JPH0564134B2 - - Google Patents
Info
- Publication number
- JPH0564134B2 JPH0564134B2 JP58138148A JP13814883A JPH0564134B2 JP H0564134 B2 JPH0564134 B2 JP H0564134B2 JP 58138148 A JP58138148 A JP 58138148A JP 13814883 A JP13814883 A JP 13814883A JP H0564134 B2 JPH0564134 B2 JP H0564134B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- formula
- optically active
- phase
- synthesized
- 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
- 150000001875 compounds Chemical group 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 239000004973 liquid crystal related substance Substances 0.000 claims description 25
- 239000004990 Smectic liquid crystal Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- -1 4-hydroxy-4'-substituted biphenyl Chemical group 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- MQNLOOJFAVAAKD-UHFFFAOYSA-N 2-methylbutyl carbonochloridate Chemical compound CCC(C)COC(Cl)=O MQNLOOJFAVAAKD-UHFFFAOYSA-N 0.000 description 4
- JZGBNMKIGIXDCL-UHFFFAOYSA-N 4-(4-tetradecoxyphenyl)phenol Chemical group C1=CC(OCCCCCCCCCCCCCC)=CC=C1C1=CC=C(O)C=C1 JZGBNMKIGIXDCL-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VKMLCPHQDWRURW-UHFFFAOYSA-N 4-(4-octoxyphenyl)phenol Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(O)C=C1 VKMLCPHQDWRURW-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- YSMHTFWPDRJCMN-UHFFFAOYSA-N butan-2-yl carbonochloridate Chemical compound CCC(C)OC(Cl)=O YSMHTFWPDRJCMN-UHFFFAOYSA-N 0.000 description 3
- 230000003098 cholesteric effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- SHFQYSOBHYYRBO-UHFFFAOYSA-N 1-[4-(4-octoxyphenyl)phenyl]ethanone Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(C)=O)C=C1 SHFQYSOBHYYRBO-UHFFFAOYSA-N 0.000 description 2
- CKSIBFLEDRJUTN-UHFFFAOYSA-N 3-chloropentan-2-one Chemical compound CCC(Cl)C(C)=O CKSIBFLEDRJUTN-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GNHSLRMCJVPUAO-UHFFFAOYSA-N [4-(4-acetylphenyl)phenyl] acetate Chemical group C1=CC(OC(=O)C)=CC=C1C1=CC=C(C(C)=O)C=C1 GNHSLRMCJVPUAO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- RSYNHXZMASRGMC-UHFFFAOYSA-N butan-2-yl hydrogen carbonate Chemical compound CCC(C)OC(O)=O RSYNHXZMASRGMC-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OKUTVLLADIKJLP-UHFFFAOYSA-N 1-[4-(4-tetradecoxyphenyl)phenyl]ethanone Chemical group C1=CC(OCCCCCCCCCCCCCC)=CC=C1C1=CC=C(C(C)=O)C=C1 OKUTVLLADIKJLP-UHFFFAOYSA-N 0.000 description 1
- XKVLZBNEPALHIO-UHFFFAOYSA-N 1-bromo-2-methylbutane Chemical compound CCC(C)CBr XKVLZBNEPALHIO-UHFFFAOYSA-N 0.000 description 1
- SLBTUZZYJLBZQV-UHFFFAOYSA-N 1-chloro-2-methylpentane Chemical compound CCCC(C)CCl SLBTUZZYJLBZQV-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-BYPYZUCNSA-N 2-Methylbutanoic acid Natural products CC[C@H](C)C(O)=O WLAMNBDJUVNPJU-BYPYZUCNSA-N 0.000 description 1
- 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 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NAJMIVLMDLWNRF-UHFFFAOYSA-N 2-methylbutyl hydrogen carbonate Chemical compound CCC(C)COC(O)=O NAJMIVLMDLWNRF-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- MFIQXAVMTLKUJR-UHFFFAOYSA-N 2-methylpentanoyl chloride Chemical compound CCCC(C)C(Cl)=O MFIQXAVMTLKUJR-UHFFFAOYSA-N 0.000 description 1
- IGIDLTISMCAULB-UHFFFAOYSA-N 3-methylvaleric acid Chemical compound CCC(C)CC(O)=O IGIDLTISMCAULB-UHFFFAOYSA-N 0.000 description 1
- DLLIPJSMDJCZRF-UHFFFAOYSA-N 4-(4-ethylphenyl)benzonitrile Chemical group C1=CC(CC)=CC=C1C1=CC=C(C#N)C=C1 DLLIPJSMDJCZRF-UHFFFAOYSA-N 0.000 description 1
- GPGGNNIMKOVSAG-UHFFFAOYSA-N 4-(4-octoxyphenyl)benzonitrile Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C#N)C=C1 GPGGNNIMKOVSAG-UHFFFAOYSA-N 0.000 description 1
- PBMCTXQDYLSLTP-UHFFFAOYSA-N 4-(4-pentylphenyl)-3-phenylbenzonitrile Chemical group C1=CC(CCCCC)=CC=C1C1=CC=C(C#N)C=C1C1=CC=CC=C1 PBMCTXQDYLSLTP-UHFFFAOYSA-N 0.000 description 1
- HHPCNRKYVYWYAU-UHFFFAOYSA-N 4-cyano-4'-pentylbiphenyl Chemical group C1=CC(CCCCC)=CC=C1C1=CC=C(C#N)C=C1 HHPCNRKYVYWYAU-UHFFFAOYSA-N 0.000 description 1
- 241001270131 Agaricus moelleri Species 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PFZAXLFGUSIZRN-MHZLTWQESA-N [4-(4-tetradecoxyphenyl)phenyl] (2s)-2-methylpentanoate Chemical group C1=CC(OCCCCCCCCCCCCCC)=CC=C1C1=CC=C(OC(=O)[C@@H](C)CCC)C=C1 PFZAXLFGUSIZRN-MHZLTWQESA-N 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
