JPH01121248A - Optically active compound - Google Patents
Optically active compoundInfo
- Publication number
- JPH01121248A JPH01121248A JP27937887A JP27937887A JPH01121248A JP H01121248 A JPH01121248 A JP H01121248A JP 27937887 A JP27937887 A JP 27937887A JP 27937887 A JP27937887 A JP 27937887A JP H01121248 A JPH01121248 A JP H01121248A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- formula
- acid
- compound
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 3
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 9
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000003333 secondary alcohols Chemical class 0.000 abstract description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000005711 Benzoic acid Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004990 Smectic liquid crystal Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PRNCMAKCNVRZFX-JTQLQIEISA-N (3s)-3,7-dimethyloctan-1-ol Chemical compound CC(C)CCC[C@H](C)CCO PRNCMAKCNVRZFX-JTQLQIEISA-N 0.000 description 2
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 description 2
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 description 2
- RYFZXYQQFYLUHM-UHFFFAOYSA-N 7,7-dimethyloctan-1-ol Chemical compound CC(C)(C)CCCCCCO RYFZXYQQFYLUHM-UHFFFAOYSA-N 0.000 description 2
- 239000005264 High molar mass liquid crystal Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 etc. Chemical group 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- JZEUFFFBEMAJHS-UHFFFAOYSA-N 2-methyldecan-1-ol Chemical compound CCCCCCCCC(C)CO JZEUFFFBEMAJHS-UHFFFAOYSA-N 0.000 description 1
- SCHAAFQMJJWGJM-UHFFFAOYSA-N 2-methyldodecan-1-ol Chemical compound CCCCCCCCCCC(C)CO SCHAAFQMJJWGJM-UHFFFAOYSA-N 0.000 description 1
- BEGNRPGEHZBNKK-UHFFFAOYSA-N 2-methylnonan-1-ol Chemical compound CCCCCCCC(C)CO BEGNRPGEHZBNKK-UHFFFAOYSA-N 0.000 description 1
- YLQGFOSNRNDJDV-UHFFFAOYSA-N 2-methyltridecan-1-ol Chemical compound CCCCCCCCCCCC(C)CO YLQGFOSNRNDJDV-UHFFFAOYSA-N 0.000 description 1
- IMACNEKKOHOIMA-UHFFFAOYSA-N 3-methyldecan-1-ol Chemical compound CCCCCCCC(C)CCO IMACNEKKOHOIMA-UHFFFAOYSA-N 0.000 description 1
- BXQPYGLPOMTAPU-UHFFFAOYSA-N 3-methylnonan-1-ol Chemical compound CCCCCCC(C)CCO BXQPYGLPOMTAPU-UHFFFAOYSA-N 0.000 description 1
- CHZLPOXCLAVPRG-UHFFFAOYSA-N 4-methyldecan-1-ol Chemical compound CCCCCCC(C)CCCO CHZLPOXCLAVPRG-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- NHZQLBHSBDMUGE-UHFFFAOYSA-N 6-phenylmethoxynaphthalene-2-carbonyl chloride Chemical compound C1=CC2=CC(C(=O)Cl)=CC=C2C=C1OCC1=CC=CC=C1 NHZQLBHSBDMUGE-UHFFFAOYSA-N 0.000 description 1
- ZAMRNNPFCAMROT-UHFFFAOYSA-N 6-phenylmethoxynaphthalene-2-carboxylic acid Chemical compound C1=CC2=CC(C(=O)O)=CC=C2C=C1OCC1=CC=CC=C1 ZAMRNNPFCAMROT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XSWSEQPWKOWORN-UHFFFAOYSA-N dodecan-2-ol Chemical compound CCCCCCCCCCC(C)O XSWSEQPWKOWORN-UHFFFAOYSA-N 0.000 description 1
- GCFHZZWXZLABBL-UHFFFAOYSA-N ethanol;hexane Chemical compound CCO.CCCCCC GCFHZZWXZLABBL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- KQPMFNHZHBLVRR-UHFFFAOYSA-N oxalic acid;hydrochloride Chemical compound Cl.OC(=O)C(O)=O KQPMFNHZHBLVRR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規な光学活性化合物に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to novel optically active compounds.
さらに詳しくは、新規な光学活性液晶化合物の中間体と
して有用な光学活性化合物に関する。More specifically, the present invention relates to an optically active compound useful as an intermediate for a novel optically active liquid crystal compound.
