JPH0830037B2 - Optically active biphenyl ester compound - Google Patents
Optically active biphenyl ester compoundInfo
- Publication number
- JPH0830037B2 JPH0830037B2 JP222688A JP222688A JPH0830037B2 JP H0830037 B2 JPH0830037 B2 JP H0830037B2 JP 222688 A JP222688 A JP 222688A JP 222688 A JP222688 A JP 222688A JP H0830037 B2 JPH0830037 B2 JP H0830037B2
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- ester compound
- compound
- biphenyl ester
- chloro
- 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 - Lifetime
Links
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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】 本発明は強誘電性液晶化合物として有用な光学活性ビ
フェニルエステル化合物に関し、詳しくは、含塩素アル
コキシ基を有する光学活性ビフェニルエステル化合物に
関する。The present invention relates to an optically active biphenyl ester compound useful as a ferroelectric liquid crystal compound, and more particularly to an optically active biphenyl ester compound having a chlorine-containing alkoxy group.
不斉炭素原子を有するアルコキシベンゼン誘導体は液
晶化学物質用中間体として近年特に注目を集めており、
特に、アルコキシビフェニル化合物、アルコキシフェニ
ルピリミジン化合物、アルコキシ安息香酸誘導体等は強
誘電性スメクチック液晶化学物質として知られている。Alkoxybenzene derivatives having asymmetric carbon atoms have recently attracted particular attention as intermediates for liquid crystal chemicals.
In particular, alkoxybiphenyl compounds, alkoxyphenylpyrimidine compounds, alkoxybenzoic acid derivatives and the like are known as ferroelectric smectic liquid crystal chemical substances.
これらの液晶化合物におけるアルコキシ基としては、
６−メチルオクトキシ基、２−メチルブトキシ基等が知
られているが、これらの化合物は使用可能温度範囲が適
切でなかったり、あるいは配向安定性が劣ったりする問
題を有しており、実用的なものではなかった。As an alkoxy group in these liquid crystal compounds,
A 6-methyloctoxy group, a 2-methylbutoxy group and the like are known, but these compounds have a problem that the usable temperature range is not appropriate, or the orientation stability is poor. It wasn't what I expected.
このため、化合物の基本骨格を含め、現在強誘電性液
晶化合物について種々の検討が続けられていた。Therefore, various studies have been continued on the ferroelectric liquid crystal compound including the basic skeleton of the compound.
本発明者等は、不斉炭素原子を有するアルコキシビフ
ェニル化合物について鋭意検討を重ねた結果、次の一般
式で表される化合物が優れた液晶性を有していることを
見出した。As a result of intensive studies on the alkoxybiphenyl compound having an asymmetric carbon atom, the present inventors have found that the compound represented by the following general formula has excellent liquid crystallinity.
（式中、Ｒは炭素原子数１ないし18の直鎖アルキル基を
示し、Ｒ′は塩素含有アルキル基を示し、Ｘは−CO−Ｏ
−または−Ｏ−CO−を示し、Ｐおよびｑはそれぞれ０ま
たは１を示し、ｐ＋ｑ＝１を示し、ｎは２〜５を示し、
＊は不斉炭素原子を示す。） 上記一般式で示される化合物において、Ｒ′で示され
る塩素含有アルキル基としては、２−クロロエチル、３
−クロロプロピル、２−クロロプロピル、２−クロロブ
チル、３−クロロペンチル、２−クロロオクチル、３−
クロロデシル、２−クロロドデシル等の基があげられ
る。 (In the formula, R represents a linear alkyl group having 1 to 18 carbon atoms, R ′ represents a chlorine-containing alkyl group, and X represents —CO—O.
-Or -O-CO-, P and q each represent 0 or 1, p + q = 1, n represents 2 to 5,
* Indicates an asymmetric carbon atom. ) In the compound represented by the above general formula, the chlorine-containing alkyl group represented by R ′ is 2-chloroethyl, 3
-Chloropropyl, 2-chloropropyl, 2-chlorobutyl, 3-chloropentyl, 2-chlorooctyl, 3-
Examples thereof include groups such as chlorodecyl and 2-chlorododecyl.