本発明は新規な液晶物質及び該液晶物質を含有
する液晶組成物に関し、更に詳しくは光学活性基
を有するカイラル液晶物質及びそれらを含有する
カイラル液晶組成物に関する。
現在、液晶表示素子としてはTN(Twisted
Nematic)型表示方式が最も広く用いられてい
るが、応答速度の点に於て発光型表示素子(エレ
クトロルミネツセンス、プラズマデイスプレイ
等)と比較して劣つており、この点に於ける改善
は種々試みられているにも抱らず、大巾な改善の
可能性はあまり残つていない様である。そのため
TN型表示素子に代わる別の原理による液晶表示
装置が種々試みられているが、その一つに強誘電
性液晶を利用する表示方式がある(N.A.Clark
ら;Applied Phys.lett.,36,899(1980))。この
方式は強誘電性液晶のカイラルスメクチツクC相
(以下SC*S相と略称する)或はカイラルスメク
チツクH粗(以下SH*相と略称する)を利用する
もので、それが室温付近にあるのが望ましい。本
発明者らは、この表示方式に利用されるに適した
液晶物質の開発を主たる目的として、光学活性基
を含む液晶物質を種々探索して本発明に到達し
た。
即ち、本発明は一般式
(但し、上式に於いて、Xは炭素数1〜18のア
ルキル基又は、アルキルオキシ基であり、lは0
を、m及びnは0又は1をそれぞれ示す。又*は
光学活性炭素原子を示す。)
で表わされる化合物、及びそれを含有する液晶組
成物である。
()式の化合物は、あるものは限られた温度
範囲に於いてコレステリツク相及びスメクチツク
相を呈し、又あるものはコレステリツク相を呈さ
ず、スメクチツク相のみを呈する。しかしいずれ
にしても、そのスメクチツク相のなかにSC*相が
あることに主たる特徴を有する。
SC*相の光スイツチング効果を表示素子として
応用する場合TN表示方式にくらべて3つのすぐ
れた特徴がある。第1の特徴は非常に高速で応答
し、その応答時間は通常のTN表示方式の素子と
比較すると、応答時間は1/100以下である。第2
の特徴はメモリー効果があることであり、上記の
高速応答性とあいまつて、時分割駆動が容易であ
る。第3の特徴は濃淡の階調を容易に得られるこ
とである。TN表示方式で濃淡の階調をとるに
は、印加電圧を調節して行なうが、しきい値電圧
の温度依存性や応答速度の電圧依存性などの難問
がある。しかしSC*相の光スイツチング効果を応
用する場合には極性の反転時間を調節することに
より、容易に階調を得ることができ、グラフイツ
ク表示に非常に適している。
表示方法としては、2つの方式が考えられ、1
つの方法は2枚の偏光子を使用する複屈折型他の
1つの方法は二色性色素を使用するゲストホスト
型である。SC*相は自発分極をもつため、印加電
圧の極性を反転することにより、らせん軸を回転
軸として分子が反転する。SC*相を有する液晶組
成物を液晶分子が電極面に平行にならぶように配
向処理を施した液晶表示セルに注入し、液晶分子
のダイレクターと一方の偏光面を平行になるよう
に配置した2枚の偏光子の間に該液晶セルをはさ
み、電圧を印加して、極性を反転することによ
り、明視野および暗視野(偏光子の対向角度によ
り決まる)が得られる。一方ゲスト・ホスト型で
動作する場合には、印加電圧の極性を反転するこ
とにより明視野及び着色視野(偏光板の配置によ
り決まる)を得ることができる。
一般にスメクチツク状態で液晶分子をガラス壁
面に平行に配向させることは難かしく、数十キロ
ガウス以上の磁場中で等方性液体から非常にゆつ
くりと冷却する(1℃〜2℃/hr)ことにより、
液晶分子を配向させているが、コレステリツク相
を有する液晶物質では磁場の代わりに50V〜
100Vの直流電圧を印加しながら1℃/minの冷
却速度で冷却することにより、容易に均一に配向
したモノドメイン状態を得ることができる。
()式の化合物は4−ヒドロキシ−4′−置換
ビフエニルに、ピリジンのような塩基性溶媒中で
それぞれ相当する、光学活性なカルボン酸クロラ
イド、あるいはクロルギ酸アルキルを作用させる
ことにより、最も好適に製造される。
原料の一つである4−ヒドロキシ−4′−置換ビ
フエニルのうち4−アルキルオキシ−4′−ヒドロ
キシビフエニル(a)は以下の様な工程により
製造することができる。
(上図においてRは炭素数1〜18のアルキル基
を示す。)
即ち、ヒドロキシビフエニルに無水塩化アルミ
ニウム存在下に2倍モルの塩化アセチルを作用さ
せて、4−アセチルオキシ−4′−アセチルビフエ
ニルが合成される。これに水酸化カリウムの存在
下にアルキルブロマイドを作用させると、4−ア
セチル−4′−アルキルオキシビフエニルが合成さ
れる。
さらにこの化合物にギ酸中、過酸化水素を作用
させることにより、4−アセチルオキシ−4′−ア
ルキルオキシビフエニルが合成される。
これをアルカリで加水分解して、酸を加えるこ
とにより目的の4−アルキルオキシ−4′−ヒドロ
キシビフエニル(a)が合成される。
4−ヒビロキシ−4′−置換ビフエニルのうちの
4−アルキル−4′−ヒドロキシビフエニル(
b)は以下のような工程により合成することがで
きる。
(上図においてRは炭素数1〜17のアルキル基
を示す。)
即ち、ヒドロキシビフエニルに無水塩化アルミ
ニウムの存在下にアルキルカルボン酸クロライド
を作用させて4−アシル−4′−アシルオキシビフ
エニルを合成し、これをウオルフ−キシユナ−還
元し、次いでアルカリ中で加水分解することによ
り4−アルキル−4′−ヒドロキシビフエニル(
b)が合成される。
また、もう一方の原料である、光学活性なカル
ボン酸クロライド、あるいは光学活性なクロルギ
酸アルキルには以下のようなものがある。
The present invention relates to novel liquid crystal substances and liquid crystal compositions containing the liquid crystal substances, and more particularly to chiral liquid crystal substances having optically active groups and chiral liquid crystal compositions containing them. Currently, TN (Twisted
Nematic type display devices are the most widely used, but they are inferior to light emitting type display devices (electroluminescent displays, plasma displays, etc.) in terms of response speed, and improvements in this point are not possible. Although various attempts have been made to no avail, there does not seem to be much potential for significant improvement. Therefore
Various attempts have been made to develop liquid crystal display devices based on different principles to replace TN display elements, one of which is a display method that uses ferroelectric liquid crystals (NAClark
et al.; Applied Phys.lett., 36 , 899 (1980)). This method utilizes the chiral smectic C phase (hereinafter abbreviated as SC * S phase) or chiral smectic H phase (hereinafter abbreviated as SH * phase) of ferroelectric liquid crystal, which is Preferably nearby. The present inventors have arrived at the present invention by searching for various liquid crystal materials containing optically active groups, with the main purpose of developing a liquid crystal material suitable for use in this display method. That is, the present invention is based on the general formula (However, in the above formula, X is an alkyl group or an alkyloxy group having 1 to 18 carbon atoms, and l is 0
