JPH02275839A - Optically active liquid crystal compound and liquid crystal composition - Google Patents
Optically active liquid crystal compound and liquid crystal compositionInfo
- Publication number
- JPH02275839A JPH02275839A JP2071532A JP7153290A JPH02275839A JP H02275839 A JPH02275839 A JP H02275839A JP 2071532 A JP2071532 A JP 2071532A JP 7153290 A JP7153290 A JP 7153290A JP H02275839 A JPH02275839 A JP H02275839A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- formulas
- liquid crystal
- tables
- optically active
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 51
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 239000004990 Smectic liquid crystal Substances 0.000 claims abstract description 21
- 125000005843 halogen group Chemical group 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 5
- 230000002269 spontaneous effect Effects 0.000 abstract description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- XZXHVMAUZKUYMJ-UHFFFAOYSA-N 5-methylheptyl 2-fluoro-4-[4-(4-octoxyphenyl)benzoyl]oxybenzoate Chemical compound C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(=O)OC=2C=C(F)C(C(=O)OCCCCC(C)CC)=CC=2)C=C1 XZXHVMAUZKUYMJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 230000003449 preventive effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- -1 phenyl ester Chemical class 0.000 description 13
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004988 Nematic liquid crystal Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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 2
- 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
- GIMXWZYFIFOCBJ-UHFFFAOYSA-N 2-fluorobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(F)=C1 GIMXWZYFIFOCBJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HCMYIMLJCBPZMK-UHFFFAOYSA-N 4-(4-octoxyphenyl)benzoyl chloride Chemical compound C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(C(Cl)=O)C=C1 HCMYIMLJCBPZMK-UHFFFAOYSA-N 0.000 description 2
- NZNICZRIRMGOFG-UHFFFAOYSA-N 4-decoxybenzoic acid Chemical compound CCCCCCCCCCOC1=CC=C(C(O)=O)C=C1 NZNICZRIRMGOFG-UHFFFAOYSA-N 0.000 description 2
- QFPMTKPMXXKCNW-UHFFFAOYSA-N 4-decoxybenzoyl chloride Chemical compound CCCCCCCCCCOC1=CC=C(C(Cl)=O)C=C1 QFPMTKPMXXKCNW-UHFFFAOYSA-N 0.000 description 2
- HYDBMGBHFBGQAC-UHFFFAOYSA-N 5-methylheptyl 2-fluoro-4-hydroxybenzoate Chemical compound CCC(C)CCCCOC(=O)C1=CC=C(O)C=C1F HYDBMGBHFBGQAC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003098 cholesteric effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- FYXQIMAAEMCZLV-UHFFFAOYSA-N ethyl 4-(4-hydroxyphenyl)benzoate Chemical compound C1=CC(C(=O)OCC)=CC=C1C1=CC=C(O)C=C1 FYXQIMAAEMCZLV-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- XXDKRMQJHKMZPC-UHFFFAOYSA-N octan-2-yl 4-methylbenzenesulfonate Chemical compound CCCCCCC(C)OS(=O)(=O)C1=CC=C(C)C=C1 XXDKRMQJHKMZPC-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007858 starting material 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】
〔利用分野〕
本発明は新規な液晶物質および該液晶物質を含有する液
晶組成物に関し、さらに詳しくは光学活性基を有するカ
イラル液晶物質およびそれらを含有するカイラル液晶組
成物に関する。Detailed Description of the Invention [Field of Application] The present invention relates to a novel liquid crystal substance and a liquid crystal composition containing the liquid crystal substance, and more particularly to a chiral liquid crystal substance having an optically active group and a chiral liquid crystal composition containing the same. Regarding.
（従来の技術〕
現在、液晶表示素子としてはＴ Ｎ （Ｔｗｉｓｔｅｄ
Ｎｅｍ−ａｔｉｃ）型表示方式が最も広く用いられて
いるが、発光型表示素子（エレクトロルミネッセンス、
プラズマデイスプレィ等）と比較して応答速度が劣って
いる。この点における改善は種々試みられているにもか
かわらず、大巾な改善の可能性はあまり残っていないよ
うである。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。その一つに強
誘電性液晶を利用する表示方式（Ｎ、Ａ、Ｃ１ａｒｋら
； Ａｐｐｌｉｅｄ Ｐｈｙｓ。(Prior art) Currently, T N (Twisted
Although the nem-atic) type display system is the most widely used, there are also light-emitting display elements (electroluminescence,
The response speed is inferior to that of other devices (such as plasma displays). Although various attempts have been made to improve this point, 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 the TN type display element. One of them is a display method that uses ferroelectric liquid crystals (N, A, C1ark et al.; Applied Phys.
１ｅｔｔ、、３６，８９９（１９８０））がある、この
方式は強誘電性液晶のカイラルスメクチックＣ相（以下
ＳＣ０相と略称する）あるいはカイラルスメクチックＨ
相（以下ＳＨ“相と略称する）を利用するもので、それ
らの相が室温付近にある液晶材料が望まれている。1ett, 36, 899 (1980)), this method uses chiral smectic C phase (hereinafter abbreviated as SC0 phase) or chiral smectic H phase of ferroelectric liquid crystal.
There is a desire for a liquid crystal material that utilizes phases (hereinafter abbreviated as SH" phase) and whose phases are around room temperature.
（発明の目的）
本発明は強誘電性液晶を利用する表示方式に適した液晶
物質の提供を主たる目的として、光学活性基を有する液
晶物質を種々提供することである。(Object of the Invention) The main object of the present invention is to provide various liquid crystal materials having optically active groups, with the main purpose of providing liquid crystal materials suitable for display systems using ferroelectric liquid crystals.
本発明の化合物は、次の（１１〜（４）である。 The compounds of the present invention are the following (11 to (4)).
〔上式において、Ｘ！はハロゲン原子を示し、Ｒｔは炭
素数４〜１８のアルキル基もしくはアルコキシ基、
Ｒ１は、
（ここで、Ｒ′ は炭素数２〜１０のアルキル基、ｙは
２〜１０．、ｌは１〜１０を示す、）で表わされる光学
活性基、ｎはＯもしくは１である。〕で表わされる光学
活性液晶化合物。[In the above formula, X! represents a halogen atom, Rt is an alkyl group or alkoxy group having 4 to 18 carbon atoms, R1 is an alkyl group having 2 to 10 carbon atoms, y is 2 to 10, and l is 1 to 1. 10), n is O or 1; ] An optically active liquid crystal compound represented by
（２） 一般式 示す、）で表わされる光学活性液晶化合物。(2) General formula An optically active liquid crystal compound represented by ).
（４１（ＩＩＩ）式のＲｘ ”が
〔上式において、Ｘ２はハロゲン原子を示し、Ｒ′Ｉ
は、
（ここで、Ｒ′ は炭素数２〜１０のアルキル基、ｙ
は２〜１０を示す、）で表わされる光学活性基、Ｒ１は
炭素数４〜１８のアルキル基、アルコキシ基もしくはア
ルコキシカルボニル基、ｎはＯもしくはｌを示す、〕で
表わされる光学活性液晶化合物。(41 (III) Formula Rx '' is [In the above formula, X2 represents a halogen atom, R'I
(Here, R' is an alkyl group having 2 to 10 carbon atoms, y
is 2 to 10, R1 is an alkyl group, alkoxy group, or alkoxycarbonyl group having 4 to 18 carbon atoms, and n is O or l.