現在、各種液晶表示素子が実用化されている。 Currently, various liquid crystal display elements are in practical use.
なかでも、ネマティック液晶を用いたＴ Ｎ （Ｔｗｉ
ｓｔｅｄ Ｎｅｗａｔｉｃ ）型表示方式は消費電力が
極めて少ないという優れた性能を持ち、広く利用されて
いる。しかし、この表示方式は応答速度が遅いという欠
点がある。Among them, T N (Twi
The sted newatic) type display system has excellent performance in that it consumes extremely little power, and is widely used. However, this display method has the drawback of slow response speed.
最近の産業技術の進展は、液晶表示素子にも高速応答性
が強く要望され、このような要求に対しては、液晶材料
の改良による種々の試みがなされている。既に上記要望
に応えるものとして、光学活性スメクチック液晶を用い
た強誘電性液晶の光スイツチング現象を利用した表示デ
バイスが提案されている（アプライド・フィジクス・レ
ター（Ａｐｐｌ、Ｐｈｙｓ、Ｌｅｔｔ、、３６．８９９
（１９８０）））。Recent advances in industrial technology have strongly demanded high-speed response in liquid crystal display elements, and in response to such demands, various attempts have been made to improve liquid crystal materials. A display device that utilizes the optical switching phenomenon of ferroelectric liquid crystals using optically active smectic liquid crystals has already been proposed to meet the above requirements (Applied Physics Letters (Appl, Phys, Lett, 36.899).
(1980))).
公知の強誘電性液晶の代表的なものとして第１表に示す
ものがある。Representative examples of known ferroelectric liquid crystals include those shown in Table 1.
第１表に示した公知の強誘電性液晶化合物は、光により
短時間の内に異性化を起こしたり、また水分により加水
分解を起こし液晶相を示さなくなるという不安定要素を
持ち、表示素子としては好ましくない。The known ferroelectric liquid crystal compounds shown in Table 1 have unstable elements such as being isomerized in a short time by light or hydrolyzed by moisture and no longer exhibiting a liquid crystal phase. is not desirable.
本発明の課題はこのような不安定要素をなくした光化学
的および化学的安定性を有し、強誘電相を有する強誘電
性液晶の中間体として存用な新規な化合物を提供するこ
とである。The object of the present invention is to provide a novel compound that has photochemical and chemical stability without such unstable elements and can be used as an intermediate for ferroelectric liquid crystals having a ferroelectric phase. .
本発明者らは、上述の問題点を解決するために種々の化
合物を探索し本発明に到達した。The present inventors have searched for various compounds to solve the above-mentioned problems and have arrived at the present invention.
すなわち、本発明は一般式（Ｉ）
（式中、−ｍは１〜３の整数であり、Ｒは炭素数４１０
のアルキル基を示し、＊印は不斉炭素原子を示す。）で
表わされる光学活性化合物に関する。That is, the present invention is based on the general formula (I) (wherein -m is an integer of 1 to 3, and R has 410 carbon atoms.
represents an alkyl group, and the * mark represents an asymmetric carbon atom. ).
（Ｉ）式の化合物は種々９方法で製造できるが代表的に
は下記の合成経路により製造できる。The compound of formula (I) can be produced by nine different methods, but typically it can be produced by the following synthetic route.
（ａ）
（ｂ）
（ｄ、１
（Ｉ）
（但し、ｍ、Ｒ，＊印は前記と同じ、Ｂｚはベンジル基
を表わす。）
すなわち、２．６−ヒトロキシナフタレンカルボン酸（
ａ）をベンジル化し、化合物（ｂ）とした後、さらにチ
オニルクロライド、シュウ酸塩化物などを用い、酸クロ
ライド誘導体（Ｃ）とする。(a) (b) (d, 1 (I) (However, m, R, * marks are the same as above, Bz represents a benzyl group.) That is, 2,6-hydroxynaphthalenecarboxylic acid (
After a) is benzylated to form a compound (b), thionyl chloride, oxalate chloride, etc. are further used to form an acid chloride derivative (C).