, m and n represent 0 or 1, respectively. Also, * indicates an optically active carbon atom. ) and a liquid crystal composition containing the same. Some of the compounds of formula () exhibit a cholesteric phase and a smectic phase in a limited temperature range, and others exhibit only a smectic phase without exhibiting a cholesteric phase. However, in any case, the main feature is that the SC * phase is included in the smectic phase. When applying the optical switching effect of the SC * phase to a display element, there are three superior features compared to the TN display system. The first feature is that it responds very quickly, and its response time is less than 1/100 of that of a normal TN display type element. Second
The feature of this is that it has a memory effect, which, combined with the above-mentioned high-speed response, makes time-division driving easy. The third feature is that gradations of light and shade can be easily obtained. In the TN display method, gray scales are achieved by adjusting the applied voltage, but there are challenges such as the temperature dependence of the threshold voltage and the voltage dependence of the response speed. However, when applying the optical switching effect of the SC * phase, gradation can be easily obtained by adjusting the polarity reversal time, making it very suitable for graphical display. There are two possible display methods: 1.
One method is a birefringent method that uses two polarizers.The other method is a guest-host method that uses a dichroic dye. Since the SC * phase has spontaneous polarization, by reversing the polarity of the applied voltage, the molecule is reversed with the helical axis as the rotation axis. A liquid crystal composition having an SC * phase was injected into a liquid crystal display cell that had been subjected to alignment treatment so that the liquid crystal molecules were aligned parallel to the electrode surface, and the director of the liquid crystal molecules was arranged so that one plane of polarization was parallel to the other. By sandwiching the liquid crystal cell between two polarizers and applying a voltage to reverse the polarity, a bright field and a dark field (determined by the facing angle of the polarizers) can be obtained. On the other hand, when operating in a guest-host mode, a bright field and a colored field (determined by the arrangement of polarizing plates) can be obtained by reversing the polarity of the applied voltage. Generally, it is difficult to align liquid crystal molecules parallel to the glass wall surface in a smectic state, but it is difficult to align liquid crystal molecules parallel to the glass wall surface in a smectic state. ,
Liquid crystal molecules are aligned, but in liquid crystal materials with cholesteric phase, 50V ~ 50V is used instead of a magnetic field.
By cooling at a cooling rate of 1° C./min while applying a DC voltage of 100 V, a uniformly oriented monodomain state can be easily obtained. The compound of formula () is most preferably produced by reacting 4-hydroxy-4'-substituted biphenyl with the corresponding optically active carboxylic acid chloride or alkyl chloroformate in a basic solvent such as pyridine. Manufactured. Among the 4-hydroxy-4'-substituted biphenyls that are one of the raw materials, 4-alkyloxy-4'-hydroxybiphenyl (a) can be produced by the following steps. (In the above diagram, R represents an alkyl group having 1 to 18 carbon atoms.) That is, hydroxybiphenyl is reacted with twice the mole of acetyl chloride in the presence of anhydrous aluminum chloride to form 4-acetyloxy-4'-acetyl. Biphenyl is synthesized. When this is reacted with an alkyl bromide in the presence of potassium hydroxide, 4-acetyl-4'-alkyloxybiphenyl is synthesized. Furthermore, by reacting this compound with hydrogen peroxide in formic acid, 4-acetyloxy-4'-alkyloxybiphenyl is synthesized. By hydrolyzing this with an alkali and adding an acid, the desired 4-alkyloxy-4'-hydroxybiphenyl (a) is synthesized. 4-alkyl-4'-hydroxybiphenyl among 4-hibiloxy-4'-substituted biphenyl (
b) can be synthesized by the following steps. (In the above diagram, R represents an alkyl group having 1 to 17 carbon atoms.) That is, hydroxybiphenyl is reacted with an alkylcarboxylic acid chloride in the presence of anhydrous aluminum chloride to form 4-acyl-4'-acyloxybiphenyl. 4-alkyl-4'-hydroxybiphenyl (
b) is synthesized. The other raw material, optically active carboxylic acid chloride or optically active alkyl chloroformate, includes the following.