（３） 一般式
〔上式において、Ｘ８はハロゲン原子、ｎは０もしくは
１を示し、Ｒ，は炭素数４〜１８のアルキル基またはア
ルコキシ基、Ｒ７′は光学活性基を（ここでＸ＋ｚは０
〜１０、Ｒ′は炭素数２〜ｌＯのアルキル基を示す。）
で示される光学活性基である第３項記載の化合物。(3) General formula [In the above formula, X8 is a halogen atom, n is 0 or 1, R is an alkyl group or alkoxy group having 4 to 18 carbon atoms, R7' is an optically active group (where X+z is 0
~10, R' represents an alkyl group having 2 to 10 carbon atoms. )
4. The compound according to item 3, which is an optically active group represented by:
本発明の組成物は、つぎの（５）〜αｌである。The composition of the present invention has the following (5) to αl.
（５）前記（１）式で示される光学活性液晶化合物の少
くとも１種を１成分含有することを特徴とする少くとも
２成分以上からなるカイラルスメクチック液晶組成物。(5) A chiral smectic liquid crystal composition comprising at least two components, characterized in that it contains at least one optically active liquid crystal compound represented by the formula (1).
（６） 複数種の（Ｉ）式の化合物のみからなる前記
第（Ｉ）項記載のカイラルスメクチック液晶組成物。(6) The chiral smectic liquid crystal composition according to item (I) above, which comprises only a plurality of compounds of formula (I).
（７）前記（Ｉｆ）式で表わされる光学活性液晶化合物
の少くとも１種を１成分含有することを特徴とする、少
くとも２成分以上からなるカイラルスメクチック液晶組
成物。(7) A chiral smectic liquid crystal composition comprising at least two components, characterized in that it contains at least one optically active liquid crystal compound represented by the formula (If).
（８） 複数種の（ＩＩ）式の化合物のみからなる前
記第７項記載のカイラルスメクチック液晶組成物。(8) The chiral smectic liquid crystal composition according to item 7, which comprises only a plurality of compounds of formula (II).
（９） 前記（ＩＩＩ）式で表わされる光学活性液晶
化合物の少くとも１種を１成分含存することを特徴とす
る、少くとも２成分以上からなるカイラルスメクチック
液晶組成物。(9) A chiral smectic liquid crystal composition comprising at least two components, characterized in that it contains at least one optically active liquid crystal compound represented by formula (III).
Ｑｌ （Ｉ［［）式のＲ％が
（は（ＩＩＩ）式で表わされる光学活性液晶化合物の少
くとも１種を１成分含有する少なくとも２成分以上から
なるカイラルスメクチック液晶組成物を使用して構成さ
れることを特徴とする。Ql (I It is characterized by being
本発明の化合物をさらに具体的に示すと、つぎのように
わけられる。More specifically, the compounds of the present invention can be classified as follows.
（１）式でｎｗ−Ｑのもの
（［［）式でｙｌ ｗ Ｑのもの
（ここでＸ＋ｚは０〜１０、Ｒ′は炭素数２〜１０のア
ルキル基を示す、）で表わされる光学活性基である第９
項の液晶組成物。Optical activity represented by nw-Q in formula (1) ([[) in yl w Q (where X+z is 0 to 10 and R' represents an alkyl group having 2 to 10 carbon atoms) The 9th which is the basis
Liquid crystal composition.
αＤ 複数種の（ＩＩＩ）式の化合物のみからなる第１
０項記載のカイラルスメクチック液晶組成物。αD The first compound consisting only of multiple types of compounds of formula (III)
The chiral smectic liquid crystal composition according to item 0.
本発明の液晶素子は、前記（１）、 （Ｉｆ）もしく
Ｉ［［）式でｎ＝５Ｑのもの
（ＩＩＩ）式でｎ−１のもの
（上記各式において、ＲＩＩＲ１１Ｒ７Ｒｇ、Ｒｇ”は
前記と同じものを意味し、Ｒ２゜ＲＩＩＲ１＃は光学活
性基であり、ＸはＦ。The liquid crystal element of the present invention has the above formula (1), (If) or I means the same as , R2゜RIIR1# is an optically active group, and X is F.
ＣＺもしくはＢｒのハロゲン原子を示す）具体的な化合
物としてＣＩ）式の化合物は第１表、（ＩＩ）式の化合
物は第２表、（Ｉ［［）式の化合物は第３表に示す。Examples of specific compounds (representing a halogen atom of CZ or Br) are shown in Table 1 for compounds of formula CI), Table 2 for compounds of formula (II), and Table 3 for compounds of formula (I[[).
本発明の（Ｉ）式の化合物は下記のような経路により合
成される。The compound of formula (I) of the present invention is synthesized by the following route.
ＲＩ″■ＸキＣ０ＣＪ （Ａ ’ ）
本発明の（ＩＩＩ）式の化合物は、下記のような経路に
より合成される。RI''■XkiC0CJ (A') The compound of formula (III) of the present invention is synthesized by the following route.
Ｒ１８ｃｏｃ Ｉｔ（Ａ ’ ）
本発明の（ＩＩ）の化合物は、下記のような経路により
合成される。R18cocIt(A') The compound (II) of the present invention is synthesized by the following route.
（Ｂ） モしくは（Ｂ＃）式表わされる置換フェノール
類あるいは置換フェニルフェノール類にはっぎのような
ものがある。Substituted phenols or substituted phenylphenols represented by the formula (B) or (B#) include the following.
Ｙ。Y.
（式中Ｒはアルキル基を、Ｒ′″は炭素数４〜１８）光
学活性アルキル基を示し、ｘｚはハロゲン原子又は水素
原子を示し、ｎは０又は１である。）Ｘｔ”Ｆの化合物
として、たとえば２−フルオロハイドロキノン（３）を
原料としてっぎの工程で製造することができる。(In the formula, R represents an alkyl group, R''' represents an optically active alkyl group having 4 to 18 carbon atoms, xz represents a halogen atom or a hydrogen atom, and n is 0 or 1.) Compound of Xt''F For example, it can be produced using 2-fluorohydroquinone (3) as a raw material in the following steps.
（Ｂ′）式で表わされる化合物としてはつぎのちのがあ
る。The compounds represented by formula (B') include the following.
本発明の化合物の多くは単体でスメクチックＣ相を呈し
、その自発分極の大きさＰｓが、従来から知られている
ＳＣ“権化合物に比較して極めて大きい、それ故、本発
明の化合物はすぐれた強誘電性液晶化合物であるという
ことができる０本発明の化合物のＰｓ値は大きい、たと
えば、従来知られているｓｃ”権化合物、特開昭５３−
２２８８３号に記載されている次式の化合物
のｐｓ値が本発明者らの測定によれば約１ｎｃ／ｃｎ＋
”であり、それに比較して本発明の物質のＰｓ値が大き
いことがわかる。Many of the compounds of the present invention exhibit a smectic C phase as a single substance, and the magnitude of the spontaneous polarization Ps is extremely large compared to conventionally known SC compounds.Therefore, the compounds of the present invention are excellent. The compound of the present invention, which can be said to be a ferroelectric liquid crystal compound, has a large Ps value.
