JPS6033822B2 - Novel diphenyl ester exhibiting liquid crystal phase - Google Patents
Novel diphenyl ester exhibiting liquid crystal phaseInfo
- Publication number
- JPS6033822B2 JPS6033822B2 JP15891583A JP15891583A JPS6033822B2 JP S6033822 B2 JPS6033822 B2 JP S6033822B2 JP 15891583 A JP15891583 A JP 15891583A JP 15891583 A JP15891583 A JP 15891583A JP S6033822 B2 JPS6033822 B2 JP S6033822B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- diphenyl ester
- crystal phase
- exhibiting liquid
- synthesis
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【発明の詳細な説明】
本発明は、液晶相を示す新規ジフェニルェステルに関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel diphenyl esters exhibiting a liquid crystalline phase.
これら化合物は、単独または混合物として液晶相を示す
ことができ、この液晶相は実際には、ネマチック相と一
以上のスメクチック相のいずれか、あるいはネマチツク
相と一以上のスメクチック相の双方であり得る。These compounds, alone or as a mixture, can exhibit a liquid crystal phase, which liquid crystal phase can actually be either a nematic phase and one or more smectic phases, or both a nematic phase and one or more smectic phases. .
一般式
（ここでＲ＝Ｃ６日，３、Ｃ７日．５またはＣ８日，７
０：Ｘ＝ＢｒまたはＣＮ）で表わされるジフェニルェス
テルが提供される。General formula (where R=C6 days, 3, C7 days.5 or C8 days, 7
0:X=Br or CN) is provided.
一般的製造法
以下の中間体を合成する：
１ ４ーヒドロキシー４′ーアルキルジフエニル２ ４
ーアルコキシー３ーブロモベンゾイルク。General Preparation Method The following intermediates are synthesized: 1 4-Hydroxy-4'-alkyldiphenyl 2 4
-Alkoxy 3-bromobenzoylc.
ライド。上記二中間体から臭素化合物を合成し、次いで
臭素化合物からシアノ化合物を合成する。Ride. A bromine compound is synthesized from the above two intermediates, and then a cyano compound is synthesized from the bromine compound.
最初の中間体の合成は、関連出願（特関昭５３一１４８
２５号）のそれとは異なり、著しく高い収率を与える。The synthesis of the first intermediate was carried out in the related patent application (Spec.
No. 25) gives significantly higher yields.
ａ ４ーアルコキシカルボニルー４′ーアル力／イルジ
フェニルの合成ここでＲはアルキル基である。a Synthesis of 4-alkoxycarbonyl-4'-alkyl/yldiphenyl where R is an alkyl group.
ｂ ４ーヒドロキシー４′ーアルキルジフエニルの合成
基−ＣＨ２一Ｒは、Ｒ２＝ＣｍＨ２ｍ＋，（ｍは１〜１
０の整数）に相当する。b The synthetic group -CH2-R of 4-hydroxy-4'-alkyldiphenyl is R2=CmH2m+, (m is 1 to 1
(an integer of 0).
第２の中間体の合成は、上記出願明細書で開示したもの
と同一である。The synthesis of the second intermediate is identical to that disclosed in the above application.
三つのイヒ学反応を含むその方法を再記すれば次の通り
である。ｃ ４−アルコキシー３−フロモ安息香酸の合
成ここでＲ，はＣｎＨ２ｎ十，０。The method, including three Ichological reactions, is restated as follows. c Synthesis of 4-alkoxy 3-furomobenzoic acid where R, is CnH2n10,0.
ｄ ４−アルキルー３ープロモ安息香酸の合成ここでＲ
，はＣｎＨ２ｎ＋，ｏｅ ４−アルコキシ（またはアル
キ）−３−ブロモベンゾィルクロラィドの合成ここでＲ
，はアルコキシ基またはアルキル基のいずれかである。d Synthesis of 4-alkyl-3-promobenzoic acid where R
, is CnH2n+,oe Synthesis of 4-alkoxy (or alkyl)-3-bromobenzoyl chloride where R
, is either an alkoxy group or an alkyl group.
次いで臭素化合物を以下の反応により合成する。Next, a bromine compound is synthesized by the following reaction.
最後に、シアノ化合物を次の反応により合成する。Finally, a cyano compound is synthesized by the following reaction.
ここでＤＭＦはジメチルホルムアミド（溶媒）を表わす
合成例反応｛ａーの例：４−へキシルオキシカルボニル
ー４′ーヘキサノイルジフェニルの合成。Here, DMF represents dimethylformamide (solvent) Synthesis Example Reaction {Example a-: Synthesis of 4-hexyloxycarbonyl-4'-hexanoyldiphenyl.