そして（Ｃ）と種々の光学活性２級アルコールとを反応
させてエステル体（ｄ）とする。その後、パラジウム／
炭素の存在下、水素により脱ベンジル化し化合物（Ｉ）
を製造することができる。本発明の化合物（、Ｉ ）の
製造に用いられる２、６−ヒトロキシナフタレンカルボ
ン酸は、例えばジャーナル・オブ・ケミカル・ソサエテ
ィ（Ｊ、Ｃｈｅｍ、Ｓｏｃ、 ｌ＠ 、 ６７Ｂ）に記
載のとおり公知の物質である。Then, (C) is reacted with various optically active secondary alcohols to form an ester (d). After that, palladium/
Compound (I) was debenzylated with hydrogen in the presence of carbon.
can be manufactured. The 2,6-hydroxynaphthalenecarboxylic acid used in the production of the compound (I) of the present invention is a known compound as described in, for example, the Journal of the Chemical Society (J, Chem, Soc, 1@, 67B). It is a substance.
また原料の光学活性アルコールとして有用なものを例示
すれば、たとえば光学活性２−メチルヘキサノール、学
活性２ニメチルオクタノール、光学活性２−メチルノナ
ノール、光学活性２−メチルデカノール、光学活性２−
メチルウンデカノール、光学活性２−メチルドデカノー
ル、光学活性２−メチルトリデカノール、光学活性３−
ヘプタツール、光学活性３−メチルオクタツール、光学
活性３．７−シメチルオクタノール、光学活性３−メチ
ルノナノール、光学活性３−メチルデカノール、光学活
性４−メチルオクタツール、光学活性４−メチルノナノ
ール、光学活性４−メチルデカノールを挙げることがで
きる。Examples of useful optically active alcohols as raw materials include optically active 2-methylhexanol, optically active 2-dimethyloctanol, optically active 2-methylnonanol, optically active 2-methyldecanol, and optically active 2-dimethyloctanol.
Methylundecanol, optically active 2-methyldodecanol, optically active 2-methyltridecanol, optically active 3-
Heptatool, optically active 3-methyloctatool, optically active 3.7-dimethyloctanol, optically active 3-methylnonanol, optically active 3-methyldecanol, optically active 4-methyloctatool, optically active 4-methyl Examples include nonanol and optically active 4-methyldecanol.
この中で、好ましくは光学活性２−メチルヘキサノール
、光学活性２−メチルオクタツール、光学活性３−メチ
ルヘプタツール、光学活性３−メチルオクタツール、光
学活性３，７−シメチルオクタノール、光学活性４−メ
チルオクタツールであり、より好ましくは光学活性３．
７−シメチルオクタノールである。Among these, optically active 2-methylhexanol, optically active 2-methyloctatool, optically active 3-methylheptatool, optically active 3-methyloctatool, optically active 3,7-dimethyloctanol, optically active 4 - methyloctatool, more preferably optically active 3.
7-dimethyloctanol.
また光学活性アルコールの絶対配置が（Ｒ）体と（Ｓ）
体両方共利用できることは言うまでもない。Also, the absolute configuration of optically active alcohol is (R) and (S)
Needless to say, both bodies can be used together.
一般に液晶化合物はベンゼン環、複素環、シクロヘキサ
ン環などからなる核の部分と、アルキル鎖などからなる
棒状構造をしている。Generally, liquid crystal compounds have a rod-like structure consisting of a core consisting of a benzene ring, a heterocycle, a cyclohexane ring, etc., and an alkyl chain.
その中でもアルキル鎖の炭素数がある程度以上のものは
スメクチック相を示しやすいことがよく知られている。Among them, it is well known that those having a certain number of carbon atoms in the alkyl chain or more tend to exhibit a smectic phase.