According to measurements by the present inventors, the ps value of the compound of the following formula described in No. 22883 is approximately 1 nc/cn+
”, and it can be seen that the Ps value of the substance of the present invention is larger than that.
また、傾斜角はその値が４５°に近づくほどゲスト・ホ
スト型の光スイツチング素子のコントラストにとって好
適であることが知られているが、本発明の化合物は、そ
の点においても、強誘電性液晶材料として極めて興味の
ある値を示している。Furthermore, it is known that the closer the tilt angle is to 45°, the better the contrast of a guest-host type optical switching device is. This shows extremely interesting values as a material.
Ｓ０１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。When the optical switching effect of the S01 phase is applied to a display element, there are three advantages compared to the TN display system. The first feature is that it responds very quickly, with a response time of 1
/100 or less.
第２の特徴はメモリー効果があることであり、上記の高
速応答性とあいまって、時分割駆動が容易である。第３
の特徴は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、グラフィック表示に非常に適している。The second feature is that it has a memory effect, which, combined with the above-mentioned high-speed response, facilitates time-division driving. Third
The characteristic of the TN display method is that the gray scale is achieved by adjusting the applied voltage, but there are difficult problems such as the temperature dependence of the threshold voltage and the voltage dependence of the response speed. However, SC*
When applying the optical phase switching effect, gradation can be easily obtained by adjusting the polarity reversal time, making it very suitable for graphic display.
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
分子のグイレフ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。There are two possible display methods; one method is a birefringence type that uses two polarizers, and the other method is a guest-host type that uses a dichroic dye. Since the "sc" phase has spontaneous polarization, by reversing the polarity of the applied voltage, the molecule is reversed using the helical axis as the rotation axis.SC*
A liquid crystal composition having a phase is injected into a liquid crystal display cell that has been subjected to alignment treatment so that the liquid crystal molecules are aligned parallel to the electrode surface, and two sheets of liquid crystal are placed so that the polarization plane of one side is parallel to the gylefter of the liquid crystal molecules. By sandwiching the liquid crystal cell between 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.
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。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.
一般にスメクチッ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っくりと冷却する。（１
℃〜２℃／ｈｒ）ことにより、液晶分子を配向させてい
るが、スメクチック相を呈する温度より高温域でコレス
テリック相を有する液晶物質では磁場の代わりに５０Ｖ
〜１００■の直流電圧を印加しながら、コレステリック
相を呈する温度から１℃／肩−の冷却速度でスメチック
相を呈する温度へ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。Generally, it is difficult to align liquid crystal molecules parallel to the glass wall in a smectic state, and the isotropic liquid is cooled very slowly in a magnetic field of tens of kilogauss or more. (1
℃~2℃/hr) to align liquid crystal molecules, but for liquid crystal materials that have a cholesteric phase at a temperature higher than the temperature at which they exhibit a smectic phase, a magnetic field of 50 V is used instead of a magnetic field.
A uniformly oriented monodomain state can be easily obtained by cooling from the temperature at which a cholesteric phase is exhibited to the temperature at which a smectic phase is exhibited at a cooling rate of 1 °C/shoulder while applying a DC voltage of ~100 μm. can.
なお、本発明の化合物に対応するラセミ体は、後で示さ
れる光学活性体の製法において原料として光学活性アル
コールの代りに相当するラセミ型アルコールを使用する
ことによって、同様に製造され、（Ｉ）、 （ＩＩ）
もしくは（Ｉ［［）で示される化合物とほぼ同じ相転移
点を示す。ただし、いうまでもなくラセミ体の場合はＳ
Ｃ″Ｉ相の代りにＳＣ相を、ＳＦ”相の代りにＳＦ相を
呈する。Note that the racemate corresponding to the compound of the present invention can be similarly produced by using the corresponding racemic alcohol instead of the optically active alcohol as a raw material in the method for producing the optically active substance shown later, and (I) , (II)
Or, it exhibits almost the same phase transition point as the compound represented by (I[[). However, needless to say, in the case of a racemate, S
It exhibits an SC phase instead of a C''I phase, and an SF phase instead of an SF'' phase.
本発明の化合物は、また、光学活性炭素原子を有するた
め、これをネマチック液晶に添加することによって涙れ
た構造を誘起する能力を有する。Since the compound of the present invention also has an optically active carbon atom, it has the ability to induce a teardrop structure by adding it to a nematic liquid crystal.
捩れた構造を有するネマチック液晶、すなわち、カイラ
ルネマチック液晶はＴＮ型表示素子のいわゆるリバース
・ドメイン（ｒｅｖｅｒｓｅ ｄｏｒａａｉｎ＋ Ｌ
ま模様）を生成することがないので本発明の化合物はリ
バース・ドメイン生成の防止剤として使用できる。A nematic liquid crystal with a twisted structure, that is, a chiral nematic liquid crystal, has a so-called reverse domain (reverse domain+L) of a TN type display element.
The compounds of the present invention can be used as inhibitors of reverse domain formation.
なお、原料の光学活性アルカノール類のうち、Ｓ（＋）
−２−オクタツール、Ｒ（−）−２−オクタノール、５
（−）−２−メチルブタノールは市販品として容易に入
手できるが、他の光学活性アルカノール類は現在のとこ
ろ高価で大量の使用には向かない。本発明者らは文献（
Ｒ，Ｈ，Ｐｉｃｋａｒｄら、Ｊ、Ｃｈｅｍ Ｓｏｃ、、
９９．４５＜１９１１））記載の方法に従って２−アル
カノールのラセミ体の光学分割をおこなって得られた光
学活性２−アルカノールを原料として使用したが、これ
らの光学活性アルカノニルを使用することによって（１
）式におけるＲＩＩＲ１＋（ＩＩ）式におけるＲ＋
、Ｒ１（ＩＩＩ）式におけるＲ１ ｒ Ｒ１”の異る
諸物質が得られる。しかし２−アルカノール類に関する
限りＲ１とＲ２＋ＲＩ ＊Ｒｔ ＋ もしくはＲ１と
Ｒ２＃′の鎖長による液晶相転移温度の変化はわずかで
あるので最も容易に入手し得る２−オクタツールおよび
２−メチルブタノール以外の光学活性アルカノールを原
料とすることに格別な利点はない、その他の光学活性原
料である光学活性１級アルコール類、すなわち
ｔｂ
ＣｚＨｓＣＨ−（ＣＨｔｈ ＯＨ
型のものは、上記５（−）−２−メチルブタノール−１
を出発原料として公知の方法により製造できる。Furthermore, among the optically active alkanols used as raw materials, S(+)
-2-octatool, R(-)-2-octanol, 5
Although (-)-2-methylbutanol is easily available as a commercial product, other optically active alkanols are currently expensive and unsuitable for large-scale use. The present inventors have described the literature (
R, H, Pickard et al., J, Chem Soc.
The optically active 2-alkanol obtained by optically resolving the racemic form of 2-alkanol according to the method described in 99.45<1911) was used as a raw material.