乳夕（０．２モル）の４−ヒドロキシジフヱニルを１０
０の‘の二硫化炭素に加える。10% of 4-hydroxydiphenyl from milk powder (0.2 mol)
Add to 0' of carbon disulfide.
溶液を鷹拝し、球．５夕（０．４モル）の塩化アルミニ
ウムを５時間にわたって加える。還流温度まで加熱後、
５４夕（０．４モル）の塩化へキサノイルを１時間にわ
たって加える。次いで還流下で加熱を３時間継続する。
次いで溶液を冷却し、氷２００２および濃塩酸１００泌
の混合物に注ぎ、ベンゼンで抽出する。Pour the solution into a ball. 5 ml (0.4 mol) of aluminum chloride are added over 5 hours. After heating to reflux temperature,
54 g (0.4 mol) of hexanoyl chloride are added over 1 hour. Heating is then continued under reflux for 3 hours.
The solution is then cooled, poured onto a mixture of 2002 g of ice and 100 g of concentrated hydrochloric acid, and extracted with benzene.
ベンゼン抽出物を、次いで脱イオン水で洗い、硫酸マグ
ネシウム上で乾燥する。The benzene extract is then washed with deionized water and dried over magnesium sulfate.
溶媒を留去し、７３．６夕の混合物を回収し、ベンゼン
／エタノール（５０／５０）溶液２００ｃｃから再結晶
する。The solvent is distilled off and the mixture is recovered and recrystallized from 200 cc of benzene/ethanol (50/50) solution.
５２．５夕の純生成物が得られ、これは収率７２％に相
当する。52.5 hours of pure product were obtained, corresponding to a yield of 72%.
反応‘ｂ’の例：４ーヒドロキシー４′ヘキシルジフェ
ニルの合成４５０夕（８モル）の水酸化カリウムおよび
４５．７夕（１．２５モル）の４−へキシルオキシカル
ボニルー４′ーヘキサノイルジフェニルを、１．２その
ジェチレングリコールと２８２夕（９モル）のヒドラジ
ン水化物との溶液に加える。Example of reaction 'b': Synthesis of 4-hydroxy-4'-hexyldiphenyl 450 m (8 mol) of potassium hydroxide and 45.7 m (1.25 mol) of 4-hexyloxycarbonyl-4'-hexanoyldiphenyl is added to a solution of 1.2 gethylene glycol and 282 g (9 moles) of hydrazine hydrate.
溶液を還流下に２時間加熱し、その後物質（ｍａｓｓ）
温度が２２８℃となるまで水および過剰のヒドラジンを
蒸留する。溶液を１００℃まで放置冷却し、次いで６そ
の脱イオン水に注ぐ。１時間燈梓後、得られる溶液を濃
塩酸によりｐＨＩ〜２の酸性とする。The solution was heated under reflux for 2 hours, then mass
Water and excess hydrazine are distilled off until the temperature is 228°C. The solution is allowed to cool to 100° C. and then poured into deionized water. After heating for 1 hour, the resulting solution is made acidic to pH ˜2 with concentrated hydrochloric acid.
生成物は析出し、これをエーテルで抽出する。抽出物を
脱イオン水で洗浄し、硫酸マグネシウム上で乾燥する。The product precipitates out and is extracted with ether. The extracts are washed with deionized water and dried over magnesium sulfate.
ェ−テルを留去し、残留生成物を６００ｃｃのへキサン
から再結晶する。The ether is distilled off and the residual product is recrystallized from 600 cc of hexane.
２８．９夕の純生成物が得られ、これは収率９１％に相
当する。28.9 hours of pure product was obtained, corresponding to a yield of 91%.
臭素化合物の合成例：ｐ−へキシルジフェニルー３ーブ
ロモー４−へブチルベンゾエート
２．払夕（０．０１モル）の４ーヒドロキシー４′ーヘ
キシルジフェニルを２０叫のピリジンに溶解する。Synthesis example of bromine compound: p-hexyldiphenyl-3-bromo-4-hebutylbenzoate2. Dissolve 0.01 mole of 4-hydroxy-4'-hexyldiphenyl in 20 parts of pyridine.
３．１７５夕（０．０１モル）の３−フロモー４ーヘプ
チルベンゾイルクロライドを加え、次いで室温で３時間
蝿拝する。Add 3.175 g (0.01 mol) of 3-furomo-4-heptylbenzoyl chloride and then stir at room temperature for 3 hours.
