JPS63216849A - Fluorine-containing liquid crystal compound - Google Patents
Fluorine-containing liquid crystal compoundInfo
- Publication number
- JPS63216849A JPS63216849A JP5127387A JP5127387A JPS63216849A JP S63216849 A JPS63216849 A JP S63216849A JP 5127387 A JP5127387 A JP 5127387A JP 5127387 A JP5127387 A JP 5127387A JP S63216849 A JPS63216849 A JP S63216849A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- fluoro
- phase
- synthesis example
- compound
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 6
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 30
- 239000011737 fluorine Substances 0.000 title description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 2
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002989 phenols Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- MPJOJCZVGBOVOV-UHFFFAOYSA-N 2-phenylbenzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1C1=CC=CC=C1 MPJOJCZVGBOVOV-UHFFFAOYSA-N 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 49
- 230000015572 biosynthetic process Effects 0.000 description 38
- 238000003786 synthesis reaction Methods 0.000 description 38
- 230000004044 response Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- -1 DOBAMBG Chemical class 0.000 description 5
- 239000004990 Smectic liquid crystal Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- NXWTWYULZRDBSA-UHFFFAOYSA-N 2-fluoro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1F NXWTWYULZRDBSA-UHFFFAOYSA-N 0.000 description 2
- OPRUTERQSYYYFE-UHFFFAOYSA-N 2-fluoro-4-phenylmethoxyphenol Chemical compound C1=C(F)C(O)=CC=C1OCC1=CC=CC=C1 OPRUTERQSYYYFE-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- REIVHYDACHXPNH-UHFFFAOYSA-N 2-fluoro-4-hydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C(F)=C1 REIVHYDACHXPNH-UHFFFAOYSA-N 0.000 description 1
- IUSDEKNMCOUBEE-UHFFFAOYSA-N 3-fluoro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(F)=C1 IUSDEKNMCOUBEE-UHFFFAOYSA-N 0.000 description 1
- HPZPFOIOJPBNKK-UHFFFAOYSA-N 4-(4-dodecoxyphenyl)benzoic acid Chemical compound C1=CC(OCCCCCCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1 HPZPFOIOJPBNKK-UHFFFAOYSA-N 0.000 description 1
- YNBBQLUKHHSKPW-UHFFFAOYSA-N 4-(4-octoxyphenyl)benzoic acid Chemical compound C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1 YNBBQLUKHHSKPW-UHFFFAOYSA-N 0.000 description 1
- HXBKPYIEQLLNBK-UHFFFAOYSA-N 4-(4-octylphenyl)benzoic acid Chemical compound C1=CC(CCCCCCCC)=CC=C1C1=CC=C(C(O)=O)C=C1 HXBKPYIEQLLNBK-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- JGWRHCDKWLRLPN-UHFFFAOYSA-N CC(COC(C1=CC=CC=C1)=O)CCCC(C)C Chemical compound CC(COC(C1=CC=CC=C1)=O)CCCC(C)C JGWRHCDKWLRLPN-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、複数の分岐を持つ光学活性基を導入した、画
像表示に於ける高速応答性を示し、且つメモリー性の良
好な画像表示素子の作成に有効な液晶性化合物に関する
。従って、本発明は液晶テレビジョン受像機などに使用
される画像表示装置あるいは光プリンターヘッドなどに
利用される。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an image display element that exhibits high-speed response in image display and has good memory performance, into which an optically active group having multiple branches is introduced. This invention relates to a liquid crystalline compound effective for the production of. Therefore, the present invention is applicable to image display devices used in liquid crystal television receivers, optical printer heads, and the like.
［従来の技術］
画像表示素子の一つとして、現在液晶は広く使用されて
きている。液晶材料を用いた一般的な画像表示方式とし
ては、涙じれネマチック型（ＴＮ型）及びゲスト−ホス
ト型（Ｇ−Ｈ型）が広く採用されているが、いずれもネ
マチック液晶を利用しており、他の画像表示材料である
ＣＲＴ、プラズマディスプレー、エレクトロルミネッセ
ンスディスプレーなどと比べて応答速度が遅いのが現実
である。[Prior Art] Liquid crystals are currently widely used as one of the image display elements. As general image display methods using liquid crystal materials, the teardrop nematic type (TN type) and guest-host type (G-H type) are widely adopted, but both use nematic liquid crystals. The reality is that the response speed is slower than that of other image display materials such as CRT, plasma display, and electroluminescent display.
しかし、液晶による画像表示は、受光型の表示であるこ
とから、発光型ディスプレーと比べ眼の疲労が少なく、
また、消費電力も少ないなどの長所をもっている。近年
、更に高密度で大型のディスプレーへのニーズが高まっ
ていることから、薄型で軽量のディスプレーを構成しつ
る液晶表示素子の応答の高速化が益々求められている。However, since LCD image display is a light-receiving display, it causes less eye fatigue compared to light-emitting displays.
It also has advantages such as low power consumption. In recent years, as the need for higher density and larger displays has increased, there has been an increasing demand for faster response of liquid crystal display elements that constitute thin and lightweight displays.
こうした高速の応答性を示す液晶材料として、近頃、強
誘電性液晶が開発され、その速い光スイツチング現象を
利用した画像表示装置が提案されている。Ferroelectric liquid crystals have recently been developed as liquid crystal materials exhibiting such high-speed response, and image display devices have been proposed that utilize the fast light switching phenomenon of ferroelectric liquid crystals.
強誘電性液晶は、Ｒ，Ｂ、 Ｍｅｙｅｒらにより１９７
５年に報告され（Ｊ、 ｄｅ Ｐｈｙｓ、 Ｌｅｔｔ、
、 ３Ｂ、 ６９．１９７５）、液晶分類上、カイラル
スメクチックＣ相（ｓ ｃ”相）、カイラルスメクチッ
クＦ相（Ｓｒ”相）、カイラルスメクチック■相（Ｓビ
相）あるいはカイラルスメクチックＣ相（ｓ ａ’相）
などに属するといわれている。これらの強誘電性液晶相
の中で実用上量も可能性が高い液晶相は、その相構造及
び相構造に起因する粘度の点からＳＣ“相と考えられて
おり、最も高速に応答する。事実、Ｎ、 Ａ。Ferroelectric liquid crystals were described by R. B. Meyer et al. in 197
reported in 1995 (J, de Phys, Lett,
, 3B, 69.1975), in terms of liquid crystal classification, chiral smectic C phase (s c" phase), chiral smectic F phase (Sr" phase), chiral smectic ■ phase (S bi phase), or chiral smectic C phase (s a 'phase)
It is said that it belongs to Among these ferroelectric liquid crystal phases, the liquid crystal phase that is most likely to be present in practical quantities is considered to be the SC phase in terms of its phase structure and viscosity caused by the phase structure, and responds the fastest. Fact, N.A.