) RIIR1+ in formula (II) R+ in formula
, R1 (III), various substances with different R1 r R1'' in the formula are obtained. However, as far as 2-alkanols are concerned, the change in liquid crystal phase transition temperature depending on the chain length of R1 and R2 + RI *Rt + or R1 and R2 #' is There is no particular advantage in using optically active alkanols other than 2-octatool and 2-methylbutanol as raw materials, which are the most easily available optically active primary alcohols, which are other optically active raw materials; That is, the tb CzHsCH-(CHth OH type is the above-mentioned 5(-)-2-methylbutanol-1
It can be produced by a known method using as a starting material.
以下、実施例により本発明の光学活性液晶化合物につい
て、詳細に説明する。Hereinafter, the optically active liquid crystal compound of the present invention will be explained in detail with reference to Examples.
なお、以下の実施例においては原料の光学活性アルコー
ルとしてはＳ型のものを使用した例だけを記載するが、
Ｒ型の光学活性アルコールを原料とした場合にもそれぞ
れ同一の相転移温度のものが得られる。これは理論上か
らも当然のことである。ただし、旋光度、ら旋の捩れ向
き、自発分極の向きはＳ型とＲ型とでは逆になる。In addition, in the following examples, only examples using S type as the raw material optically active alcohol will be described,
Even when R-type optically active alcohol is used as a raw material, products with the same phase transition temperature can be obtained. This is logical from a theoretical point of view. However, the optical rotation, the direction of helical twist, and the direction of spontaneous polarization are opposite between the S type and the R type.
実施例１
〔光学活性 ４′−オクチルオキシ−４−ビフェニルカ
ルボン酸３−フルオロ−４−（５−メチルへブチルオキ
シカルボニル）フェニルエステル（次式の化合物１１ｈ
ｌ）の製造
２−フルオロ−４−ヒドロキシ安息香酸１５６ｇ（１，
０モル）に、５−５−メチルヘプタツール３０６ｇ（３
，０モル）、濃硫酸３０ｔａ１１．ベンゼン５００ｍｆ
を加え、１６時間還流し冷却したのち、２％ＮａＨＣＯ
，水、さらに水で中性になるまで洗浄する。溶媒を留去
し１８１ｇの光学活性２−フルオロ−４−ヒドロキシ安
息香酸５−メチルヘプチルエステルを得た。Example 1 [Optical activity 4'-octyloxy-4-biphenylcarboxylic acid 3-fluoro-4-(5-methylhebutyloxycarbonyl) phenyl ester (compound 11h of the following formula)
156 g of 2-fluoro-4-hydroxybenzoic acid (1,
0 mol), 306 g of 5-5-methylheptatool (3
, 0 mol), concentrated sulfuric acid 30ta11. benzene 500mf
After cooling under reflux for 16 hours, 2% NaHCO
,Wash with water, and then wash with water until it becomes neutral. The solvent was distilled off to obtain 181 g of optically active 2-fluoro-4-hydroxybenzoic acid 5-methylheptyl ester.
一方、４’−オクチルオキシ−４−ビフェニルカルボン
酸１０ ｇ （０，０３モル）に塩化チオニル５、０
ｇ （０，０４２モル）を加え１時間加熱還流したのち
過剰の塩化チオニルを留去してｌ１ｇの４′−オクチル
オキシ−４−ビフェニルカルボン酸クロリドを得た。On the other hand, 10 g (0.03 mol) of 4'-octyloxy-4-biphenylcarboxylic acid was mixed with 5.0 thionyl chloride.
g (0,042 mol) was added and heated under reflux for 1 hour, and then excess thionyl chloride was distilled off to obtain 11 g of 4'-octyloxy-4-biphenylcarboxylic acid chloride.
さきの光学活性２−フルオロ−４−ヒドロキシ安息香酸
５−メチルヘプチルエステル１０ ｇ （０，０３４モ
ル）をピリジン５０＋１１に溶解し、この溶液に４′−
オクチルオキシ−４−ビフェニルカルボン酸クロリド１
１．８ ｇ （０，０３４モル）を滴下し、５０〜６
０℃で２時間反応させた。−夜放置後トルエン３００削
！、水２００ｍｊ！を加えて撹拌し、そのトルエン層を
６Ｎ−ＨＣｌついで２Ｎ−苛性ソーダ水溶液で洗浄し、
さらに、中性になるまで水洗した。トルエンを留去し残
留物をエタノールで再結晶して目的物である光学活性４
′−オクチルオキシ−４−ビフェニルカルボン酸３−フ
ルオロ−４−（５−メチルへブチルオキシカルボニル）
フェニルエステル９．８ｇを得た。このものの相転移点
はｃ−ｓｃ”点７９．５℃、５ＣＩ−５Ａ点１４５．３
℃、５Ａ−１点１７４．２℃、であった。また、元素分
析値はつぎの如く計算値とよく一致した。10 g (0,034 mol) of optically active 2-fluoro-4-hydroxybenzoic acid 5-methylheptyl ester was dissolved in pyridine 50+11, and 4'-
Octyloxy-4-biphenylcarboxylic acid chloride 1
1.8 g (0,034 mol) was added dropwise, and 50-6
The reaction was carried out at 0°C for 2 hours. -Remove 300 toluene after leaving it overnight! , water 200mj! was added and stirred, and the toluene layer was washed with 6N-HCl and then with 2N-caustic soda aqueous solution,
Furthermore, it was washed with water until it became neutral. The toluene was distilled off and the residue was recrystallized with ethanol to obtain the target product, optically active 4.
'-Octyloxy-4-biphenylcarboxylic acid 3-fluoro-4-(5-methylhebutyloxycarbonyl)
9.8 g of phenyl ester was obtained. The phase transition point of this product is c-sc” point 79.5℃, 5CI-5A point 145.3
℃, 5A-1 point 174.2℃. Furthermore, the elemental analysis values were in good agreement with the calculated values as shown below.
実測値 計算値 （Ｃ３６ＨｅｓＯｓＦとして）
Ｃ７４，９０％ ７４．９７％
Ｈ７，９０％ ７．８７％
Ｆ ３．２０％ ３．２９％実施例２ （
使用例１）
４−エチＪト４ ′ −シアノビフェニル
２０重１％４−ベンチルー４ ′ −シア
ノビフェニル ４０重１％４−才
クチルオキシ−４′ −シアノビフェニル
２５１Ｆ１％４−ベンチルー４′ −シアノターフ
ェニル １５重１％からなるネマチ
ック液晶組成物を配向処理剤として、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電極間隔１０μｍの
セルに注入して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・ツイストドメインを生
じているのが観察された。Actual value Calculated value (as C36HesOsF)
C74,90% 74.97% H7,90% 7.87% F 3.20% 3.29%Example 2 (
Usage example 1) 4-ethyl-4'-cyanobiphenyl
20wt 1% 4-benthyl-4'-cyanobiphenyl 40wt 1% 4-cutyloxy-4'-cyanobiphenyl
A transparent electrode in which a nematic liquid crystal composition consisting of 251F 1% 4-benzene 4'-cyanoterphenyl 15% by weight was applied as an alignment agent, polyvinyl alcohol (PVA) was applied, and the surface was rubbed to perform parallel alignment treatment. When the cell was injected into a cell with an electrode spacing of 10 μm to obtain a TN type display cell and observed under a polarizing microscope, it was observed that a reverse twisted domain was formed.