【式】(α−メチルブタノイル クロライド) (a)[Formula] (α-methylbutanoyl chloride) (a)
【式】(β−メチルペンタ ノイルクロライド) (b)[Formula] (β-methylpenta noyl chloride) (b)
【式】(クロルギ酸1−メチ ルプロピル) (g)[Formula] (1-methychloroformate (lupropyl) (g)
【式】(クロルギ酸2−メ
チルブチル)
(h)
(上図において*は光学活性炭素をあらわす、
以下同様)
上記の光学活性α−メチルブタノイルクロライ
ド(a)は、次のような工程で合成される。
即ち、光学活性2−メチルブチルアルコールを
過マンガン酸カリウムで酸化して光学活性2−メ
チルブタン酸とし、これに塩化チオニルを作用さ
せて、光学活性−α−メチルブタノイルクロライ
ド(a)が合成される。
又、光学活性−β−メチルペンタノイルコロラ
イド(b)は次のような工程で合成される。
即ち、光学活性1−ブロモ−2−メチルブタン
にマグネシウムを作用させ、グリニヤー試薬を調
製し、これにドライアイスを作用させることによ
り、光学活性β−メチルペンタン酸が合成され
る。これに塩化チオニルを作用させて光学活性−
β−メチルペンタニルクロライド(b)が合成
される。
又、光学活性クロルギ酸−1−メチルプロピル
(g)は以下のような工程により合成される。
即ち光学活性2−メチル−1−ブタノールにホ
スゲンを作用させることにより合成される。
又、光学活性クロルギ酸−2−メチルブチル
(h)は以下のような工程により合成される。
即ち、光学活性2−ブタノールにホスゲンを作
用させることにより合成される。
以上の2種の()式の化合物と各種の()
式の化合物を組み合せてエステル化することによ
り()式の化合物を得ることが出来る。
即ち、化合物(a)と化合物(a)あるい
は(b)をエステル化することによつて次の化
合物(()式でl=m=n=0の化合物)を合
成することができる。(実施例1,5〜7)
4−アルキル−4′−α−メチルブタノイルオキ
シビフエニル、
4−アルキルオキシ−4′−α−メチルブタノイ
ルオキシビフエニル。
化合物(b)と化合物(a)あるいは(
b)をエステル化することによつて次の化合物
(()式でl=m=0,n=1の化合物)を合成
することができる。(実施例3,11〜13)
4−アルキル−4′−β−メチルペンタノイルオ
キシビフエニル、
4−アルキルオキシ−4′−β−メチルペンタノ
イルオキシビフエニル。
又、化合物(g)と化合物(a)あるいは
(b)をエステル化することにより以下の化合
物(()式でl=0,m=1,n=0のもの)
を合成することができる。
4−アルキル−4′−ビフエニリル(1−メチル
プロピル)カルボナート、
4−アルキルオキシ−4′−ビフエニリル(1−
メチルプロピル)カルボナート。
又、化合物(h)と化合物(a)あるいは
(b)をエステル化することにより以下の化合
物(()式でl=0,m=n=1のもの)を合
成することができる。
4−アルキル−4′−ビフエニリル(2−メチル
ブチル)カルボナート、
4−アルキルオキシ−4′−ビフエニリル(2−
メチルブチル)カルボナート、
これら本発明の()式の化合物の代表的なも
のの相転移温度を表1に示す。[Formula] (2-methylbutyl chloroformate) (h) (In the above figure, * represents optically active carbon,
The same applies hereinafter) The above optically active α-methylbutanoyl chloride (a) is synthesized in the following steps. That is, optically active 2-methylbutyl alcohol is oxidized with potassium permanganate to give optically active 2-methylbutanoic acid, and this is treated with thionyl chloride to synthesize optically active -α-methylbutanoyl chloride (a). Ru. Further, optically active β-methylpentanoyl colloid (b) is synthesized by the following steps. That is, optically active β-methylpentanoic acid is synthesized by reacting optically active 1-bromo-2-methylbutane with magnesium to prepare a Grignard reagent, and reacting dry ice with this. This is optically activated by the action of thionyl chloride.
β-Methylpentanyl chloride (b) is synthesized. Moreover, optically active 1-methylpropyl chloroformate (g) is synthesized by the following steps. That is, it is synthesized by reacting optically active 2-methyl-1-butanol with phosgene. Moreover, optically active 2-methylbutyl chloroformate (h) is synthesized by the following steps. That is, it is synthesized by reacting optically active 2-butanol with phosgene. The above two types of compounds of formula () and various types of ()
By combining the compounds of the formula and esterifying them, the compound of the formula () can be obtained. That is, by esterifying compound (a) and compound (a) or (b), the following compound (a compound where l=m=n=0 in formula ()) can be synthesized. (Examples 1, 5 to 7) 4-Alkyl-4'-α-methylbutanoyloxybiphenyl, 4-alkyloxy-4'-α-methylbutanoyloxybiphenyl. Compound (b) and compound (a) or (
By esterifying b), the following compound (compound with l=m=0 and n=1 in formula ()) can be synthesized. (Example 3, 11-13) 4-Alkyl-4'-β-methylpentanoyloxybiphenyl, 4-alkyloxy-4'-β-methylpentanoyloxybiphenyl. Also, by esterifying compound (g) and compound (a) or (b), the following compounds (those with l = 0, m = 1, n = 0 in formula ())
can be synthesized. 4-Alkyl-4'-biphenylyl (1-methylpropyl) carbonate, 4-alkyloxy-4'-biphenylyl (1-
Methylpropyl) carbonate. Further, the following compound (1=0, m=n=1 in formula ()) can be synthesized by esterifying compound (h) and compound (a) or (b). 4-Alkyl-4'-biphenylyl (2-methylbutyl) carbonate, 4-alkyloxy-4'-biphenylyl (2-
Table 1 shows the phase transition temperatures of representative compounds of formula (2) of the present invention.