上記一般式で表される化合物は、例えば、アルコキシ
ビフェニルカルボン酸と光学活性な含塩素アルコキシフ
ェノールとを反応させるた、あるいは光学活性な含塩素
アルコキシ安息香酸とアルコキシビフェノールとを脱水
剤の存在下に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 is, for example, an alkoxybiphenylcarboxylic acid reacted with an optically active chlorine-containing alkoxyphenol, or an optically active chlorine-containing alkoxybenzoic acid and an alkoxybiphenol in the presence of a dehydrating agent. It can be easily produced by reacting.
次に、本発明を実施例によって説明する。 Next, the present invention will be described with reference to examples.
実施例１ （Ｒ）−４−ｎ−オクチルオキシビフェニルカルボン酸
−４−（６′−クロロ−４′−メチルデシルオキシ）フ
ェニルエステルの合成 0.65gの４−ｎ−オクチルオキシビフェニルカルボン
酸、0.60gの（Ｒ）−４−（６′−クロロ−４′−メチ
ルデシルオキシ）フェノール、0.04gのN,N′−ジシクロ
ヘキシルカルボジイミド及び0.04gの４−ピロリジノピ
リジンをジクロルメタン20mlに加え、室温で３時間反応
した。析出したジシクロヘキシル尿素をろ別後、ろ液を
脱溶媒した。得られた粗生成物をエタノール／アセトン
（7/3）混合溶媒から再結晶を繰り返して、目的の
（Ｒ）−４−ｎ−オクチルオキシビフェニルカルボン酸
−４−（６′−クロロ−４′−メチルデシルオキシ）フ
ェニルエステルを得た。Example 1 Synthesis of (R) -4-n-octyloxybiphenylcarboxylic acid-4- (6'-chloro-4'-methyldecyloxy) phenyl ester 0.65 g 4-n-octyloxybiphenylcarboxylic acid, 0.60 g (R) -4- (6'-chloro-4'-methyldecyloxy) phenol, 0.04 g N, N'-dicyclohexylcarbodiimide and 0.04 g 4-pyrrolidinopyridine were added to 20 ml dichloromethane at room temperature. Reacted for 3 hours. The precipitated dicyclohexylurea was filtered off, and the filtrate was desolvated. The obtained crude product was repeatedly recrystallized from a mixed solvent of ethanol / acetone (7/3) to obtain the desired (R) -4-n-octyloxybiphenylcarboxylic acid-4- (6′-chloro-4 ′). -Methyldecyloxy) phenyl ester 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 absorptions and was confirmed to be the target product.
この化合物を二枚のガラス板に挟み、偏光顕微鏡によ
る相形態観察を行った結果、以下の相転移を確認した。 The compound was sandwiched between two glass plates and the phase morphology was observed with a polarization microscope. As a result, the following phase transitions were confirmed.
この化合物を、ラビングにより配向処理を施した厚さ
２μｍのガラス透明電極セルに注入した後に、180℃に
加熱して等方性液体とした。この液晶セルを150℃まで
徐冷し、直交ニコル下で±15V、1Hzの矩形波を印加した
ところ、明瞭なスイッチング動作が確認された。また三
角波法を用いて自発分極を測定したところ、1.7nC/cm2
であった。また110℃での応答速度（電界印加から90％
立ち上がりまでの時間）は200μsecであった。 This compound was injected into a 2 μm-thick glass transparent electrode cell that had been subjected to an alignment treatment by rubbing, and then heated to 180 ° C. to obtain an isotropic liquid. When this liquid crystal cell was gradually cooled to 150 ° C. and a rectangular wave of ± 15 V and 1 Hz was applied under crossed Nicols, a clear switching operation was confirmed. When the spontaneous polarization was measured using the triangular wave method, it was 1.7 nC / cm 2
Met. In addition, the response speed at 110 ℃ (90% from electric field application)
The time to rise) was 200 μsec.