この上記のネマチック液晶組成物に本発明の下記の化学
式で示される。The above nematic liquid crystal composition is represented by the following chemical formula of the present invention.
（化合動磁１４）
４光学活性液晶化合物を１重量％添加し、同様にＴＮ型
セルにて観察したところ、リバース・ツイストドメイン
は解消され、均一なネマチック相が観察された。(Combined magnetodynamic 14) When 1% by weight of the 4 optically active liquid crystal compound was added and similarly observed in a TN cell, the reverse twist domain was eliminated and a uniform nematic phase was observed.
実施例３
光学活性４’−（１−メチルへブチルオキシ）−４−ビ
フェニルカルボン酸３−フルオロ−４−へキシルオキシ
フェニルエステル（次式の化合物陽１９）の製造
Ｓ−（＋）−２−オクタツール２００ｇ（１，５４モル
）を乾燥ピリジン６００１１１１に溶解し、そこへ系内
の温度が１０℃以上にならないようにしながらＰ−）ル
エンスルホン酸クロリド２９２．８ ｇ（１，５４モル
）を乾燥トルエン４４０ｍ１に溶解した溶液を滴下する
０滴下終了後、室温で１時間撹拌したのち、系内の温度
を５０℃に加温し、そのまま２時間保ってから放冷する
。さらに水１１とトルエン５００ｔｓｌを加えて撹拌す
る０分離したトルエン層を６Ｎ−Ｈ（Ｊ、ついで２ Ｎ
−ＮａＯＨ水溶液で洗浄し、更に中性になるまで水洗
する。トルエンを留去すると残香として３２１．０ ｇ
の光学活性Ｐ−トルエンスルホン酸１−メチルヘプチル
エステルを得た。Example 3 Production of optically active 4'-(1-methylhebutyloxy)-4-biphenylcarboxylic acid 3-fluoro-4-hexyloxyphenyl ester (compound 19 of the following formula) S-(+)-2- 200 g (1.54 mol) of octatool was dissolved in dry pyridine 6001111, and 292.8 g (1.54 mol) of P-)luenesulfonic acid chloride was added thereto while ensuring that the temperature in the system did not rise above 10°C. After dropping a solution dissolved in 440 ml of dry toluene, the mixture was stirred at room temperature for 1 hour, and then the temperature inside the system was raised to 50° C., kept as it was for 2 hours, and then allowed to cool. Furthermore, add 11 tsl of water and 500 tsl of toluene and stir.The separated toluene layer is heated with 6N-H (J, then 2N
-Wash with an aqueous NaOH solution and further wash with water until neutral. When toluene is distilled off, 321.0 g remains as a residual aroma.
Optically active P-toluenesulfonic acid 1-methylheptyl ester was obtained.
一方、４ ’−ヒドロキシー４−ビフェニルカルボン酸
エチルエステル３８．７ ｇ （０，１６モル）をエタ
ノール２００ｓ＋ｊ！に溶解し、さらに水酸化カリウム
９ｇ（０，１６モル）を加え溶解する。これにさきに得
られた光学活性Ｐ−）ルエンスルホン酸１−メチルヘプ
チルエステル５０ｇ（０，１８％ル）を加えて還流しな
がら４時間反応を行なったが、その後冷却して、トルエ
ン２００ｍｊ！と６Ｎ−Ｈ（Ｊ ５０ ｍｌを加え、ト
ルエン層を２ Ｎ −ＮａＯ）１水溶液で洗浄したのち
中性になるまで水洗した。On the other hand, 38.7 g (0.16 mol) of 4'-hydroxy-4-biphenylcarboxylic acid ethyl ester was mixed with ethanol 200s+j! Further, 9 g (0.16 mol) of potassium hydroxide is added and dissolved. To this was added 50 g (0.18%) of the optically active P-)luenesulfonic acid 1-methylheptyl ester obtained earlier, and the reaction was carried out under reflux for 4 hours. and 6N-H (J 50 ml) were added, and the toluene layer was washed with 1 aqueous solution of 2N-NaO and then with water until it became neutral.
トルエンを留去し残香にエタノール６１ｍ１％水酸化ナ
トリウム５．３ｇ（０，１３モル）水２５ｍ１を加え１
０分間加熱還流した。冷却し６Ｎ−ＨＣｌを加え析出し
た結晶を炉別し、さらに酢酸から再結晶を行ない、光学
活性４’−（１−メチルへブチルオキシ）−４−ビフェ
ニルカルボン酸２３．４ ｇを得た。このものは液晶相
を示しその相転移点は、Ｃ−５ｃ点１６０℃、 ｓｃ”
″−ｃｈ点１７７り、ｃｈ−■点１９６℃であった。Toluene was distilled off, and to the residual aroma was added 61 ml of ethanol, 5.3 g (0.13 mol) of 1% sodium hydroxide, and 25 ml of water.
The mixture was heated to reflux for 0 minutes. After cooling, 6N-HCl was added, and the precipitated crystals were separated in a furnace and further recrystallized from acetic acid to obtain 23.4 g of optically active 4'-(1-methylhebutyloxy)-4-biphenylcarboxylic acid. This material exhibits a liquid crystal phase and its phase transition point is C-5c point at 160°C, sc”
''-ch point was 177 degrees Celsius, and ch-ch point was 196 degrees Celsius.
この光学活性４’−（１−メチルへブチルオキシ）−４
−ビフェニルカルボン酸２０ ｇ （０，０６３モル）
に塩化チオニル１１．３ ｇ （０，０９５モル）を加
え、１時間加熱還流したのち過剰の塩化チオニルを留去
して２１ｇの光学活性４’−（１−メチルへブチルオキ
シ）−４−ビフェニルカルボン酸クロリドを得た。This optically active 4'-(1-methylhebutyloxy)-4
-20 g (0,063 mol) of biphenylcarboxylic acid
11.3 g (0,095 mol) of thionyl chloride was added to the solution, heated under reflux for 1 hour, and then excess thionyl chloride was distilled off to give 21 g of optically active 4'-(1-methylhebutyloxy)-4-biphenylcarboxylic acid. Acid chloride was obtained.
０−フルオロフェノール３００ｇ（２，６８モル）。300 g (2,68 mol) of 0-fluorophenol.
ヘキシルブロマイド４８５．９ ｇ （２，９４モル）
。Hexyl bromide 485.9 g (2.94 mol)
.
水酸化カリウム１６５．２（２，９４モル）、エタノー
ル１．８１の混合物を１０時間還流した。エタノールを
留去したのち残香にトルエンを加え撹拌したのち２ Ｎ
−Ｎａ０）１水溶液次いで水で洗浄した。無水硫酸マグ
ネシウム上乾燥したのちトルエンを留去し、残香を蒸留
にてＯ−フルオロヘキシルオキシベンゼン４９７ｇを得
た。ｂｐ １ ｍｍＨｇ ７８．０℃であった。A mixture of 165.2 (2.94 moles) of potassium hydroxide and 1.81 of ethanol was refluxed for 10 hours. After distilling off the ethanol, toluene was added to the residual aroma and stirred, then 2N
-Na0)1 aqueous solution and then washed with water. After drying over anhydrous magnesium sulfate, toluene was distilled off and the residual aroma was distilled to obtain 497 g of O-fluorohexyloxybenzene. bp 1 mmHg 78.0°C.