(i) 4−(アセチルオキシ)−4′−アセチルビフエ
ニルの合成
ヒドロキシビフエニル503.6g(2.96mol)を、
1,2−ジクロルエタン2に懸濁させ、これに
塩化アセチル278g(3.54mol)を滴下し、50℃
で2時間加熱攪拌した。液が透明となつたので、
10℃まで冷却して、無水塩化アルミニウム850g
(6.37mol)を粉砕、小分けして1時間で投入し
た。10℃〜15℃に保持して、塩化アセチル278g
(3.54mol)を1時間で滴下し、2時間室温で攪
拌、50℃で2時間攪拌した。冷却して、6規定塩
酸約3に反応液を注ぎ、よくかきまぜた。生成
した固体を吸引濾過して集め、よく水洗、乾燥し
て、エタノール3から再結晶すると、4−(ア
セチルオキシ)−4′−アセチルビフエニル581.6g
が得られた。収率77.4%、mp.127.5℃。
(ii) 4−n−オクチルオキシ−4′−アセチルビフ
エニルの合成
4−アセチルオキシ−4′−アセチルビフエニル
80.0g(0.315mol)をエチレングリコールモノエ
チルエーテル300mlに懸濁させ、加熱攪拌した。
均一になつたところへ、水酸化カリウム50%水溶
液70gを注入し、30分間加熱還流した。ここへ1
−ブロモ−n−オクタン62.7g(0.325mol)を滴
下して5時間加熱還流した。空冷して、液を1
の氷中へあけ、トルエン2で抽出し、トルエン
層を酸洗い、アルカリ洗いして、水洗、中性にし
た。これをトルエン留去して固化させ、トルエン
1と活性炭で熱過、再結晶して、4−n−オ
クチルオキシ−4′−アセチルビフエニル77.5gを
得た。収率75.71%。このものはスメクチツクB
液晶相(SB)を示し、そのC−SB点は92.5℃,
SB−I点は132.9℃であつた。
(iii) 4−ヒドロキシ−4′−n−オクチルオキシビ
フエニルの合成
4−n−オクチルオキシ−4′−アセチルビフエ
ニル38.5g(0.119mol)とギ酸238g(5.17mol)、
トルエン200mlを60℃に加熱し、ここへ35%H2O2
水溶液160.7g(1.04mol)を70〜75℃に液温を保
ちながら、1.5時間で滴下した。こののち60〜70
℃で3時間加熱攪拌してから室温に冷却し、トル
エン1.5で抽出し、中性まで水洗して、乾燥し
た。トルエン除去後、エタノール200mlを加えて
加熱還流させ、少し冷却し40%水酸化ナトリウム
水溶液80mlを加え再び2時間、加熱還流した。こ
の液を6N塩酸1に注ぎよくかきまぜた。生成
した固体を吸引過して集め、トルエン300mlを
加えて、水を抜いて、再結晶して、4−ヒドロキ
シ−4′−n−オクチルオキシビフエニル18.5gを
得た。収率50.6%,mp.153.6℃。
(iv) (+)−S−α−メチルブタノイルクロライ
ドの合成
S−(−)−2−メチル−1−ブタノール167g
に水360mlを加えさらに炭酸ナトリウム41.3gを
加えて、室温で攪拌した。ここにあらかじめ約8
の水に溶しておいた過マンガン酸カリウム362
gを15〜20℃で1時間30分で滴下した。これを室
温で6時間攪拌し、つづけて45〜55℃の水浴で2
時間加熱攪拌した。その後吸引過して、過を
酸性とし、トルエン2で抽出して、常圧で蒸留
して、(+)−S−α−メチルブタン酸を得た。
収量73.5g(収率38.0%)、bp.173〜174℃,
〔α〕23 D(+)17.6。
これを170gの塩化チオニルと4時間加熱還流
させ、その後減圧下に過剰の塩化チオニルを留去
して粗製物を得た。これを精留して(+)−S−
α−メチルブタノイルクロライドを得た。
収量75.1g(収率86.5%)、bp,114〜116℃,
〔α〕23 D(+)17.2。
(v) 4−n−オクチルオキシ−4′−S−α−メチ
ルブタノイルオキシビフエニルの合成
4−ヒドロキシ−4′−(n−オクチルオキシ)
ビフエニル2.0g(6.71mmol)を乾燥ピリジン15
mlに溶解し()で合成した(+)−S−α−メ
チルブタノイルクロライド0.9g(7.47mmol)の
乾燥トルエン溶液10mlを滴下した。室温でよく振
とうし、60℃の水浴上で4時間加熱した。これに
トルエン50mlを加えて酸洗、アルカリ洗、水洗を
経た後、硫酸ナトリウム上で乾燥した。トルエン
除去後エタノール60mlと活性炭から熱過し、更
にエタノール50mlから再結晶して目的物である4
−n−オクチルオキシ−4−S−α−メチルブタ
ノイルオキシビフエニル0.8gを得た。このもの
はSC*相を示し、その相転移点は表1に示す通り
である。又その元素分析値は次の如く理論値とほ
ぼ一致した。
分析値 理論値(C25H35O3として)
C 78.4% 78.29%
H 9.1% 9.20%
実施例1と同様にして表1の実施例2〜4の化
合物を得た。
実施例 5
〔4−n−テトラデシルオキシ−4′−β−メチ
ルペンタノイルオキシビフエニル(()式で
l=0,m=0,n=1でX=C14H29Oのも
の)の合成〕
(i) 4−ヒドロキシ−4′−n−テトラデシルオキ
シビフエニルの合成
実施例1()〜()で合成した4−ヒドロ
キシ−4′−n−オクチルオキシビフエニルと同様
な方法で4−ヒドロキシ−4′−テトラデシルオキ
シビフエニルを合成した。
4−アセチル−4′−n−テトラデシルオキシビ
フエニル
C−SB点112.1℃,SB−点123.2℃4−ヒド
ロキシ−4′−n−テトラデシルオキシビフエニル
mp.144
(ii) (+)−S−β−メチルペンタノイルクロラ
イドの合成
フラスコに金属マグネシウムリボン12.4gを入
れ攪拌し、乾燥した。これを冷却して乾燥エーテ
ル50mlを入れて、ヨウ化エチルを少量添加し、温
めて、市販の(−)−S−1−ブロモー2−メチ
ルブタン70gを冷却しながら加えた。その後1.5
時間室温で攪拌した。別にドライアイスを粉砕し
ておき、ここに上記のものを注入した。これを
6N塩酸で酸性として、トルエン200mlで抽出し、
水洗してトルエンを留去した。
これを過剰の塩化チオニルと3時間加熱還流し
てその後、減圧下に塩化チオニルを留去し、減圧
蒸留することにより、(+)−S−β−メチルペン
タノイルクロライドを得た。
収量25.3g(収率43.6%),b.p.197〜198℃,
〔α〕29 D+5.4°。
(iii) エステル化
()の4−ヒドロキシ−4′−n−テトラデシ
ルオキシビフエニル0.5gを乾燥ピリジン20mlに
溶解して、これに()で合成した(+)−S−
β−メチルペンタノイルクロライド0.2gを滴下、
さらに乾燥トルエン15mlを注入して、室温でよく
振とうし、更に60℃の水浴上で3時間、加熱し
た。これを室温に冷却、トルエン50mlを加えて、
6N塩酸100mlで2度洗浄、さらに2Nアルカリ水
で2度洗浄した後、飽和食塩水で数回洗浄して中
性とし、硫酸ナトリウム上で乾燥した。これをト
ルエン留去して、エタノール40mlを用いて熱
過、再結晶して、目的の(S)−4−テトラデシ
ルオキシ−4′−β−メチルペンタノイルオキシビ
フエニル0.2gを得た。相転移点は表1に示した
通りである。又、その元素分析値は次の如く理論
値とほぼ一致した。
分析値 理論値(C49H48O3として)