Ｃ１ａｒｋらは（Ａｐｐｌ、 Ｐｈｙｓ、 Ｌｅｔｔ、
、 ３８．８９９゜１９８０）において、この強誘電性
液晶化合物の一種でＳｒ相を示すｐ−デシルオキシベン
ジリデン−ｐ′−アミノ−２−メチルブチルシンナメー
ト（ＤＯＢＡＭＢＣと略記する）を非常に薄い薄膜セル
に入れ、マイクロセカンド・オーダーの光スイツチング
現象を観察している。強誘電性液晶（特に５ｃＩＩ相）
のこうした高速応答性を利用した液晶テレビ、光プリン
ターヘッド、非線形光学素子などのオプトエレクトロニ
クス材料への応用が既に検討され始めている。しかし、
ＤＯＢＡＭＢＧをはじめとする従来開発された強誘電性
液晶化合物は、水。C1ark et al. (Appl, Phys, Lett,
, 38.899° 1980), a very thin film of p-decyloxybenzylidene-p'-amino-2-methylbutylcinnamate (abbreviated as DOBAMBC), which is a type of ferroelectric liquid crystal compound and exhibits an Sr phase, was developed. They put it in a cell and observe the optical switching phenomenon on the microsecond order. Ferroelectric liquid crystal (especially 5cII phase)
Applications to optoelectronic materials such as liquid crystal televisions, optical printer heads, and nonlinear optical elements that take advantage of this high-speed response have already begun to be considered. but,
Previously developed ferroelectric liquid crystal compounds, including DOBAMBG, are based on water.
光などに対する化学安定性の面に難点があり、実用的で
はなかった。It had problems with chemical stability against light, etc., and was not practical.
最近、エステル系の強誘電性を示す液晶性化合物がＬｉ
ｑｕｉｄ Ｃｒｙｓｔａｌｓ ａｎｄ ０ｒｄｅｒｅｄ
Ｆｌｕｉｄｓ” ｂｙＪ、 Ｗ、 Ｇｏｏｄｂｙ ａ
ｎｄ Ｔ、 Ｍ、 Ｌｅｓｌｉｅ： Ｖｏｌ、４や、特
開昭５９−１２８３５７号、特開昭６０−３２７４８号
などに報告されているが、これらの強誘電性液晶化合物
の化学安定性については改善されたが、室温付近での応
答速度は１〜２ ｍ５ｅｃで、強誘電性液晶として実用
に耐え得るものではない。また、特開昭６１−３０５５
９号には次の含フツ素光学活性液晶性化合物を使用した
配合例を示し、印加電圧３０Ｖで９０μｓｅｃの応答速
度を示すに至っているが、印加電圧が比較的高い点から
見て実用上必ずしも好ましいとはいえない。Recently, ester-based liquid crystalline compounds exhibiting ferroelectricity have been
Quid Crystals and 0rdered
Fluids” by J, W, Goodby a
nd T, M, Leslie: Vol. 4, JP-A-59-128357, JP-A-60-32748, etc., but the chemical stability of these ferroelectric liquid crystal compounds has not been improved. However, the response speed near room temperature is 1 to 2 m5ec, which is not suitable for practical use as a ferroelectric liquid crystal. Also, JP-A-61-3055
No. 9 shows a formulation example using the following fluorine-containing optically active liquid crystal compound, and it shows a response speed of 90 μsec at an applied voltage of 30 V, but considering the relatively high applied voltage, it is not necessarily practical in practice. It cannot be said that it is desirable.
［発明が解決しようとする問題点］
かかる現状に鑑み、化学的安定性にすぐれ、単独又は他
の強誘電性液晶との混合により室温付近において安定な
Ｓｃ“相を持ち、且つ比較的低印加電圧で高速応答性に
すぐれている液晶性化合物の出現が待望されている。[Problems to be Solved by the Invention] In view of the current situation, a liquid crystal that has excellent chemical stability, has an Sc phase that is stable at around room temperature when used alone or in combination with other ferroelectric liquid crystals, and can be applied at a relatively low voltage. The emergence of liquid crystalline compounds with excellent high-speed voltage response has been eagerly awaited.
［問題点を解決するための手段］
強誘電性液晶を得るための基本的条件は、分子が光学活
性体であること、分子長軸と垂直な双極子モーメントが
存在すること及び、Ｓ♂相＋Ｓ（１′相あるいはＳ、Ｉ
Ｉ相（カイラルスメクチックＩ相）を取ることであると
考えられている。これらの条件を満足する液晶化合物を
求めて、多くの化合物が研究開発されつつあるが、いず
れの化合物も室温付近での高速応答性は充分ではない。[Means for solving the problem] The basic conditions for obtaining a ferroelectric liquid crystal are that the molecule is an optically active substance, that there is a dipole moment perpendicular to the long axis of the molecule, and that the S♂ phase is present. +S (1' phase or S, I
It is considered that the I phase (chiral smectic I phase) is formed. Many compounds are being researched and developed in search of liquid crystal compounds that satisfy these conditions, but none of these compounds have sufficient high-speed response near room temperature.
そこで、本発明者らは、光学活性基も含めて強誘電性液
晶化合物の分子構造を検討し、高速応答性を持つ液晶性
化合物について、多くの研究を続けてきた。その結果と
して、複数の分枝を持つ光学活性基を有し、コアにフッ
素置換基を有する液晶性化合物が単独または他の強誘電
性液晶性化合物と混合することにより、広い温度範囲で
安定なＳｃ“相をとり、印加電圧５０μｓｅｃ前後の高
速応答性を示す事を見出し、本発明を完成したものであ
る。Therefore, the present inventors have studied the molecular structure of ferroelectric liquid crystal compounds, including optically active groups, and have continued extensive research into liquid crystal compounds with high-speed response. As a result, liquid crystalline compounds that have optically active groups with multiple branches and a fluorine substituent in their cores are stable over a wide temperature range when used alone or in combination with other ferroelectric liquid crystalline compounds. The inventors have completed the present invention by discovering that the material has a Sc" phase and exhibits a high-speed response of approximately 50 μsec to an applied voltage.
即ち、本発明は、室温付近で高速応答性を示す一般式（
Ｉ）
（式中、Ｒは炭素数６〜１２のアルキル基又はアルコキ
シル基を示し、Ｒｏは複数の分枝を持ち、炭素数９〜１
１の不斉炭素原子を有する光学活性基を示し、Ｘ、Ｙは
どちらか一方が水素又はフッ素原子を示し、ｎはＯある
いは１である。）で表される液晶化合物を提供するもの
である。That is, the present invention provides the general formula (
I) (In the formula, R represents an alkyl group or an alkoxyl group having 6 to 12 carbon atoms, and Ro has multiple branches and has 9 to 1 carbon atoms.
It represents an optically active group having one asymmetric carbon atom, one of X and Y represents hydrogen or a fluorine atom, and n is O or 1. ) is provided.