すなわち、一般式（１）で表される化合物を例えばアル
キルカルボン酸、アルコキシカルボン酸、４−アルキル
安息香酸、４−アルコキシ安息香酸、４−アルキルカル
ボニルオキシ安息香酸、４−アルコキシカルボニル安息
香酸、４−アルコキシカルボニルオキシ安息香酸、６−
アルキル−ナフタレン−２−カルボン酸、６−アルコキ
シ−ナフタレン−２−カルボン酸、６−アルキルカルボ
ニルオキシ−ナフタレン−２−カルボン酸、６−アルコ
キシカルボニル−ナフタレン−２−カルボン酸、６−ア
ルコキジカルボニルオキシ−ナフタレン−２−カルボン
酸、４−（４’−アルキルフェニル）安息香酸、４−（
４”−アルコキシフェニル）安息香酸、４−（４’−ア
ルキルカルボニルオキシフェニル）安息香酸、・４−（
４’−アルコキシカルボニルフェニル）安息香１４−（
４’−アルコキシカルボニルオキシフェニル）安息香酸
、トランス−４−（４’−アルキルフェニル）シクロヘ
キシルカルボン酸、トランス−４−（４’−アルコキシ
フェニル）シクロヘキシルカルボン酸、トランス−４−
（４’−アルキルカルボニルオキシフェニル）シクロへ
キシルカルボン酸、トランス−４−（４’−アルコキシ
カルボニルフェニル）シクロへキシルカルボン酸、トラ
ンス−４−（４°−アルコキシカルボニルオキシフェニ
ル）シクロヘキシルカルボン酸、４−（）ランス−４°
−アルキルシクロヘキシル）安息香酸、４−（５”−ア
ルキルピリミジン−２゛−イル）安息香酸、４−（５”
−アルコキシピリミジン−２′−イル）安息香酸、４−
（トランス−５゛−アルキル−１゛、３”−ジオキサン
−２°−イル）安息香酸、４−（トランス−５′−アル
キル−Ｉｆ、３″−ジチアオキサン−２′−イル）安息
香酸、４−（トランス−５′−アルキル−１”、３”ジ
チアン−２°−イル）安息香酸、４−（５°−アルキル
−１’、３’、２°−ジオキサボリナン−２°−イル）
安息香酸またはこれらの化合物のベンゼン環あるいはナ
フタレンに環にハロゲン原子、シアノ基、ニトロ基、メ
チル基、エチル基を置換した誘導体と反応させることに
より、非常に有用な強誘電性液晶を得ることができる。That is, the compound represented by the general formula (1) can be used, for example, as an alkylcarboxylic acid, an alkoxycarboxylic acid, 4-alkylbenzoic acid, 4-alkoxybenzoic acid, 4-alkylcarbonyloxybenzoic acid, 4-alkoxycarbonylbenzoic acid, -Alkoxycarbonyloxybenzoic acid, 6-
Alkyl-naphthalene-2-carboxylic acid, 6-alkoxy-naphthalene-2-carboxylic acid, 6-alkylcarbonyloxy-naphthalene-2-carboxylic acid, 6-alkoxycarbonyl-naphthalene-2-carboxylic acid, 6-alkoxycarbonyl Oxy-naphthalene-2-carboxylic acid, 4-(4'-alkylphenyl)benzoic acid, 4-(
4''-alkoxyphenyl)benzoic acid, 4-(4'-alkylcarbonyloxyphenyl)benzoic acid, 4-(
4'-alkoxycarbonylphenyl)benzoic 14-(
4'-alkoxycarbonyloxyphenyl)benzoic acid, trans-4-(4'-alkylphenyl)cyclohexylcarboxylic acid, trans-4-(4'-alkoxyphenyl)cyclohexylcarboxylic acid, trans-4-
(4'-alkylcarbonyloxyphenyl)cyclohexylcarboxylic acid, trans-4-(4'-alkoxycarbonylphenyl)cyclohexylcarboxylic acid, trans-4-(4°-alkoxycarbonyloxyphenyl)cyclohexylcarboxylic acid, 4-() Lance-4°
-alkylcyclohexyl)benzoic acid, 4-(5"-alkylpyrimidin-2'-yl)benzoic acid, 4-(5"
-alkoxypyrimidin-2'-yl)benzoic acid, 4-
(trans-5′-alkyl-1′,3″-dioxan-2′-yl)benzoic acid, 4-(trans-5′-alkyl-If,3″-dithiaoxan-2′-yl)benzoic acid, 4 -(trans-5′-alkyl-1”,3”dithian-2°-yl)benzoic acid, 4-(5°-alkyl-1′,3′,2°-dioxaborinan-2°-yl)
Very useful ferroelectric liquid crystals can be obtained by reacting benzoic acid or derivatives of these compounds in which the benzene ring or naphthalene is substituted with a halogen atom, cyano group, nitro group, methyl group, or ethyl group. can.
例えば、本発明の化合物（１）と４−アルコキシ安息香
酸から製造される一般式（Ｉｆ）で示される化合物
（式中、Ｒ１は炭素数１〜２０のアルキル基、ｎは１〜
３の整数、Ｒ７は炭素数４〜１０のアルキル基を示し、
＊印は不斉炭素原子を示す。）は、第２表中の具体例で
示されるようにカイラルスメクチッりＣ相を有し、室温
付近で動作する強誘電性液晶混合物を調製する際の構成
成分として重要である。For example, a compound represented by the general formula (If) produced from the compound (1) of the present invention and 4-alkoxybenzoic acid (wherein R1 is an alkyl group having 1 to 20 carbon atoms, and n is 1 to
an integer of 3, R7 represents an alkyl group having 4 to 10 carbon atoms,
* indicates an asymmetric carbon atom. ) has a chiral smectic C phase, as shown in the specific examples in Table 2, and is important as a constituent when preparing a ferroelectric liquid crystal mixture that operates near room temperature.