溶液を、氷７０夕と濃硫酸８ｃｃとの混合物に注ぐ。縄
梓後、反応混合物をベンゼンで抽出する。５．７夕の粗
生成物が得られ、シリカ済でのクロマトグラフィ−によ
り精製し、次いでエタノールから再結晶して３．５夕の
純生成物を得る。Pour the solution into a mixture of 70 g of ice and 8 cc of concentrated sulfuric acid. After rinsing, the reaction mixture is extracted with benzene. A crude product of 5.7% is obtained, purified by chromatography on silica and then recrystallized from ethanol to give a pure product of 3.5%.
これは収率６５％に相当する。シアノ化合物の合成例：
ｐ−へキシルジフェニルー３ーシアノー４一へプチルベ
ンゾェートの合成
２．６５夕（５×１０‐３モル）のｐーヘキシルジフエ
ニル一３ーフロモ−４ーヘプチルベンゾヱートおよび０
．６夕（６．７×１０‐３モル）の塩化第一銅を１０の
‘のジメチルフオルムアミドに加える。This corresponds to a yield of 65%. Synthesis example of cyano compound:
Synthesis of p-hexyldiphenyl-3-cyano-4-heptylbenzoate 2.65 units (5 x 10-3 mol) of p-hexyldiphenyl-3-furomo-4-heptylbenzoate and 0
．． Six cups (6.7 x 10-3 moles) of cuprous chloride are added to 10' of dimethylformamide.
溶液を、還流下に７．虫時間加熱後、冷却し、脱イオン
水６０ｃｃとェヂレンジアミン５．５ｃｃの混合物中に
注ぐ。濃枠後、溶液をエーテルで抽出すると、２．２夕
の粗生成物が得られ、これをシリカ塔でのクロマトグラ
フィ−により精製し、更にエタノールから再結晶して１
．６夕の純生成物を得る。これは収率６６％に相当する
。化合物および混合物の性質
記載の理解を容易とするために、以下で次の記号を使用
する。7. Bring the solution under reflux. After heating for an hour, it is cooled and poured into a mixture of 60 cc of deionized water and 5.5 cc of ethylenediamine. After a concentrated period of time, the solution was extracted with ether to give a crude product of 2.2 mL, which was purified by chromatography on a silica column and further recrystallized from ethanol to yield 1.
．． 6 hours of pure product is obtained. This corresponds to a yield of 66%. To facilitate the understanding of the description of the properties of compounds and mixtures, the following symbols are used below:
Ｋ ：結晶相
Ｓ＾：スメクチツク相Ａ
Ｓｃ：スメクチツク相Ｃ
Ｎ ：ネマチツク相
１ ： 等方液相
ｆ刊：２４ｑｏにおける「平行」誘電率
ごＰ班ｐ：２４ｑｏにおける「直交」誘電率ごａ ：４
議電異方性、すなわち、ごＰａｒ−ごＰａｒｐ第１表中
において相記号の間に記した数字は、℃で表わした転移
温度を示す。K: Crystalline phase S^: Smectic phase A Sc: Smectic phase C N: Nematic phase 1: Isotropic liquid phase 4
The numbers written between the phase symbols in Table 1 indicate the transition temperature in degrees Celsius.
第 １ 表
本発明の化合物は、なかでも以下の電気光学装置におい
て使用される。Table 1 The compounds of the invention are used inter alia in the following electro-optical devices:
−光の動的散乱に基づく表示系。-Display system based on dynamic scattering of light.
これは広い温度範囲と負の誘電異万性を要する。特にネ
マチツク液晶と本発明の化合物の混合物は、これらの一
つの性質を示す。−液晶の誘電異万性が、液晶中の電界
が数千ないし数百ヘルツ程度の周波数であるかどうかに
よって、多少顕著になる性質を利用する電気光学装置。This requires a wide temperature range and negative dielectric anisotropy. In particular, mixtures of nematic liquid crystals and compounds of the invention exhibit one of these properties. - An electro-optical device that utilizes the property that the dielectric anisotropy of liquid crystal becomes more or less pronounced depending on whether the electric field in the liquid crystal has a frequency of several thousand to several hundred hertz.
−スメクチック相を有する本発明の化合物（表１の化合
物Ｂ，Ｄ，Ｆ）の場合のいわゆる電気効果メモリー型表
示系あるいは熱光学メモリー型表示系。- So-called electrical effect memory type display systems or thermo-optic memory type display systems in the case of the compounds of the invention having a smectic phase (compounds B, D, F of Table 1).