０−フルオロへキシルオキシベンゼン２５０ｇ（１，３
モル）、無水塩化アルミニウム１９０．７ ｇ（１，４
３モル）、二硫化炭素６００ｍｊ！の混合物に１１℃以
下で塩化アセチル１０７．２ｇ（１，４モル）を滴下し
た。室温で２時間３０分撹拌したのち氷水に投入し、析
出した結晶を決別しエタノールより再結晶を行ない１０
３ｇの３−フルオロ−４−ヘキシルオキシアセトフェノ
ンを得た。250 g of 0-fluorohexyloxybenzene (1,3
mol), anhydrous aluminum chloride 190.7 g (1,4
3 mol), carbon disulfide 600mj! 107.2 g (1.4 mol) of acetyl chloride was added dropwise to the mixture at 11° C. or below. After stirring at room temperature for 2 hours and 30 minutes, the mixture was poured into ice water, separated from the precipitated crystals, and recrystallized from ethanol.
3 g of 3-fluoro-4-hexyloxyacetophenone was obtained.
ａｐ１２７℃であった。ap was 127°C.
この３−フルオロ−４−ヘキシルオキシアセトフェノン
５０ｇ（０，２１モル）、ギ酸６４４ｇの混合物に注意
深く過酸化水素２３８ｇを加えた後５０℃で４時間４５
分撹拌した。この反応液に亜硫酸水素ナトリウム２１８
．５ ｇ （２，１モル）、水４００ｍｊ！の混合物を
１０℃以下で加えトルエン１５０ｍ１！を加え抽出した
。トルエンを留去し３−フルオロ−４−へキシルオキシ
アセトキシベンゼン５０．１ ｇを得た。After carefully adding 238 g of hydrogen peroxide to a mixture of 50 g (0.21 mol) of 3-fluoro-4-hexyloxyacetophenone and 644 g of formic acid, the mixture was heated at 50°C for 4 hours.
Stir for 1 minute. Add 218 sodium bisulfite to this reaction solution.
．． 5 g (2.1 mol), 400 mj of water! Add the mixture below 10℃ and add 150ml of toluene! was added and extracted. Toluene was distilled off to obtain 50.1 g of 3-fluoro-4-hexyloxyacetoxybenzene.
このもの５１ｇ（０，２０モル）、エタノール１００＋
ｗｌ、水酸化ナトリウム４０ｇ、水３００Ｉｌｌの混合
物を３時間還流し、その後６Ｎ−ＩＣＩを加え酸性とし
トルエンを用いて抽出を行なった。51g (0.20mol) of this stuff, 100+ ethanol
A mixture of 40 g of sodium hydroxide and 300 Ill of water was refluxed for 3 hours, and then acidified with 6N-ICI and extracted with toluene.
トルエンを留去したのち蒸留にて３−フルオロ−４−へ
キシルオキシフェノール３８．３ ｇを得た。After removing toluene, 38.3 g of 3-fluoro-4-hexyloxyphenol was obtained by distillation.
ｂｐ２ｍｍＨｇ １２２℃であった。bp2mmHg 122℃.
３−フルオロ−４−へキシルオキシフェノール７．１ｇ
（０，０３モル）をヒリジン１０１１＋１に溶解したも
のに、さきに合成した光学活性４’−（１−メチルへブ
チルオキシ）−４−ビフェニルカルボン酸クロリド１０
．５ ｇ （０，０３モル）を加え反応させた。加熱撹
拌してから一晩放置後トルエン５０ｍＣ水５０Ｉｌｌｌ
を加えて撹拌し、そのトルエン層を６Ｎ−ＨＣＪ、つい
で２ Ｎ −ＮａＯＨ水溶液で洗浄し、さらに中性にな
るまで水洗した。トルエンを留去し残香をエタノールで
再結晶して光学活性４’−（１−メチルへブチルオキシ
）−４−ビフェニルカルボン酸３−フルオロ−４−ヘキ
シルオキシフェニルエステル８．７ｇを得た。このもの
の相転移点は、Ｃｒ −ＳＣ”点６３．４℃。3-fluoro-4-hexyloxyphenol 7.1g
(0.03 mol) dissolved in hyridine 1011+1, optically active 4'-(1-methylhebutyloxy)-4-biphenylcarboxylic acid chloride 10 synthesized earlier
．． 5 g (0.03 mol) was added and reacted. After heating and stirring and leaving it overnight, add toluene 50mC water 50Illl
was added and stirred, and the toluene layer was washed with 6N-HCJ, then with 2N-NaOH aqueous solution, and further washed with water until neutral. Toluene was distilled off and the residual aroma was recrystallized with ethanol to obtain 8.7 g of optically active 4'-(1-methylhebutyloxy)-4-biphenylcarboxylic acid 3-fluoro-4-hexyloxyphenyl ester. The phase transition point of this product is 63.4°C.
ＳＣ” −ＳＡ点９６．７℃、 ５Ａ−Ｃｈ点１０６．
７℃、ｃｈ−１点１０７．５℃であった。SC”-SA point 96.7°C, 5A-Ch point 106.
It was 7°C, and the temperature at ch-1 point was 107.5°C.
また、元素分析値はつぎの如く計算値とよく−致した。Furthermore, the elemental analysis values agreed well with the calculated values as shown below.
実測値
Ｃ７６，００％
Ｈ７，９０％
Ｆ ３．７０％
計算値（ＣｓＪ４＋０ｔＦ
７６．１２％
７．９４％
３．６５％
として）
実施例４
光学活性４−デシルオキシ安息香酸３−フルオロ−４−
（４−メチルへキシルオキシカルボニル）フェニルエス
テル（次式で示される化合物１１ｈ２５）の製造
２−フルオロ−４−ヒドロキシ安息香酸１５６ｇ（１，
０モル）に、５−４−メチルヘキサノール２６４ｇ（３
，０モル）、濃硫酸３Ｑａ＋Ｉ！、ベンゼン５００ｍｊ
！を加え１６時間還流した。その後冷却し２％ＮａＨＣ
Ｏｓ水溶液さらに水で中性になるまで洗浄した。溶媒を
留去し１６５ｇの光学活性２−フロオワ−４−ヒドロキ
シ安息香酸４−メチルヘキシルエステルを得た。Actual value C76,00% H7,90% F 3.70% Calculated value (as CsJ4+0tF 76.12% 7.94% 3.65%) Example 4 Optically active 4-decyloxybenzoic acid 3-fluoro-4-
Production of (4-methylhexyloxycarbonyl)phenyl ester (compound 11h25 represented by the following formula) 156 g of 2-fluoro-4-hydroxybenzoic acid (1,
0 mole), 264 g of 5-4-methylhexanol (3
,0 mol), concentrated sulfuric acid 3Qa+I! , benzene 500mj
! was added and refluxed for 16 hours. Then cool and add 2% NaHC
The Os aqueous solution was further washed with water until it became neutral. The solvent was distilled off to obtain 165 g of optically active 2-fluoro-4-hydroxybenzoic acid 4-methylhexyl ester.