C 83.5% 83.28%
H 8.2% 8.39%
実施例5と同様にして表1の実施例6〜8の化
合物を得た。
実施例9 (使用例1)
4−エチル−4′−シアノビフエニル 20重量%
4−ペンチル−4′−シアノビフエニル 40重量%
4−オクチルオキシ−4′−シアノビフエニル
25重量%
4−ペンチル−4′−シアノターフエニル
15重量%
からなるネマチツク液晶組成物をポリビニルアル
コール(PVA)を塗布し、その表面をラビング
して平行配向処理を施した透明電極からなるセル
(電極間隔10μm)に注入してTN型表示セルと
し、これを偏光顕微鏡下で観察したところ、リバ
ース・ドメインを生じているものが観察された。
上記のネマチツク液晶組成物に本願の実施例1
の化合物を0.1重量%添加したものを使用して同
様にTNセルとして観察したところリバース・ド
メインは解消され、均一なネマチツク相が観察さ
れた。
実施例10 (使用例2)
化学式
(但し、*は光学活性炭素を示す)
で表わされる化合物80重量%、本願実施例2の化
合物及び実施例6の化合物各10重量%からなる混
合物は、44℃までSC*相を示し、それ以上の温度
でSA相を示し、69℃で等方性液体となる。
この混合物を、PVAを塗布し、表面をラビン
グして平行配向処理を施した透明電極を備えたセ
ルに注入し、50Vの直流電圧を印加しながら、
SC*相になるまで徐冷したところ均一なモノドメ
インセルが得られた。この液晶セルを直交ニコル
状態に配置した2枚の偏光子の間にはさみ15V,
0.5Hzの低周波数の交流を印加したところ、明瞭
なスイツチング動作が観察され、非常にコントラ
ストも良く、応答速度が速い(2msec)液晶表
示素子が得られた。
尚、この液晶組成物の自発分極の直交Psは
4.5nc/cm2であつた。
実施例11 (使用例3)
本願実施例1、実施例3、実施例6、実施例5
の化合物各々20重量%及び以下の式で示される二
つの化合物
各々10重量%からなる混合物は86℃までSC*相
を示し、それ以上の温度でSA相を示し、101℃で
等方性液体となる。
この混合物にアントラキノン系色素のD−16
(BDH社製品)を3重量%添加していわゆるゲス
ト・ホスト型にしたものを使用例2と同様なセル
に注入し、1枚の偏光子を偏光面が分子軸に垂直
になるように配置し、0.5Hz,15Vの低周波数の
交流を印加したところ、明瞭なスイツチング動作
が観察され、非常にコントラストが良く、応答速
度が速い(2msec)カラー液晶表示素子が得ら
れた。
尚、この液晶組成物の自発分極の値Psは
3.6nc/cm2であつた。
(i) Synthesis of 4-(acetyloxy)-4'-acetylbiphenyl 503.6g (2.96mol) of hydroxybiphenyl,
Suspended in 1,2-dichloroethane 2, added dropwise 278 g (3.54 mol) of acetyl chloride, and heated at 50°C.
The mixture was heated and stirred for 2 hours. The liquid became clear, so
Cool to 10℃ and add 850g of anhydrous aluminum chloride.
(6.37 mol) was pulverized, divided into portions, and added over 1 hour. Acetyl chloride 278g kept at 10℃~15℃
(3.54 mol) was added dropwise over 1 hour, and the mixture was stirred at room temperature for 2 hours and then at 50°C for 2 hours. After cooling, the reaction solution was poured into about 3 liters of 6N hydrochloric acid and stirred well. The generated solid was collected by suction filtration, thoroughly washed with water, dried, and recrystallized from ethanol 3 to yield 581.6 g of 4-(acetyloxy)-4'-acetylbiphenyl.
was gotten. Yield 77.4%, mp.127.5℃. (ii) Synthesis of 4-n-octyloxy-4'-acetylbiphenyl 4-acetyloxy-4'-acetylbiphenyl
80.0 g (0.315 mol) was suspended in 300 ml of ethylene glycol monoethyl ether and stirred with heating.
When the mixture became homogeneous, 70 g of a 50% potassium hydroxide aqueous solution was injected, and the mixture was heated under reflux for 30 minutes. here 1
62.7 g (0.325 mol) of -bromo-n-octane was added dropwise, and the mixture was heated under reflux for 5 hours. Cool in air and reduce the liquid to 1
The mixture was poured into ice, extracted with 2 portions of toluene, and the toluene layer was washed with acid, alkali, and water to make it neutral. This was solidified by distilling off toluene and recrystallized by heating with 1 toluene and activated carbon to obtain 77.5 g of 4-n-octyloxy-4'-acetylbiphenyl. Yield 75.71%. This thing is Smekchitsuku B
It shows a liquid crystal phase (SB), and its C-SB point is 92.5℃,
The SB-I point was 132.9°C. (iii) Synthesis of 4-hydroxy-4'-n-octyloxybiphenyl 38.5 g (0.119 mol) of 4-n-octyloxy-4'-acetylbiphenyl and 238 g (5.17 mol) of formic acid.