上記一般式（Ｉ）で表される化合物において、Ｒ′″と
して特に好ましいものに２．６−ジメチルへブチル基が
ある。このようなアルキル基の使用は、特に安定したＳ
Ｃ′相の出現を観察することができ、複数の分子により
低粘化がおこり高速応答化の要因になっている。コアの
フッ素置換基は、低粘作用はそれ程大きくなくむしろ、
フッ素原子の電気陰性度により分子間に相互作用を生じ
させ、無置換の化合物に比ベピッチ幅の増大が観察され
、コントラストの大幅な改善に寄与している。特にフッ
素置換基の位置がコアの真中に近いほどその効果は大き
い。In the compound represented by the above general formula (I), 2,6-dimethylhebutyl group is particularly preferable as R'''.
The appearance of the C' phase can be observed, and the viscosity is lowered by multiple molecules, which is a factor in the faster response. The fluorine substituent in the core does not have a significant viscosity-lowering effect;
The electronegativity of fluorine atoms causes interactions between molecules, and an increase in the relative pitch width is observed in unsubstituted compounds, contributing to a significant improvement in contrast. In particular, the closer the position of the fluorine substituent is to the center of the core, the greater the effect.
一方、一般式（１）においてＲＯ−で表わされるアルコ
キシ基の中のＲは、炭素数６〜１２のアルキル基であり
、炭素数５以下、あるいは１３以上のアルキル基を導入
すると、ＳＣ′相の温度範囲が狭まるので好ましくない
。On the other hand, R in the alkoxy group represented by RO- in general formula (1) is an alkyl group having 6 to 12 carbon atoms, and when an alkyl group having 5 or less carbon atoms or 13 or more carbon atoms is introduced, the SC' phase This is not preferable because it narrows the temperature range.
なお、本発明に係る液晶性化合物は既存の強誘電性液晶
あるいは強誘電性を示さない単なるＳＣ相を経る化合物
と混合使用することによりＳｃ”相の温度範囲を拡げ、
ディスプレー等に実用可能な液晶組成物を得ることがで
きる。また、本発明に係る化合物で液晶性の乏しいもの
でも、ＳＣ相あるいはＳＣ″相を経る化合物に５〜２０
％程度加えることにより大きな自発分極を有する強誘電
性液晶組成物を得ることができる。The liquid crystal compound according to the present invention can be used in combination with existing ferroelectric liquid crystals or compounds that do not exhibit ferroelectricity and undergo a simple SC phase, thereby expanding the temperature range of the Sc'' phase.
A liquid crystal composition that can be used practically for displays etc. can be obtained. In addition, even if the compound according to the present invention has poor liquid crystallinity, the compound that passes through the SC phase or SC'' phase has a 5 to 20
%, a ferroelectric liquid crystal composition having a large spontaneous polarization can be obtained.
本液晶性化合物の一般的製造方法を以下にＮ単にのべる
。A general method for producing the present liquid crystal compound will be briefly described below.
置換フェノール部 の合成
置換フェノールエーテルはＡ、 Ｅ、 Ｆｅｉｒｉｎｇ
、 Ｊ。Synthesis of substituted phenol moiety Substituted phenol ethers are A, E, Feiring.
, J.
Ｏｒｇ、 Ｃｈｅｆｆｌ、、 ４０．２５４．１９７５
記載の方法に従い、２−フルオロハイドロキノンを原料
としてフッ素置換位置の異なった化合物（ＩＩ −ａ
）並びに（■−ｂ）を合成した。また、置換フェノール
エステル（ＩＩ −Ｃ）の化合物は、Ｊ、 Ｔ、 Ｍｉ
ｎｏｒ、 Ｊ、 Ｏｒｇ、Ｃｈｅ＋＋、、 １７．１４
２５．１’１５２記載の方法に従い、３−フルオロ−４
−ヒドロキシ安息香酸を原料として光学活性アルコール
と硫酸触媒によるエステル化反応により合成した。同じ
＜（１１−ｄ）の化合物は３−フルオロ−４−シアノフ
ェノールを加水分解して得た２−フルオロ−４−ヒドロ
キシ安息香酸を原料として合成した。以下にその工程を
略記する。Org, Cheffl, 40.254.1975
According to the described method, compounds with different fluorine substitution positions (II-a
) and (■-b) were synthesized. Moreover, the compound of substituted phenol ester (II-C) is J, T, Mi
nor, J, Org, Che++,, 17.14
According to the method described in 25.1'152, 3-fluoro-4
-Synthesized using hydroxybenzoic acid as a raw material through an esterification reaction using an optically active alcohol and a sulfuric acid catalyst. The same compound <(11-d) was synthesized using 2-fluoro-4-hydroxybenzoic acid obtained by hydrolyzing 3-fluoro-4-cyanophenol as a raw material. The process is abbreviated below.
一般式（１）の化合物は、置換ビフェニルカルボン酸ク
ロライドと前記の置換フェノール部分［（ＩＩ−ａ）〜
（ｏ−ｄ）］の化合物をピリジンのごとき塩基性触媒を
用いて反応せしめることにより合成した。以下にその工
程を略記する。The compound of general formula (1) comprises a substituted biphenylcarboxylic acid chloride and the substituted phenol moiety [(II-a) to
(od)] was synthesized by reacting the compound using a basic catalyst such as pyridine. The process is abbreviated below.
一般式（りで表される液晶性化合物の代表例を次に例示
する。Representative examples of liquid crystalline compounds represented by the general formula (R) are illustrated below.
比ＣａＨ，７０母舎ｃｏｏ−づ一〇＋
Ｆ
１２、 ＣｓＨ＋ｔＯ賛ｃｏｏ４ ｏへ早汰１３、 Ｃ
８Ｈ１７０号合ｃｏｏｎ ｃｏｏグ乃′１４、 ＣａＨ
１７０＄Ｃ００薔ｃｏｏ八ｉ大１５、 （：１２Ｈ２Ｂ
Ｏ畷Ｈ）ｃｏｏ４ ｃｏｏ八トへ１６、 Ｃｌ５ＤＩ
？号舎ｃｏｏ４ ｏ年穿１７、 Ｃ５Ｈ１０号÷ｃｏ
ｏ４ ｏグ穿１８、 Ｃ６Ｈ，ベパ）Ｏｃｏｏ４０八
し人１９、 Ｃｌ０８２１号÷ｃｏｏ４ｃｏｏ年穿２０
、 ＣａＨｔｔ号÷ｃｏｏ４ｃｏｏんし仄［実施例］
以下に合成例、実施例及び応用例を以て本発明を更に具
体的に説明する。ratio CaH, 70 main building coo-zu 10 + F 12, CsH + tO support coo4 o to Hayata 13, C
8H170 Coon Coo Guno'14, CaH
170$C00 薔 coo 8i large 15, (:12H2B
Onawate H) coo4 coo eight to 16, Cl5DI
? No.sha coo4 o year 17, C5H10 ÷co
o4 ogubo 18, C6H, Bepa) Ocoo40 eight people 19, Cl0821 ÷ coo4coo year 20
, CaHtt ÷ coo 4 coon 组 [Examples] The present invention will be explained in more detail below using synthesis examples, examples, and application examples.