実施例２ （Ｒ）−４−（６′−クロロ−３′−メチルヘキシルオ
キシ）ビフェニルカルボン酸−４−ｎ−デシルオキシフ
ェニルエステルの合成 0.35gの（Ｒ）−４−（６′−クロロ−３′−メチル
ヘキシルオキシ）ビフェニルカルボン酸、0.25gの４−
ｎ−デシルオキシフェノール、0.21gのN,N′−ジシクロ
ヘキシルカルボジイミドおよび0.02gの４−ピロリジノ
ピリジンをジクロルメタン10mlに加え、実施例１と同様
の操作を行った。得られた粗生成物をヘキサン／ジクロ
ルメタン（1/1）を展開溶媒としてシリカゲルカラムを
用いて精製し、目的の（Ｒ）−４−（６′−クロロ−
３′−メチルヘキシルオキシ）ビフェニルカルボン酸−
４−ｎ−デシルオキシフェニルエステルを得た。Example 2 Synthesis of (R) -4- (6'-chloro-3'-methylhexyloxy) biphenylcarboxylic acid-4-n-decyloxyphenyl ester 0.35 g of (R) -4- (6'-chloro) -3'-methylhexyloxy) biphenylcarboxylic acid, 0.25 g of 4-
The same operation as in Example 1 was carried out by adding n-decyloxyphenol, 0.21 g of N, N'-dicyclohexylcarbodiimide and 0.02 g of 4-pyrrolidinopyridine to 10 ml of dichloromethane. The obtained crude product was purified using a silica gel column with hexane / dichloromethane (1/1) as a developing solvent to obtain the desired (R) -4- (6'-chloro-).
3'-methylhexyloxy) biphenylcarboxylic acid-
4-n-decyloxyphenyl ester 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 absorptions and was confirmed to be the target product.
この化合物を二枚のガラス板間に挟み、偏光顕微鏡に
よる相形態観察を行った結果、以下の相転移を確認し
た。 The compound was sandwiched between two glass plates, and the phase morphology was observed with a polarization microscope. As a result, the following phase transitions were confirmed.
実施例３ （Ｒ）−４−（６′−クロロ−４′−メチルオクチルオ
キシ）−安息香酸−４−ｎ−オクチルオキシビフェニル
エステルの合成 0.60gの（Ｒ）−４−（６′−クロロ−４′−メチル
オクチルオキシ）安息香酸、0.60gの４−ｎ−オクチル
オキシビフェノール、0.41gのN,N′−ジシクロヘキシル
カルボジイミドおよび0.04gの４−ピロリジノピリジン
をジクロルメタン20mlに加え、実施例１と同様の操作を
行い、目的の（Ｒ）−４−（６′−クロロ−４′−メチ
ルオキシ）−安息香酸−４−ｎ−オクチルオキシビフェ
ニルエステルを得た。 Example 3 Synthesis of (R) -4- (6'-chloro-4'-methyloctyloxy) -benzoic acid-4-n-octyloxybiphenyl ester 0.60 g of (R) -4- (6'-chloro) -4'-Methyloctyloxy) benzoic acid, 0.60 g of 4-n-octyloxybiphenol, 0.41 g of N, N'-dicyclohexylcarbodiimide and 0.04 g of 4-pyrrolidinopyridine were added to 20 ml of dichloromethane, Example 1 The same operation as above was performed to obtain the desired (R) -4- (6'-chloro-4'-methyloxy) -benzoic acid-4-n-octyloxybiphenyl ester.
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 absorptions and was confirmed to be the target product.
この化合物を二枚のガラス板間に挟み、偏光顕微鏡に
よる相形態観察を行った結果、以下の相転移を確認し
た。 The compound was sandwiched between two glass plates, and the phase morphology was observed with a polarization microscope. As a result, the following phase transitions were confirmed.
この化合物を、ラビングにより配向処理を施した厚さ
２μｍのガラス透明電極セルに注入した後に、180℃に
加熱して等方性液体とした。この液晶セルを100℃まで
徐冷し、直交ニコル下で±15V、1Hzの矩形波を印加した
ところ、明瞭なスイッチング動作が確認された。その時
の応答速度は350μsecであった。三角波法を用いて自発
分極した測定したところ、12.8nC/cm2であった。 This compound was injected into a 2 μm-thick glass transparent electrode cell that had been subjected to an alignment treatment by rubbing, and then heated to 180 ° C. to obtain an isotropic liquid. When this liquid crystal cell was gradually cooled to 100 ° C. and a rectangular wave of ± 15 V, 1 Hz was applied under crossed Nicols, a clear switching operation was confirmed. The response speed at that time was 350 μsec. It was 12.8 nC / cm 2 as measured by spontaneous polarization using the triangular wave method.