Heat 200ml of toluene to 60℃ and add 35% H2O2 here
160.7 g (1.04 mol) of an aqueous solution was added dropwise over 1.5 hours while maintaining the liquid temperature at 70 to 75°C. 60-70 later
The mixture was heated and stirred at ℃ for 3 hours, cooled to room temperature, extracted with 1.5 g of toluene, washed with water until neutral, and dried. After removing toluene, 200 ml of ethanol was added and the mixture was heated to reflux, cooled slightly, 80 ml of 40% aqueous sodium hydroxide solution was added, and the mixture was heated to reflux again for 2 hours. This solution was poured into 1 part of 6N hydrochloric acid and stirred well. The produced solid was collected by suction, 300 ml of toluene was added, water was removed and recrystallized to obtain 18.5 g of 4-hydroxy-4'-n-octyloxybiphenyl. Yield 50.6%, mp.153.6℃. (iv) Synthesis of (+)-S-α-methylbutanoyl chloride S-(-)-2-methyl-1-butanol 167g
360 ml of water was added to the mixture, followed by 41.3 g of sodium carbonate, and the mixture was stirred at room temperature. Approximately 8
Potassium permanganate 362 dissolved in water
g was added dropwise at 15 to 20°C over 1 hour and 30 minutes. This was stirred at room temperature for 6 hours and then placed in a water bath at 45-55°C for 2 hours.
The mixture was heated and stirred for hours. Thereafter, the residue was filtered under suction, acidified, extracted with 2 toluene, and distilled at normal pressure to obtain (+)-S-α-methylbutanoic acid. Yield 73.5g (yield 38.0%), bp.173-174℃,
[α] 23 D (+) 17.6. This was heated under reflux with 170 g of thionyl chloride for 4 hours, and then excess thionyl chloride was distilled off under reduced pressure to obtain a crude product. This is rectified and (+)-S-
α-Methylbutanoyl chloride was obtained. Yield 75.1g (yield 86.5%), bp, 114-116℃,
[α] 23 D (+) 17.2. (v) Synthesis of 4-n-octyloxy-4'-S-α-methylbutanoyloxybiphenyl 4-hydroxy-4'-(n-octyloxy)
2.0g (6.71mmol) of biphenyl in dry pyridine 15
10 ml of a dry toluene solution containing 0.9 g (7.47 mmol) of (+)-S-α-methylbutanoyl chloride synthesized in () was added dropwise. The mixture was shaken well at room temperature and heated on a 60°C water bath for 4 hours. To this was added 50 ml of toluene, and the mixture was washed with acid, alkaline, and water, and then dried over sodium sulfate. After removing toluene, heat from 60 ml of ethanol and activated carbon, and then recrystallize from 50 ml of ethanol to obtain the desired product 4.
0.8 g of -n-octyloxy-4-S-α-methylbutanoyloxybiphenyl was obtained. This material exhibits an SC * phase, and its phase transition point is as shown in Table 1. Moreover, the elemental analysis values almost agreed with the theoretical values as shown below. Analytical value Theoretical value (as C25H35O3 ) C 78.4% 78.29% H 9.1% 9.20% Compounds of Examples 2 to 4 in Table 1 were obtained in the same manner as in Example 1. Example 5 [4-n-tetradecyloxy-4'-β-methylpentanoyloxybiphenyl (formula () where l=0, m=0, n=1 and X=C 14 H 29 O) (i) Synthesis of 4-hydroxy-4'-n-tetradecyloxybiphenyl Same method as 4-hydroxy-4'-n-octyloxybiphenyl synthesized in Example 1 () to (). 4-hydroxy-4'-tetradecyloxybiphenyl was synthesized. 4-Acetyl-4'-n-tetradecyloxybiphenyl C-SB point 112.1℃, SB-point 123.2℃ 4-Hydroxy-4'-n-tetradecyloxybiphenyl mp.144 (ii) (+)- Synthesis of S-β-methylpentanoyl chloride 12.4 g of metal magnesium ribbon was placed in a flask, stirred, and dried. After cooling, 50 ml of dry ether was added, a small amount of ethyl iodide was added, the mixture was warmed, and 70 g of commercially available (-)-S-1-bromo-2-methylbutane was added with cooling. then 1.5
Stirred at room temperature for an hour. Separately, dry ice was crushed, and the above items were injected into it. this
Acidified with 6N hydrochloric acid, extracted with 200ml of toluene,
It was washed with water and toluene was distilled off. This was heated under reflux with excess thionyl chloride for 3 hours, then thionyl chloride was distilled off under reduced pressure, and (+)-S-β-methylpentanoyl chloride was obtained by distilling under reduced pressure. Yield 25.3g (yield 43.6%), bp197-198℃,
[α] 29 D +5.4°. (iii) Esterification Dissolve 0.5 g of 4-hydroxy-4'-n-tetradecyloxybiphenyl in () in 20 ml of dry pyridine, and add (+)-S- synthesized in ().