Claims (1)
たはＣ＿８Ｈ＿１＿７Ｏ：Ｘ＝ＢｒまたはＣＮ）で表わ
される、少なくとも一の液晶相を示すジフエニルエステ
ル。 ２ 一般式 ▲数式、化学式、表等があります▼ （ここでＲ＝Ｃ＿６Ｈ＿１＿３、Ｃ＿７Ｈ＿１＿５ま
たはＣ＿８Ｈ＿１＿７Ｏ：Ｘ＝ＢｒまたはＣＮ）で表わ
されるジフエニルエステルからなる液晶物質。 ３ 一般式 ▲数式、化学式、表等があります▼ で表わされる化合物を添加剤として含有する特許請求の
範囲第２項記載の液晶物質。[Claims] 1. A diphenyl ester that exhibits at least one liquid crystal phase and is represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R = C_6H_1_3, C_7H_1_5 or C_8H_1_7O: . 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R = C_6H_1_3, C_7H_1_5 or C_8H_1_7O: X = Br or CN) A liquid crystal material consisting of diphenyl ester. 3. The liquid crystal substance according to claim 2, which contains a compound represented by the general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ as an additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7801880 | 1978-01-24 | ||
| FR7801880A FR2415133A2 (en) | 1978-01-24 | 1978-01-24 | NEW FAMILY OF LIQUID CRYSTALS WITH LARGE NEGATIVE DIELECTRIC ANISOTROPY, AND DEVICES USING SUCH CRYSTALS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5962550A JPS5962550A (en) | 1984-04-10 |
| JPS6033822B2 true JPS6033822B2 (en) | 1985-08-05 |
Family
ID=9203764
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP698479A Pending JPS5536464A (en) | 1978-01-24 | 1979-01-24 | Novel diphenylester showing liquid crystal phase |
| JP15891583A Expired JPS6033822B2 (en) | 1978-01-24 | 1983-08-30 | Novel diphenyl ester exhibiting liquid crystal phase |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP698479A Pending JPS5536464A (en) | 1978-01-24 | 1979-01-24 | Novel diphenylester showing liquid crystal phase |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JPS5536464A (en) |
| DE (1) | DE2902490A1 (en) |
| FR (1) | FR2415133A2 (en) |
| GB (1) | GB2015510B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101431674B1 (en) * | 2013-01-07 | 2014-08-20 | (주)플로닉스 | Rubber diaphragm having fluoropolymer coat layer and Method for manufacturing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2939782A1 (en) * | 1979-09-07 | 1981-04-02 | BBC AG Brown, Boveri & Cie., Baden, Aargau | Anisotropic cpds. with three aromatic rings and polarising side gps. - have high negative dielectric constant anisotropy, useful in liquid crystal compsn. |
| JPS56122334A (en) * | 1980-02-29 | 1981-09-25 | Chisso Corp | Liquid crystal 4-alkylcyclohexyl ester |
| US4670581A (en) * | 1983-01-27 | 1987-06-02 | Sugai Chemical Industry Co., Ltd. | Biphenyl compounds and process for producing the same |
| FR2561657B1 (en) * | 1984-03-20 | 1988-02-19 | Thomson Csf | PROCESS FOR OBTAINING A SMECTIC LIQUID CRYSTAL C CHIRAL FERROELECTRIC LIQUID CRYSTAL OBTAINED BY THIS METHOD AND VISUALIZATION DEVICE USING THE LIQUID CRYSTAL |
-
1978
- 1978-01-24 FR FR7801880A patent/FR2415133A2/en active Granted
-
1979
- 1979-01-23 DE DE19792902490 patent/DE2902490A1/en not_active Ceased
- 1979-01-24 JP JP698479A patent/JPS5536464A/en active Pending
- 1979-01-24 GB GB7902465A patent/GB2015510B/en not_active Expired
-
1983
- 1983-08-30 JP JP15891583A patent/JPS6033822B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101431674B1 (en) * | 2013-01-07 | 2014-08-20 | (주)플로닉스 | Rubber diaphragm having fluoropolymer coat layer and Method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2015510A (en) | 1979-09-12 |
| DE2902490A1 (en) | 1979-07-26 |
| JPS5536464A (en) | 1980-03-14 |
| FR2415133A2 (en) | 1979-08-17 |
| GB2015510B (en) | 1982-09-15 |
| FR2415133B2 (en) | 1980-08-22 |
| JPS5962550A (en) | 1984-04-10 |
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