合成例１
２−フルオロ−４−（２，６−シメチルヘプチルオキシ
フェノールの合成
２．６−シメチルヘブタノール１４．４ｇ、ピリジン１
１．８ｇ及びトルエン３０ｍｉの混合物を１５〜２０℃
に冷却シ、攪拌下にＰ−トルエンスルホニルクロライド
を数回に分けて投入した。その後、室温にて３時間反応
を続け、内容物を水に注いだ。分液後トルエン層を水洗
し、濃縮して粗製の２．６−ジメチルへブチル−ｐ−ト
ルエンスルホネート２９．０ｇを得た。Synthesis Example 1 Synthesis of 2-fluoro-4-(2,6-dimethylheptyloxyphenol) 2.6-dimethylhebutanol 14.4g, pyridine 1
A mixture of 1.8 g and 30 mi of toluene was heated to 15-20°C.
After cooling, P-toluenesulfonyl chloride was added in several portions while stirring. Thereafter, the reaction was continued for 3 hours at room temperature, and the contents were poured into water. After separation, the toluene layer was washed with water and concentrated to obtain 29.0 g of crude 2,6-dimethylhebutyl-p-toluenesulfonate.
２−フルオロ−１，４−ハイドロキノン１２．８ｇ 。12.8 g of 2-fluoro-1,4-hydroquinone.
８５％水酸化カリウム９．９ｇ、水１５ｍｊ＋及びエタ
ノール１５０ｍＪの混合物に２，６−ジメチルへブチル
−ｐ−トルエンスルホネート２９ｇを滴下し、滴下終了
後１７時間遠流した。反応終了後、内容物を水にあけ、
トルエン１００１で抽出した。トルエン層を分離し、水
洗後濃縮して粗生成物２５．６ｇを得た。これをクロロ
ホルムを溶出剤としてシリカゲルカラムクロマトグラフ
ィーにより分離し、淡黄色の油、２−フルオロ−４−（
２，６−ジメチルへブチルオキシ）フェノール１１．６
ｇを得た。29 g of 2,6-dimethylhebutyl-p-toluenesulfonate was added dropwise to a mixture of 9.9 g of 85% potassium hydroxide, 15 mJ+ of water, and 150 mJ of ethanol, and the mixture was subjected to distant flow for 17 hours after the completion of the dropwise addition. After the reaction is complete, pour the contents into water,
Extracted with toluene 1001. The toluene layer was separated, washed with water, and concentrated to obtain 25.6 g of a crude product. This was separated by silica gel column chromatography using chloroform as the eluent, resulting in a pale yellow oil, 2-fluoro-4-(
2,6-dimethylhebutyloxy)phenol 11.6
I got g.
合成例２
４−（４′−ｎ−オクチルオキシビフェニル−４′−カ
ルボニルオキシ）−３−フルオロフェニル−２，６−ジ
メチルへブチルエーテルの合成４’−ｎ−オクチルオキ
シビフェニル−４−カルボン酸９．６２ ｇに塩化チオ
ニル２０１を加え３時間速流したのち濃縮し、７０ＩＩ
Ｉｉ！のトルエンに溶解し、酸クロライドートルエン溶
液を調製した。２−フルオロ−４−（２，６−ジメチル
へブチルオキシ）フェノール７．５ｇ、ピリジン３．５
ｇをトルエン８０ｍＲに溶解し、これに前記酸クロライ
ドートルエン溶液を滴下し、室温にて１５時間攪拌した
。反応終了後、水洗し、硫酸マグネシウムで乾燥し濃縮
した。得られた粗結晶をクロロホルムを溶出剤としてシ
リカゲルカラムクロマトグラフィーにより分離し、エタ
ノールより再結晶して７．３ｇの４−（４″−ｎ−オク
チルオキシビフェニル−４′−カルボニルオキシ）−３
−フルオロフェニル−２，６−ジメチルへブチルエーテ
ルを得た。Synthesis Example 2 Synthesis of 4-(4'-n-octyloxybiphenyl-4'-carbonyloxy)-3-fluorophenyl-2,6-dimethylhebutyl ether 4'-n-octyloxybiphenyl-4-carboxylic acid 9 Thionyl chloride 201 was added to .62 g, flowed at high speed for 3 hours, concentrated, and 70II
Ii! was dissolved in toluene to prepare an acid chloride toluene solution. 2-fluoro-4-(2,6-dimethylhebutyloxy)phenol 7.5g, pyridine 3.5g
g was dissolved in 80 mR of toluene, and the acid chloride toluene solution was added dropwise thereto, followed by stirring at room temperature for 15 hours. After the reaction was completed, the mixture was washed with water, dried over magnesium sulfate, and concentrated. The obtained crude crystals were separated by silica gel column chromatography using chloroform as an eluent, and recrystallized from ethanol to obtain 7.3 g of 4-(4″-n-octyloxybiphenyl-4′-carbonyloxy)-3.
-fluorophenyl-2,6-dimethylbutyl ether was obtained.
ＭＳ ７５６２ （Ｍ”）
ＮＭＲ： ０．９０（９）１． ｔ、 Ｊ−８，６１１
Ｚ）、 １．０５（３）１． ｄ。MS 7562 (M”) NMR: 0.90(9)1.t, J-8,611
Z), 1.05(3)1. d.
Ｊ−６，９Ｈｚ）、 １．２９（１２Ｈ，ｍ）、 １．
５４（６Ｈ，ｍ）。J-6,9Hz), 1.29 (12H, m), 1.
54 (6H, m).
１．８２（２）１． ｍ）、 １．９９（ＩＨ，ｍ）、
３．８０（ＩＨ，ｍ）。1.82(2)1. m), 1.99 (IH, m),
3.80 (IH, m).
３．９２（ＩＩ（、ｍ）、 ４．０３（２Ｌ ｍ）、
６．９８（５Ｈ，ｍ）。3.92 (II (, m), 4.03 (2L m),
6.98 (5H, m).
７．５９（２）１． ｍ）、 ７．８９（２）１． Ｉ
Ｉ＋）、 ｓ、２２．（２ｎ、 ｍ）合成例３
３−フルオロ−４−（２，８−ジメチルへブチルオキシ
）フェノールの合
２−フルオロ−１，４−ハイドロキノン２Ｓ、Ｂｇ。7.59(2)1. m), 7.89(2)1. I
I+), s, 22. (2n, m) Synthesis Example 3 Synthesis of 3-fluoro-4-(2,8-dimethylhebutyloxy)phenol 2-fluoro-1,4-hydroquinone 2S, Bg.