Drop 0.2 g of β-methylpentanoyl chloride,
Furthermore, 15 ml of dry toluene was injected, the mixture was thoroughly shaken at room temperature, and further heated on a 60°C water bath for 3 hours. Cool this to room temperature, add 50ml of toluene,
After washing twice with 100 ml of 6N hydrochloric acid and twice with 2N alkaline water, it was washed several times with saturated saline to make it neutral, and dried over sodium sulfate. This was distilled off with toluene, heated and recrystallized using 40 ml of ethanol to obtain 0.2 g of the desired (S)-4-tetradecyloxy-4'-β-methylpentanoyloxybiphenyl. The phase transition points are shown in Table 1. Moreover, the elemental analysis values almost agreed with the theoretical values as shown below. Analytical value Theoretical value (as C49H48O3 ) C 83.5% 83.28% H 8.2% 8.39% Compounds of Examples 6 to 8 in Table 1 were obtained in the same manner as in Example 5. Example 9 (Use example 1) 4-ethyl-4'-cyanobiphenyl 20% by weight 4-pentyl-4'-cyanobiphenyl 40% by weight 4-octyloxy-4'-cyanobiphenyl
25% by weight 4-pentyl-4'-cyanoterphenyl
A nematic liquid crystal composition consisting of 15% by weight was injected into a cell (electrode spacing 10 μm) consisting of transparent electrodes (electrode spacing 10 μm) coated with polyvinyl alcohol (PVA) and subjected to parallel alignment treatment by rubbing the surface. When this was observed under a polarizing microscope, a reverse domain was observed. Example 1 of the present invention for the above nematic liquid crystal composition
When 0.1% by weight of the compound was added and observed in the same manner as a TN cell, the reverse domain was eliminated and a uniform nematic phase was observed. Example 10 (Usage example 2) Chemical formula (However, * indicates optically active carbon.) A mixture consisting of 80% by weight of the compound represented by and 10% by weight each of the compound of Example 2 and the compound of Example 6 exhibited an SC * phase up to 44°C, and It exhibits SA phase at temperatures above, and becomes an isotropic liquid at 69℃. This mixture was injected into a cell equipped with transparent electrodes coated with PVA and subjected to parallel alignment treatment by rubbing the surface, and while applying a DC voltage of 50V.
When it was slowly cooled until it reached the SC * phase, a uniform monodomain cell was obtained. This liquid crystal cell was sandwiched between two polarizers arranged in a crossed Nicol state at 15V.
When a low frequency alternating current of 0.5 Hz was applied, a clear switching operation was observed, and a liquid crystal display element with very good contrast and fast response speed (2 msec) was obtained. The orthogonal Ps of the spontaneous polarization of this liquid crystal composition is
It was 4.5nc/ cm2 . Example 11 (Usage example 3) Example 1, Example 3, Example 6, Example 5
20% by weight each of the compounds and two compounds represented by the following formulas: A mixture consisting of 10% by weight of each exhibits an SC * phase up to 86°C, an SA phase above that temperature, and becomes an isotropic liquid at 101°C. Add the anthraquinone dye D-16 to this mixture.
(BDH product) was added in a so-called guest-host type by adding 3% by weight and injected into the same cell as in Example 2, and one polarizer was placed so that the plane of polarization was perpendicular to the molecular axis. However, when a low frequency alternating current of 0.5 Hz and 15 V was applied, a clear switching operation was observed, and a color liquid crystal display element with very good contrast and a fast response speed (2 msec) was obtained. The spontaneous polarization value Ps of this liquid crystal composition is
It was 3.6nc/ cm2 .
Claims (1)
ルキル基又は、アルキルオキシ基を示し、lは0
を、m及びnは0又は1をそれぞれ示す。又、*
は光学活性炭素原子を示す。)で表わされる化合
物。 2 一般式 (但し、上式に於いて、Xは炭素数1〜18のア
ルキル基又は、アルキルオキシ基を示し、lは0
を、m及びnは0又は1をそれぞれ示す。又、*
は光学活性炭素原子を示す。)で表わされる化合
物を少なくとも1種含有することを特徴とする液
晶組成物。 3 複数の()式の化合物からなる特許請求の
範囲第2項記載のカイラルスメクチツク液晶組成
物。 4 複数のネマチツク液晶化合物を含む特許請求
の範囲第2項に記載のカイラルネマチツク液晶組
成物。[Claims] 1. General formula (However, in the above formula, X represents an alkyl group having 1 to 18 carbon atoms or an alkyloxy group, and l is 0
, m and n represent 0 or 1, respectively. or,*
indicates an optically active carbon atom. ). 2 General formula (However, in the above formula, X represents an alkyl group having 1 to 18 carbon atoms or an alkyloxy group, and l is 0
, m and n represent 0 or 1, respectively. or,*
indicates an optically active carbon atom. ) A liquid crystal composition containing at least one compound represented by: 3. The chiral smectic liquid crystal composition according to claim 2, which comprises a plurality of compounds of formula (). 4. The chiral nematic liquid crystal composition according to claim 2, which contains a plurality of nematic liquid crystal compounds.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13814883A JPS6051147A (en) | 1983-07-28 | 1983-07-28 | Liquid crystal substance and liquid crystal composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13814883A JPS6051147A (en) | 1983-07-28 | 1983-07-28 | Liquid crystal substance and liquid crystal composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6051147A JPS6051147A (en) | 1985-03-22 |
JPH0564134B2 true JPH0564134B2 (en) | 1993-09-14 |
Family
ID=15215128
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13814883A Granted JPS6051147A (en) | 1983-07-28 | 1983-07-28 | Liquid crystal substance and liquid crystal composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6051147A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60218358A (en) * | 1984-04-13 | 1985-11-01 | Ajinomoto Co Inc | Liquid crystal |
JPS6143A (en) * | 1984-06-11 | 1986-01-06 | Chisso Corp | Ferroelectric liquid crystal and liquid crystal composition |
JPH0717905B2 (en) * | 1985-05-09 | 1995-03-01 | 旭硝子株式会社 | Liquid crystal composition |
JPS63165345A (en) * | 1986-12-26 | 1988-07-08 | Chisso Corp | Optically active-2-methyl-alkanoates and utilized substance thereof |
US5397504A (en) * | 1987-05-29 | 1995-03-14 | Kanto Kagaku Kabushiki Kaisha | Biphenyl compound |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5219641A (en) * | 1975-08-06 | 1977-02-15 | Merck Patent Gmbh | Biphenyl esters |
-
1983
- 1983-07-28 JP JP13814883A patent/JPS6051147A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5219641A (en) * | 1975-08-06 | 1977-02-15 | Merck Patent Gmbh | Biphenyl esters |
Also Published As
Publication number | Publication date |
---|---|
JPS6051147A (en) | 1985-03-22 |
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