka Argus Chem Co Ltd | Alkenoxycyanobiphenyl compound |
-
1987
- 1987-06-10 JP JP14494887A patent/JPH0791258B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02231460A (en) * | 1989-03-03 | 1990-09-13 | Adeka Argus Chem Co Ltd | Alkenoxycyanobiphenyl compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791258B2 (en) | 1995-10-04 |
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