アセトン３００ｍｊ！ 、炭酸カリウム２７．６ｇの混
合物にベンジルクロライド２５．３ｇを加えて３時間速
流した。反応終了後、濾過して得た濾液を濃縮し、残渣
を水にあけ、トルエン２００ｍＪで抽出した。得られた
粗結晶をメタノールにて再結晶して融点８０℃の２−フ
ルオロ−４−ベンジルオキシフェノール３２．７ｇを得
た。Acetone 300mj! , 25.3 g of benzyl chloride was added to a mixture of 27.6 g of potassium carbonate, and the mixture was rapidly flowed for 3 hours. After the reaction was completed, the filtrate obtained by filtration was concentrated, the residue was poured into water, and extracted with 200 mJ of toluene. The obtained crude crystals were recrystallized from methanol to obtain 32.7 g of 2-fluoro-4-benzyloxyphenol having a melting point of 80°C.
２−フルオロ−４−ベンジルオキシフェノール２３．４
ｇ 、 ８５％水酸化カリウム９．９ｇ、水１５ｍＩ！
及びエタノール２ＱＱｍｆｆｉの混合物に２．６−ジメ
チルへブチル−ｐ−トルエンスルホネート２９ｇを滴下
し、滴下終了後１５時間遠流した。反応終了後、内容物
を水にあけ、トルエン１００ｍ１’で抽出した。トルエ
ン層を分離し、水洗後濃縮して粗生成物３４．０ｇを得
た。これをクロロホルムを溶出剤としてシリカゲルカラ
ムクロマトグラフィーにより分離し、エタノールより再
結晶して２１ｇの３−フルオロ−４−（２，６−ジメチ
ルへブチルオキシ）フェノールベンジルエーテルを得た
。この３−フルオロ−４−（２，６−ジメチルへブチル
オキシ）フェノールベンジルエーテル１２ｇをメタノー
ル２００ｍＡ’に溶解し、１０％Ｐｄ−Ｃ１ｇを加えて
常圧にて還元した。2-Fluoro-4-benzyloxyphenol 23.4
g, 9.9 g of 85% potassium hydroxide, 15 mI of water!
29 g of 2,6-dimethylhebutyl-p-toluenesulfonate was added dropwise to the mixture of ethanol and 2QQmffi, and the mixture was subjected to distant flow for 15 hours after the completion of the dropwise addition. After the reaction was completed, the contents were poured into water and extracted with 100ml of toluene. The toluene layer was separated, washed with water, and concentrated to obtain 34.0 g of a crude product. This was separated by silica gel column chromatography using chloroform as an eluent, and recrystallized from ethanol to obtain 21 g of 3-fluoro-4-(2,6-dimethylhebutyloxy)phenol benzyl ether. 12 g of this 3-fluoro-4-(2,6-dimethylhebutyloxy)phenol benzyl ether was dissolved in 200 mA' of methanol, 1 g of 10% Pd-C was added, and the mixture was reduced at normal pressure.
反応液を濾過し、濃縮して７．５ｇの３−フルオロ−４
−（２，６−ジメチルへブチルオキシ）フェノールを得
た。The reaction solution was filtered and concentrated to give 7.5 g of 3-fluoro-4
-(2,6-dimethylhebutyloxy)phenol was obtained.
合成例４
４−（４”−ｎ−オクチルオキシビフェニル−４−カル
ボニルオキシ）−２−フルオロフェニル−２，６−ジメ
チルへブチルエーテルの合成合成例２の２−フルオロ−
４−（２，６−ジメチルへブチルオキシ）フェノールに
代えて、３−フルオロ−４−（２，６−ジメチルへブチ
ルオキシ）フェノール７．５ｇを用いたこと以外は合成
例２と同様の方法にて合成し、７．０ｇの４−（４″−
ｎ−オクチルオキシビフェニル−４−カルボニルオキシ
）−２−フルオロフェニル−２，６−ジメチルへブチル
エーテルを得た。Synthesis Example 4 Synthesis of 4-(4''-n-octyloxybiphenyl-4-carbonyloxy)-2-fluorophenyl-2,6-dimethylhebutyl ether 2-fluoro- of Synthesis Example 2
In the same manner as Synthesis Example 2 except that 7.5 g of 3-fluoro-4-(2,6-dimethylhebutyloxy)phenol was used instead of 4-(2,6-dimethylhebutyloxy)phenol. Synthesized, 7.0g of 4-(4″-
n-octyloxybiphenyl-4-carbonyloxy)-2-fluorophenyl-2,6-dimethylhebutyl ether was obtained.
ＭＳ ：５Ｂ２ （Ｍ“）
ＮＭＲ： ０．８８（９１（、ｔ、 Ｊ−６，７）１ｚ
）、 １．０６（３８，ｄ。MS: 5B2 (M") NMR: 0.88 (91(,t, J-6,7)1z
), 1.06 (38, d.
Ｊ−８，７Ｈｚ）、 １．４０（１８Ｈ，ｍ）、 １．
８２（２Ｌ ｍ）。J-8,7Hz), 1.40 (18H, m), 1.
82 (2L m).
１．９９（ＩＨ，ｍ）、 ３．８０（１８，ｍ）、 ３
．９２（ＩＬ ｍ）。1.99 (IH, m), 3.80 (18, m), 3
．． 92 (IL m).
４．０３（２Ｈ，ｍ）、 ６．９８（５１１，ｍ）、
７．５９（２Ｈ，ｍ）。4.03 (2H, m), 6.98 (511, m),
7.59 (2H, m).
７．６８（２Ｈ，ｍ）、 ８．２２（２）１． ｍ）合
成例５
４−（４”−ｎ−オクチルオキシビフェニル−４′−カ
ルボニルオキシ）−２−フルオロ安息香酸−２．６−ジ
メチルへブチルエステルの合成３−フルオロ−４−ヒド
ロキシ安息香１９１５．６ｇ。7.68 (2H, m), 8.22 (2) 1. m) Synthesis Example 5 Synthesis of 4-(4''-n-octyloxybiphenyl-4'-carbonyloxy)-2-fluorobenzoic acid-2,6-dimethylhebutyl ester 3-fluoro-4-hydroxybenzoic acid 1915. 6g.
トルエン１８０ｍｊ＋ 、 ２．６−シメチルヘプタノ
ール（α”： −９，５） ２０ｇ及び硫酸１．２ｇを
加熱還流し、１０時間かけて水抜きを行った。反応終了
後、希炭酸ナトリウム水溶液にて洗浄し、水洗を行い、
トルエンを留去し、濃縮物３２．８ｇを得た。これをｎ
−ヘプタン６０１に溶解させ、−２０℃にて静置再結晶
を行い、３−フルオロ−４−ヒドロキシ安息香酸−２，
６−ジメチルへブチルエステル２６ｇを得た。180 mj+ of toluene, 20 g of 2.6-dimethylheptanol (α": -9,5) and 1.2 g of sulfuric acid were heated to reflux and water was removed over 10 hours. After the reaction was completed, the mixture was poured into a dilute aqueous sodium carbonate solution. and rinse with water.