実施例４ （Ｒ）−４−ｎ−ヘキシルオキシ安息香酸−４−（６′
−クロロ−４′−メチルヘキシルオキシ）−ビフェニル
エステルの合成 0.44gのｎ−ヘキシルオキシ安息香酸、0.64gの（Ｒ）
−４−（６′−クロロ−４′−メチルヘキシルオキシ）
ビフェノール、0.41gのN,N′−ジシクロヘキシルシルカ
ルボジイミドおよび0.04gの４−ピロリジノピリジンを
ジクロルメタン20mlに加え、実施例１と全く同様の操作
を行い、目的の（Ｒ）−４−ｎ−ヘキシルオキシ安息香
酸−４−（６′−クロロ−４′−メチルヘキシルオキ
シ）ビフェニルエステルを得た。Example 4 (R) -4-n-hexyloxybenzoic acid-4- (6 ′)
-Chloro-4'-methylhexyloxy) -biphenyl ester synthesis 0.44 g n-hexyloxybenzoic acid, 0.64 g (R)
-4- (6'-chloro-4'-methylhexyloxy)
Biphenol, 0.41 g of N, N'-dicyclohexylsylcarbodiimide and 0.04 g of 4-pyrrolidinopyridine were added to 20 ml of dichloromethane, and the same operation as in Example 1 was performed to obtain the desired (R) -4-n-hexyl Oxybenzoic acid-4- (6'-chloro-4'-methylhexyloxy) biphenyl ester 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 absorptions and was confirmed to be the target product.
この化合物を二枚のガラス板間に挟み、偏光顕微鏡に
よる相形態観察を行った結果、以下の相転移を確認し
た。 The compound was sandwiched between two glass plates, and the phase morphology was observed with a polarization microscope. As a result, the following phase transitions were confirmed.
この化合物群は、高温で広いスメクチック相を示し、
SmC*相の自発分極は大きいので強誘電性液晶の一成分と
して用いるのに適している。 This group of compounds exhibits a broad smectic phase at high temperatures,
Since the SmC * phase has a large spontaneous polarization, it is suitable for use as a component of a ferroelectric liquid crystal.
Claims (1)
エステル化合物。 （式中、Ｒは炭素原子数１ないし18の直鎖アルキル基を
示し、Ｒ′は塩素含有アルキル基を示し、Ｘは−CO−Ｏ
−または−Ｏ−CO−を示し、Ｐおよびｑはそれぞれ０ま
たは１を示し、ｐ＋ｑ＝１を示し、ｎは２〜５を示し、
＊は不斉炭素原子を示す。）1. An optically active biphenyl ester compound represented by the following general formula. (In the formula, R represents a linear alkyl group having 1 to 18 carbon atoms, R ′ represents a chlorine-containing alkyl group, and X represents —CO—O.
-Or -O-CO-, P and q each represent 0 or 1, p + q = 1, n represents 2 to 5,
* Indicates an asymmetric carbon atom. )
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP222688A JPH0830037B2 (en) | 1988-01-08 | 1988-01-08 | Optically active biphenyl ester compound |
| US07/242,177 US4959173A (en) | 1987-09-29 | 1988-09-08 | Optically active ester compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP222688A JPH0830037B2 (en) | 1988-01-08 | 1988-01-08 | Optically active biphenyl ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01180858A JPH01180858A (en) | 1989-07-18 |
| JPH0830037B2 true JPH0830037B2 (en) | 1996-03-27 |
Family
ID=11523442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP222688A Expired - Lifetime JPH0830037B2 (en) | 1987-09-29 | 1988-01-08 | Optically active biphenyl ester compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0830037B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4755266B2 (en) * | 2009-02-23 | 2011-08-24 | 公益財団法人鉄道総合技術研究所 | Conductive structure |
-
1988
- 1988-01-08 JP JP222688A patent/JPH0830037B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01180858A (en) | 1989-07-18 |
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