一方、４−デシルオキシ安息香酸８．４ ｇ （０，０
３モル）を塩化チオニル５．０ ｇ （０，０４２モル
）を加え１時間還流したのち過剰の塩化チオニルを留去
して８．８ｇの４−デシルオキシ安息香酸クロリドを得
た。On the other hand, 8.4 g of 4-decyloxybenzoic acid (0,0
After adding 5.0 g (0,042 mol) of thionyl chloride and refluxing for 1 hour, excess thionyl chloride was distilled off to obtain 8.8 g of 4-decyloxybenzoic acid chloride.
さきに合成した光学活性２−フルオロ−４−ヒドロキシ
安息香酸４−メチルヘキシルエステル９、５ ｇ （０
，０３４モル）をピリジン５０１１１１に溶解し、これ
に４−デシルオキシ安息香酸クロリド１０、１ ｇ （
０，０３４モル）を滴下し５０〜６０℃で２時間反応さ
せた。−夜放置後トルエン３００ｒａ１水２００＋ｌｌ
ｌを加えて撹拌し、そのトルエン層を６Ｎ−ＩＣ１次い
で２ Ｎ−ＮａＯＨ水溶液で洗浄し、さらに中性になる
まで水洗した。トルエンを留去し残留物をエタノールで
再結晶して光学活性４−デシルオキシ安息香酸３−フル
オロ−４−（４−メチルへキシルオキシカルボニル）フ
ェニルエステル８．１ｇを得た。このものの相転移点は
、Ｃ−３ｃ１１点、２５．０℃、 ＳＣ”−５Ａ点４２
．７℃、５Ａ−Ｉ点５０．６℃であった。9.5 g of optically active 2-fluoro-4-hydroxybenzoic acid 4-methylhexyl ester synthesized earlier (0
,034 mol) was dissolved in pyridine 501111, and 10.1 g of 4-decyloxybenzoic acid chloride (
0,034 mol) was added dropwise and reacted at 50 to 60°C for 2 hours. - After leaving it overnight, toluene 300ra1 water 200+ll
The toluene layer was washed with 6N-IC1, then with 2N-NaOH aqueous solution, and further washed with water until neutral. Toluene was distilled off and the residue was recrystallized with ethanol to obtain 8.1 g of optically active 4-decyloxybenzoic acid 3-fluoro-4-(4-methylhexyloxycarbonyl)phenyl ester. The phase transition point of this product is C-3c11 point, 25.0℃, SC''-5A point 42
．． 7°C, 5A-I point 50.6°C.
また、元素分析値は次の如くよく計算値と一敗した。In addition, the elemental analysis values were in direct agreement with the calculated values as shown below.
実測値
７２．３０％
８．４０％
３．７０％
計算値（Ｃ３＋ＨａｓＯｓＦ
７２．３４％
８．４２％
３．６９％
として）
手続補正書（自発）
事件の表示
平成２年特許願第７１５３２号
発明の名称
光学活性液晶化合物および液晶組成物
補正をする者
事件との関係 特許出願人
大阪府大阪市北区中之島三丁目６番３２号（〒５３０）
（２０７）チッソ株式会社
代表者野木貞雄Actual value 72.30% 8.40% 3.70% Calculated value (as C3+HasOsF 72.34% 8.42% 3.69%) Procedural amendment (spontaneous) Indication of case 1990 Patent Application No. 71532 Invention Name of optically active liquid crystal compound and relation to the case of a person correcting liquid crystal composition Patent applicant 3-6-32 Nakanoshima, Kita-ku, Osaka-shi, Osaka (530)
(207) Chisso Corporation Representative Sadao Nogi
Claims (12)
は炭素数４〜１８のアルキル基もしくはアルコキシ基、
Ｒ＿２は、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ ▲数式、化学式、表等があります▼もしくは▲数式、化
学式、表等があります▼ （ここで、Ｒ′は炭素数２〜１０のアルキル基、ｙは２
〜１０、ｌは１〜１０を示す。）で表わされる光学活性
基、ｎは０もしくは１である。〕で表わされる光学活性
液晶化合物。(1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the above formula, X_2 represents a halogen atom, R_1
is an alkyl group or alkoxy group having 4 to 18 carbon atoms,
R_2 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R' is an alkyl group with 2 to 10 carbon atoms, and y is 2
~10, 1 represents 1-10. ), n is 0 or 1. ] An optically active liquid crystal compound represented by
″は、 ▲数式、化学式、表等があります▼もしくは▲数式、化
学式、表等があります▼ （ここで、Ｒ′は炭素数２〜１０のアルキル基、ｙは２
〜１０を示す。）で表わされる光学活性基、Ｒ＿２″は
炭素数４〜１８のアルキル基、アルコキシ基もしくはア
ルコキシカルボニル基、ｎは０もしくは１を示す。〕で
表わされる光学活性液晶化合物。(2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the above formula, X_2 represents a halogen atom, R_1
'' is ▲There are mathematical formulas, chemical formulas, tables, etc.▼or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R' is an alkyl group with 2 to 10 carbon atoms, and y is 2
~10 is shown. ), R_2'' is an alkyl group having 4 to 18 carbon atoms, an alkoxy group, or an alkoxycarbonyl group, and n is 0 or 1.] An optically active liquid crystal compound represented by the following.
は１を示し、Ｒ＿１は炭素数４〜１８のアルキル基また
はアルコキシ基、Ｒ＿２″′は光学活性基を示す。）で
表わされる光学活性液晶化合物。(3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) [In the above formula, An optically active liquid crystal compound represented by R_2'' represents an optically active group.
表等があります▼、 ▲数式、化学式、表等があります▼もしくは▲数式、化
学式、表等があります▼ （ここでＸ＋Ｚは０〜１０）Ｒ′は炭素数２〜１０のア
ルキル基を示す。）である特許請求の範囲第３項記載の
化合物。(4) Optically active groups have ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, X + Z is 0 to 10) R' represents an alkyl group having 2 to 10 carbon atoms. ) is the compound according to claim 3.
は炭素数４〜１８のアルキル基もしくはアルコキシ基、 Ｒ＿２は、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼もしくは▲数式、化
学式、表等があります▼ （ここで、Ｒ′は炭素数２〜１０のアルキル基、ｙは２
〜１０、ｌは１〜１０を示す。）で表わされる光学活性
基、ｎは０もしくは１である。〕で表わされる光学活性
液晶化合物の少くとも１種を１成分含有することを特徴
とする少くとも２成分以上からなるカイラルスメクチッ
ク液晶組成物。(5) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the above formula, X_2 represents a halogen atom, R_1
is an alkyl group or alkoxy group having 4 to 18 carbon atoms, R_2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R' is an alkyl group with 2 to 10 carbon atoms, and y is 2
~10, 1 represents 1-10. ), n is 0 or 1. A chiral smectic liquid crystal composition comprising at least two components, characterized in that it contains at least one optically active liquid crystal compound represented by the following formula.