Toluene was distilled off to obtain 32.8 g of concentrate. This is n
-Dissolved in heptane 601 and recrystallized at -20°C, 3-fluoro-4-hydroxybenzoic acid-2,
26 g of 6-dimethyl hebutyl ester was obtained.
３−フルオロ−４−ヒドロキシ安息香酸−２，６−シメ
チルヘプチルエステル７．８ｇ、ピリジン３．５ｇをト
ルエン８０ｍｊ＋に溶解し、これに合成例２で調製した
酸クロライドートルエン溶液を滴下した。その後、室温
にて１５時間攪拌し、反応を行った。反応終了後、希塩
酸水溶液にて洗浄し、さらに水洗を行い、硫酸マグネシ
ウムにて脱水した後、トルエンを留去した。得られた粗
結晶をクロロホルムを溶出剤としてシリカゲルカラムク
ロマトグラフィーにより分離し、エタノールより再結晶
して７．１ｇの４−（４”−ｎ−オクチルオキシビフェ
ニル−４−カルボニルオキシ）−２−フルオロ安息香酸
−２，６−シメチルヘプチルエステルを得た。7.8 g of 3-fluoro-4-hydroxybenzoic acid-2,6-dimethylheptyl ester and 3.5 g of pyridine were dissolved in 80 mj+ of toluene, and the acid chloride toluene solution prepared in Synthesis Example 2 was added dropwise thereto. Thereafter, the mixture was stirred at room temperature for 15 hours to carry out the reaction. After the reaction was completed, the mixture was washed with a dilute aqueous hydrochloric acid solution, further washed with water, dehydrated with magnesium sulfate, and then toluene was distilled off. The obtained crude crystals were separated by silica gel column chromatography using chloroform as an eluent, and recrystallized from ethanol to give 7.1 g of 4-(4''-n-octyloxybiphenyl-4-carbonyloxy)-2-fluoro. Benzoic acid-2,6-dimethylheptyl ester was obtained.
ＭＳ ：５７２ （Ｍ”）
ＮＭＲ： ０．９０（９Ｈ，ｔ、 Ｊ−６，５Ｈｚ）、
１．０３（３１１，ｄ、 Ｊ−６，７Ｈｚ）、 １
．３８（１７Ｈ，ｍ）、 １．８２（２）１． ｍ）
。MS: 572 (M”) NMR: 0.90 (9H,t, J-6,5Hz),
1.03 (311, d, J-6,7Hz), 1
．． 38 (17H, m), 1.82 (2) 1. m)
.
１．９５（ＬＨ，ｍ）、 ４．０３（２＋１． ｍ）、
４．１３（１）１． ｍ）。1.95 (LH, m), 4.03 (2+1. m),
4.13(1)1. m).
４．２３（Ｈｌ、 ｍ）、 ７．０２（２Ｈ，ｍ）、
７．３７（ＩＨ，ｍ）。4.23 (Hl, m), 7.02 (2H, m),
7.37 (IH, m).
７．６１（２Ｈ，ｍ）、 ７．７３（２Ｈ，ｍ）、 ７
．９２（２Ｈ，ｍ）。7.61 (2H, m), 7.73 (2H, m), 7
．． 92 (2H, m).
８．２５ （２Ｎ、 ｍ）
合成例６
４−（４”−ｎ−才クチルオキシビフェニル−４−カル
ボニルオキシ）−３−フルオロ安息香酸−２，６−ジメ
チルへブチルエステルの合合成例５の３−フルオロ−４
−ヒドロキシ安息香酸に代えて、２−フルオロ−４−ヒ
ドロキシ安息香酸１５．６ｇを用い、合成例５と同様の
方法にて合成し、融点７０．０℃の４−（４”−ｎ−才
クチルオキシビフェニル−４−カルボニルオキシ）−３
−フルオロ安息香酸−２，６−ジメチルへブチルエステ
ル６．８ｇを得た。8.25 (2N, m) Synthesis Example 6 Synthesis Example 5 of 4-(4''-n-year-old ctyloxybiphenyl-4-carbonyloxy)-3-fluorobenzoic acid-2,6-dimethylhebutyl ester 3-fluoro-4
Synthesized in the same manner as in Synthesis Example 5 using 15.6 g of 2-fluoro-4-hydroxybenzoic acid in place of -hydroxybenzoic acid, Cutyloxybiphenyl-4-carbonyloxy)-3
6.8 g of -fluorobenzoic acid-2,6-dimethylbutyl ester was obtained.
ＭＳ ：５７２ （Ｍ”）
ＮＭＲ： ０．８８（９Ｌ ｔ、 Ｊ−６，７Ｈｚ）、
１．０４（３Ｈ，ｄ、 Ｊ−６，８８Ｚ）、 １．
３８（１７Ｈ，ｍ）、 １．８２（２Ｈ，ｍ）。MS: 572 (M”) NMR: 0.88 (9Lt, J-6,7Hz),
1.04 (3H, d, J-6,88Z), 1.
38 (17H, m), 1.82 (2H, m).
１．９５（ｌ）Ｉ、 ｍ）、 ４．０３（２Ｈ，ｍ）、
４．１４（１Ｂ、 ｍ）。1.95 (l) I, m), 4.03 (2H, m),
4.14 (1B, m).
４．２４（ＩＨ，ｍ）、 ７．０２（２Ｈ，ｍ）、 ７
．１３（２Ｈ，ｍ）。4.24 (IH, m), 7.02 (2H, m), 7
．． 13 (2H, m).
７．６０（２ｔｌ、 ＩＩＩ）、 ７．７２（２８，ｍ
）、 ８．０４（ＩＨ，ｍ）。7.60 (2tl, III), 7.72 (28, m
), 8.04 (IH, m).
８．２２（２８，ｍ）
合成例７
４−（４′−ｎ−オクチルオキシビフェニル−４−カル
ボニルオキシ）−２−フルオロフェニル−２，６−ジメ
チルへブチルエーテルの合成４′−ｎ−才クチル−４−
シアノビフェニルをＧｒａｙ ｅｔ ａｌ、 Ｍｏ１．
Ｃｒｙｓｔ、 Ｌｉｑ、 Ｃｒｙｓｔ、、 ３７．１
８９−２１１．１９７６の方法にしたがって加水分解し
て得た４’−ｎ−オクチルビフェニル−４−カルボン酸
７．７５ｇを用い、合成例２と同様にして酸クロライド
ートルエン溶液を調製した。8.22 (28, m) Synthesis Example 7 Synthesis of 4-(4'-n-octyloxybiphenyl-4-carbonyloxy)-2-fluorophenyl-2,6-dimethylhebutyl ether 4'-n-octyloxybiphenyl-4-carbonyloxy -4-
Cyanobiphenyl was prepared by Gray et al, Mo1.
Cryst, Liq, Cryst, 37.1
An acid chloride toluene solution was prepared in the same manner as in Synthesis Example 2 using 7.75 g of 4'-n-octylbiphenyl-4-carboxylic acid obtained by hydrolysis according to the method of 89-211.1976.
合成例２の２−フルオロ−４−（２，６−ジメチルへブ
チルオキシ）フェノールに代えて、合成例３で得た３−
フルオロ−４−（２，６−ジメチルへブチルオキシ）フ
ェノール７．５ｇ及び前記酸クロライドートルエン溶液
を用い、合成例２と同様の方法にて合成し、６．９ｇの
４−（４″−ｎ−才クチルオキシビフェニル−４′−カ
ルボニルオキシ）−２−フルオロフェニル−２，６−ジ
メチルへブチルエーテルを得た。In place of 2-fluoro-4-(2,6-dimethylhebutyloxy)phenol in Synthesis Example 2, 3-fluoro-4-(2,6-dimethylhebutyloxy)phenol obtained in Synthesis Example 3 was used.
Synthesis was carried out in the same manner as in Synthesis Example 2 using 7.5 g of fluoro-4-(2,6-dimethylhebutyloxy)phenol and the above acid chloride toluene solution, and 6.9 g of 4-(4''-n -2-fluorophenyl-2,6-dimethylbutyl ether was obtained.
ＭＳ ：５４６ （Ｍ”）
ＮＭＲ： ０．９０（９Ｈ，ｔ、 Ｊ−６，７Ｈｚ）、
１．０５（３Ｈ，ｄ、 Ｊ−６，７Ｈｚ）、 １．
４．３（１９）１． ｍ）、 １．９８（１）１． ｍ
）。MS: 546 (M”) NMR: 0.90 (9H, t, J-6,7Hz),
1.05 (3H, d, J-6,7Hz), 1.
4.3(19)1. m), 1.98(1)1. m
).
２．６７（２Ｈ，ｍ）、 ３．８２（ＩＨ，ｍ）、 ３
．９２（ＩＩＩ、 ｍ）。2.67 (2H, m), 3.82 (IH, m), 3
．． 92 (III, m).
８．９８（３８，ｍ）、 ７．３０（２Ｈ，ｍ）、 ７
．５７（２Ｈ，ＩＩＩ）。8.98 (38, m), 7.30 (2H, m), 7
．． 57 (2H, III).
７．７３（２Ｈ，ｍ）、 ８．２２（２８，ｍ）合成例
８
４−（４″−ｎ−デシルオキシビフェニル−４′−カル
ボニルオキシ）−２−フルオロフェニル−２，６−ジメ
チルへブチルエーテルの合成
合成例２の４′−ｎ−才クチルオキシビフェニルー４−
カルボン酸に代えて、４′−ｎ−デシルオキシビフェニ
ル−４−カルボン酸１０．４ ｇを、合成例２の２−フ
ルオロ−４−（２，６−ジメチルへブチルオキシ）フェ
ノールに代えて、合成例３で得た３−フルオロ−４−（
２，６−ジメチルへブチルオキシ）フェノール７．５ｇ
を用いたほかは合成例２と同様の方法で合成を行い、８
．２ｇの４−（４″−ｎ−デシルオキシビフェニル−４
′−カルボニルオキシ）−２−フルオロフェニル−２，
６−ジメチルへブチルエーテルを得た。7.73 (2H, m), 8.22 (28, m) Synthesis Example 8 To 4-(4″-n-decyloxybiphenyl-4′-carbonyloxy)-2-fluorophenyl-2,6-dimethyl Synthesis of butyl ether 4'-n-year-old ctyloxybiphenyl-4-
Synthesis was carried out by replacing carboxylic acid with 10.4 g of 4'-n-decyloxybiphenyl-4-carboxylic acid and replacing 2-fluoro-4-(2,6-dimethylhebutyloxy)phenol in Synthesis Example 2. 3-Fluoro-4-( obtained in Example 3)
2,6-dimethylhebutyloxy)phenol 7.5g
Synthesis was carried out in the same manner as in Synthesis Example 2 except that 8
．． 2g of 4-(4″-n-decyloxybiphenyl-4
'-carbonyloxy)-2-fluorophenyl-2,
6-dimethyl hebutyl ether was obtained.
ＭＳ ：５７２ （Ｍ”）
ＮＭＲ： ０．９０（９１（、ｔ、 Ｊ−６，８１１Ｚ
）、 １．０４（３Ｈ，ｄ、 Ｊ−８，７Ｈ２）、 １
．３７（２１１１，ｍ）、 １．８２（２Ｈ，ｍ）。MS: 572 (M”) NMR: 0.90 (91(,t, J-6,811Z
), 1.04 (3H, d, J-8, 7H2), 1
．． 37 (2111, m), 1.82 (2H, m).
１．９８（ＩＨ，ｌ１１）、 ３．８１（１）１． ｍ
）、 ３．９１（ＬＨ，ｍ）。1.98 (IH, l11), 3.81 (1) 1. m
), 3.91 (LH, m).
４．０３（２Ｎ、 ｍ）、 ８．９８（５Ｌ ｍ）、
７．５８（２Ｈ，ｍ）。4.03 (2N, m), 8.98 (5L m),
7.58 (2H, m).
７．６８（２Ｈ，ｉｔ）、 ８．２１（２Ｈ，ｍ）合成
例９
４−（４″−ｎ−オクチルオキシビフェニル−４′−カ
ルボニルオキシ）−３−フルオロ安息香酸−３，７−ジ
メチルオクチルエステルの合成合成例５の３−フルオロ
−４−ヒドロキシ安息香酸−２，６−ジメチルへブチル
エステルに代えて、２−フルオロ−４−ヒドロキシ安息
香酸−３，７−シメチルオクチルエステル８．１ ｇを
用いたほかは合成例５と同様の方法で合成を行い、８．
６ｇの４−（４”−ｎ−オクチルオキシビフェニル−４
′−カルボニルオキシ）−３−フルオロ安息香酸−３，
７−ジメチルオクチルエステルを得た。7.68 (2H, it), 8.21 (2H, m) Synthesis Example 9 4-(4″-n-octyloxybiphenyl-4′-carbonyloxy)-3-fluorobenzoic acid-3,7-dimethyl Synthesis of Octyl Ester 2-fluoro-4-hydroxybenzoic acid-3,7-dimethyloctyl ester was substituted for 3-fluoro-4-hydroxybenzoic acid-2,6-dimethylhebutyl ester in Synthesis Example 5.8. Synthesis was carried out in the same manner as in Synthesis Example 5 except that 1 g was used, and 8.
6 g of 4-(4”-n-octyloxybiphenyl-4
'-carbonyloxy)-3-fluorobenzoic acid-3,
7-dimethyloctyl ester was obtained.