求の範囲第５項記載のカイラルスメクチック液晶組成物
。(6) A chiral smectic liquid crystal composition according to claim 5, which comprises only a plurality of compounds of formula (I).
″は、 ▲数式、化学式、表等があります▼もしくは▲数式、化
学式、表等があります▼ （ここで、Ｒ′は炭素数２〜１０のアルキル基、ｙは２
〜１０を示す。）で表わされる光学活性基、Ｒ＿２″は
炭素数４〜１８のアルキル基、アルコキシ基もしくはア
ルコキシカルボニル基、ｎは０もしくは１を示す。〕で
表わされる光学活性液晶化合物の少くとも１種を１成分
含有することを特徴とする、少くとも２成分以上からな
るカイラルスメクチック液晶組成物。(7) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) [In the above formula, X_2 represents a halogen atom, R_1
'' is ▲There are mathematical formulas, chemical formulas, tables, etc.▼or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R' is an alkyl group with 2 to 10 carbon atoms, and y is 2
~10 is shown. ), R_2″ is an alkyl group having 4 to 18 carbon atoms, an alkoxy group, or an alkoxycarbonyl group, and n is 0 or 1. A chiral smectic liquid crystal composition comprising at least two components.
の範囲第７項記載のカイラルスメクチック液晶組成物。(8) The chiral smectic liquid crystal composition according to claim 7, which comprises only a plurality of compounds of formula (II).
１を示し、Ｒ＿１は炭素数４〜１８のアルキル基または
アルコキシ基、Ｒ＿２″′は光学活性基を示す。）で表
わされる光学活性液晶化合物の少くとも１種を１成分含
有することを特徴とする、少くとも２成分以上からなる
カイラルスメクチック液晶組成物。(9) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (In the above formula, A chiral smectic liquid crystal composition comprising at least two components, characterized in that it contains one component of at least one optically active liquid crystal compound represented by ``'' represents an optically active group.
ルキル基を示す。）で表わされる光学活性基である特許
請求範囲第９項の液晶組成物。(10) R_2″′ in general formula (III) is ▲There is a mathematical formula, chemical formula, table, etc.▼, ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼ (Here, X + Z is 10-10, R' represents an alkyl group having 2-10 carbon atoms).
請求の範囲第１０項記載のカイラルスメクチック液晶組
成物。(11) The chiral smectic liquid crystal composition according to claim 10, which comprises only a plurality of compounds of formula (III).
もしくは１を表わし、Ｒ＿１は炭素数４〜１８のアルキ
ル基もしくはアルコキシ基、 Ｒ＿２は、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ ▲数式、化学式、表等があります▼もしくは▲数式、化
学式、表等があります▼ で表わされる光学活性基、 Ｒ＿１″は、 ▲数式、化学式、表等があります▼もしくは▲数式、化
学式、表等があります▼ Ｒ＿２″は、炭素数４〜１８のアルキル基、アルコキシ
基もしくはアルコキシカルボニル基、Ｒ＿２″′は光学
活性基、（ここで、Ｒ′は炭素数２〜１０のアルキル基
、ｙは２〜１０、ｌは１〜１０を示す。）を表わす。〕
で表わされる光学活性液晶化合物の少くとも１種を１成
分含有する少なくとも２成分以上からなるカイラルスメ
クチック液晶組成物を使用して構成された光スイッチン
グ素子。(12) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [These formulas , X_2 is a halogen atom, n is 0
or 1, R_1 is an alkyl group or alkoxy group having 4 to 18 carbon atoms, and R_2 is ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The optically active group R_1″ represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formula , chemical formulas, tables, etc. ▼ R_2″ is an alkyl group, alkoxy group, or alkoxycarbonyl group having 4 to 18 carbon atoms, R_2″′ is an optically active group, (here, R′ is an alkyl group having 2 to 10 carbon atoms, group, y represents 2 to 10, l represents 1 to 10.]
An optical switching element constructed using a chiral smectic liquid crystal composition consisting of at least two components, each of which contains at least one optically active liquid crystal compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2071532A JPH02275839A (en) | 1985-03-14 | 1990-03-20 | Optically active liquid crystal compound and liquid crystal composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60051512A JPS61210056A (en) | 1985-03-14 | 1985-03-14 | Halogen-containing optically active liquid crystal compound and liquid crystal composition |
| JP2071532A JPH02275839A (en) | 1985-03-14 | 1990-03-20 | Optically active liquid crystal compound and liquid crystal composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60051512A Division JPS61210056A (en) | 1985-03-14 | 1985-03-14 | Halogen-containing optically active liquid crystal compound and liquid crystal composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02275839A true JPH02275839A (en) | 1990-11-09 |
Family
ID=26392053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2071532A Pending JPH02275839A (en) | 1985-03-14 | 1990-03-20 | Optically active liquid crystal compound and liquid crystal composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02275839A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716545A (en) * | 1995-12-28 | 1998-02-10 | Nippon Soken, Inc. | Antiferroelectric liquid crystal composition |
| US6129859A (en) * | 1996-07-25 | 2000-10-10 | Nippon Soken, Inc. | Antiferroelectric liquid crystal composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61161244A (en) * | 1985-01-09 | 1986-07-21 | Dainippon Ink & Chem Inc | Novel compound, preparation thereof, and liquid crystal composition |
| JPS61210056A (en) * | 1985-03-14 | 1986-09-18 | Chisso Corp | Halogen-containing optically active liquid crystal compound and liquid crystal composition |
| JPS61229842A (en) * | 1985-04-05 | 1986-10-14 | Asahi Glass Co Ltd | Optically active fluorine-containing ether compound and liquid crystal composition using same |
| JPS63175095A (en) * | 1987-01-14 | 1988-07-19 | Dainippon Ink & Chem Inc | Optically active liquid crystal compound |
| JPH01256590A (en) * | 1988-04-06 | 1989-10-13 | Chisso Corp | Ferroelectric liquid crystal composition and liquid crystal element |
-
1990
- 1990-03-20 JP JP2071532A patent/JPH02275839A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61161244A (en) * | 1985-01-09 | 1986-07-21 | Dainippon Ink & Chem Inc | Novel compound, preparation thereof, and liquid crystal composition |
| JPS61210056A (en) * | 1985-03-14 | 1986-09-18 | Chisso Corp | Halogen-containing optically active liquid crystal compound and liquid crystal composition |
| JPS61229842A (en) * | 1985-04-05 | 1986-10-14 | Asahi Glass Co Ltd | Optically active fluorine-containing ether compound and liquid crystal composition using same |
| JPS63175095A (en) * | 1987-01-14 | 1988-07-19 | Dainippon Ink & Chem Inc | Optically active liquid crystal compound |
| JPH01256590A (en) * | 1988-04-06 | 1989-10-13 | Chisso Corp | Ferroelectric liquid crystal composition and liquid crystal element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716545A (en) * | 1995-12-28 | 1998-02-10 | Nippon Soken, Inc. | Antiferroelectric liquid crystal composition |
| US6129859A (en) * | 1996-07-25 | 2000-10-10 | Nippon Soken, Inc. | Antiferroelectric liquid crystal composition |
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