ＭＳ ：５８Ｂ （Ｍ“）
ＮＭＲ： ０．９１（９Ｈ，ｔ、 Ｊ−６，８Ｈｚ）、
Ｑ、９９（３１（、ｄ、 Ｊ−６，４Ｈｚ）、 １．
１５〜１６３（１９Ｈ，ｍ）、 １．８３（３１１゜ｍ
ｌ、 ４．（１５（２ｔ（、ｍ）、 ４．４３（２８，
ｍ）、 ７．０４（０１゜ｍ）、 ７．２４（１１（、
ｍ）、 ？、ｆ＋２（２）１． ｍ）、 ７．７３（２
Ｈ。MS: 58B (M") NMR: 0.91 (9H, t, J-6, 8Hz),
Q, 99 (31 (, d, J-6, 4Hz), 1.
15-163 (19H, m), 1.83 (311゜m)
l, 4. (15(2t(,m), 4.43(28,
m), 7.04 (01゜m), 7.24 (11 (,
m), ? , f+2(2)1. m), 7.73(2
H.
ｍ）、 ｌｓ、１ｏ（２１（、ｍ）、 ８．２７（
２）１． １１１）液晶諸特性の測定は、以下の通りで
行った。m), ls, 1o(21(,m), 8.27(
2)1. 111) Measurement of liquid crystal properties was performed as follows.
液晶セルとしては、ガラス板上に透明電極を設け、更に
高分子膜をコーティングし、一定方向にラビングした後
、２枚の基板のラビング方向が平行になるようにしてス
ペーサーを用いて一定の愚さに組み立てたものを用いた
。セル間隔は、３μｌである。このセルに前述の液晶材
料を注入し、ヘリウム−ネオンレーザ−及び光電子増倍
管を用い、±２０Ｖの矩形波の交流を印加して電気光学
効果を観察したところ、明確なコントラストに加え、高
速な応答が確認され液晶表示素子として使用可能である
ことがわかった。As a liquid crystal cell, a transparent electrode is provided on a glass plate, a polymer film is further coated, and the two substrates are rubbed in a certain direction, and then a spacer is used to make the rubbing direction of the two substrates parallel. I used the one that I had assembled. Cell spacing is 3 μl. When we injected the above-mentioned liquid crystal material into this cell and applied a ±20V square wave alternating current using a helium-neon laser and a photomultiplier tube to observe the electro-optic effect, we found that in addition to clear contrast, high speed A positive response was confirmed, indicating that it can be used as a liquid crystal display element.
応答速度の測定は、室温付近あるいはＴｃ−Ｔ；５°で
行りた。（ＴＣはＳＣ”相からＳＡ相への転穆温度であ
る。）
また、相転移温度は示差走査熱量計および偏光顕＠鏡に
よる観察で求めた。The response speed was measured near room temperature or at Tc-T: 5°. (TC is the transition temperature from the SC'' phase to the SA phase.) Further, the phase transition temperature was determined by observation using a differential scanning calorimeter and a polarizing microscope.
実施例１〜７
各液晶性化合物について相転移温度、自発分極、チルト
角及び応答速度を前記液晶諸特性の測定方法にしたがっ
て測定した。その結果を表−１に示した。Examples 1 to 7 The phase transition temperature, spontaneous polarization, tilt angle, and response speed of each liquid crystal compound were measured according to the method for measuring liquid crystal properties described above. The results are shown in Table-1.
応用例１〜２
表示装置の、実際の使用温度のより広い範囲にわたり、
高速応答性を示す液晶組成物を得る目的で、各種の液晶
性化合物を混合し、その性能を調べた。また、実施例に
より得た液晶性化合物を用いて、液晶表示素子としての
応答特性を評価した。その代表例につき表−２にその一
部を記した。また、各応用例に用いた液晶性化合物の混
合組成は次の通りである。Application examples 1 and 2 Over a wider range of actual operating temperatures of display devices,
In order to obtain a liquid crystal composition exhibiting high-speed response, various liquid crystal compounds were mixed and their performance was investigated. Furthermore, using the liquid crystal compounds obtained in Examples, response characteristics as a liquid crystal display element were evaluated. Some representative examples are listed in Table 2. Further, the mixed composition of the liquid crystalline compounds used in each application example is as follows.
液晶性化合物の混合組
混合例１
ｎ−Ｃ＋ｏｌｈ＋へ）Ｏｃ ｏ ２＋ｃ Ｏ２／’γヅ
Ｙ ４９．１ｗｔ％合成例４の化合物
１５．６ ／／混合例２
ｎ−ＣＪｔｓへ）６０２舎Ｃ０２ハ’？””ｌ’ ２０
．８ ／／ｎ−（＋２Ｈ２ｓＯ号ｃｏへ）ｃｏ２”ｔ〜
Ｙ ２１．１７／合成例７の化合物
２４．１ ／／［発明の効果コ
本発明の液晶性化合物は、画像表示に於ける高速応答性
を示し、今後の高密度で大型のディスプレー用素材とし
ての需要に応えることのできるものである。Mixed set of liquid crystal compounds Mixing example 1 To n-C+olh+)Oco 2+c O2/'γㅅY 49.1wt% Compound of synthesis example 4
15.6 //Mixing example 2 n-CJts) 602 building C02 Ha'? ""l' 20
．． 8 //n- (+2H2sO No. co) co2”t~
Y 21.17/Compound of Synthesis Example 7
24.1 // [Effects of the Invention] The liquid crystal compound of the present invention exhibits high-speed response in image display and can meet future demands as a material for high-density, large-sized displays. .
Claims (1)
シル基を示し、Ｒ＾＊は複数の分枝を持ち、炭素数９〜
１１の不斉炭素原子を有する光学活性基を示し、Ｘ、Ｙ
はどちらか一方が水素又はフッ素原子を示し、ｎは０あ
るいは１である。）で表わされる液晶性化合物。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R represents an alkyl group or an alkoxyl group having 6 to 12 carbon atoms, and R^* represents a plurality of components. Has branches, carbon number 9~
Indicates an optically active group having 11 asymmetric carbon atoms, X, Y
Either one of these represents a hydrogen or fluorine atom, and n is 0 or 1. ) is a liquid crystalline compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5127387A JPH064565B2 (en) | 1987-03-06 | 1987-03-06 | Fluorine-containing liquid crystalline compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5127387A JPH064565B2 (en) | 1987-03-06 | 1987-03-06 | Fluorine-containing liquid crystalline compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63216849A true JPS63216849A (en) | 1988-09-09 |
| JPH064565B2 JPH064565B2 (en) | 1994-01-19 |
Family
ID=12882338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5127387A Expired - Fee Related JPH064565B2 (en) | 1987-03-06 | 1987-03-06 | Fluorine-containing liquid crystalline compounds |
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| Country | Link |
|---|---|
| JP (1) | JPH064565B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01261493A (en) * | 1988-04-12 | 1989-10-18 | Nippon Telegr & Teleph Corp <Ntt> | Liquid crystal composition |
-
1987
- 1987-03-06 JP JP5127387A patent/JPH064565B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01261493A (en) * | 1988-04-12 | 1989-10-18 | Nippon Telegr & Teleph Corp <Ntt> | Liquid crystal composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH064565B2 (en) | 1994-01-19 |
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