第２表中、Ｃは結晶相、ＳＣ”はカイラルスメクチック
Ｃ相、ＳＡはスメクチックＡ相、■は等方性液体を表し
、各相の・印とその右側の数字がその相から右側の相へ
の転移温度を示す。In Table 2, C is a crystalline phase, SC'' is a chiral smectic C phase, SA is a smectic A phase, and ■ is an isotropic liquid. indicates the transition temperature to .
なお（）内の値はモノトロピック相転位温度である。Note that the value in parentheses is the monotropic phase transition temperature.
本発明の化合物は光学活性液晶化合物の製造における中
間体として非常に有用である。本発明の化合物は分子内
に光学活性基を有しており、特に強誘電性液晶、カイラ
ルネマチック液晶の製造における中間体として特に有用
である。The compounds of the present invention are very useful as intermediates in the production of optically active liquid crystal compounds. The compound of the present invention has an optically active group in its molecule and is particularly useful as an intermediate in the production of ferroelectric liquid crystals and chiral nematic liquid crystals.
また本発明の化合物を高分子液晶に導入すると、電気光
学効果を示す高分子液晶を製造することもできる。Furthermore, by introducing the compound of the present invention into a polymer liquid crystal, it is also possible to produce a polymer liquid crystal exhibiting an electro-optic effect.
＝１０−
〔実施例〕
以下実施例により、本発明の化合物につき、更に詳細に
説明するが、本発明はこれらの実施例により限定される
ものではない。=10- [Example] The compounds of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.
実施例１
（ｓ）−６−ヒトロキシナフタレンー２−カルボン酸−
３’、 ７’−ジメチルオクチルエステル（（Ｉ）式に
おけるｍ＝２、Ｒ＝−（ＣＨｚ）ｚｃｌｌ（ＣＨｓ）ｚ
の化合物）の製造 ）
（１）６−ベンジルオキシナフタレン−２−カルボン酸
の製造。Example 1 (s)-6-hydroxynaphthalene-2-carboxylic acid-
3', 7'-dimethyloctyl ester (m=2 in formula (I), R=-(CHz)zcll(CHs)z
(1) Production of 6-benzyloxynaphthalene-2-carboxylic acid.
２．６−ヒトロキシナフタレンカルボン酸１００ｇ 。2.6-Hydroxinaphthalenecarboxylic acid 100g.
８５％水酸化カリウム７０ｇを水１０ｈ＋Ｊ！、エタノ
ール７００威に溶解させ、これに１１０ｇのベンジルブ
ロマイドを加え８時間加熱還流した。その後さらに３５
ｇの水酸化カリウムを加え５時間加熱還流を続けた。70g of 85% potassium hydroxide and 10h of water + J! The mixture was dissolved in 700 g of ethanol, 110 g of benzyl bromide was added thereto, and the mixture was heated under reflux for 8 hours. Then another 35
g of potassium hydroxide was added, and heating and refluxing was continued for 5 hours.
室温まで冷却後、濃塩酸で酸性とし析出した固体を濾別
した。さらに水、エタノール、ベンゼンの順で洗浄し、
目的物を得た。このものをさらに精製することなく次の
反応に用いた。After cooling to room temperature, the mixture was acidified with concentrated hydrochloric acid and the precipitated solid was separated by filtration. Furthermore, wash with water, ethanol, and benzene in that order.
Obtained the object. This product was used in the next reaction without further purification.
（ｉｉ）６−ベンジルオキシナフタレン−２−カルボン
酸塩化物の製造
（ｉ）で得た化合物６−ベンジルオキシ−１−７タレン
ー２−カルボン酸６５ ｇ ｔ−５０ｄのトルエン中３
０ｍ１！の塩化チオニルと３時間加熱還流し過剰の塩化
チオニルとトルエンを減圧上留去し、酸塩化物を得た。(ii) Preparation of 6-benzyloxynaphthalene-2-carboxylic acid chloride Compound 6-benzyloxy-1-7talene-2-carboxylic acid obtained in (i) 65 g t-50d in toluene 3
0m1! The mixture was heated under reflux with thionyl chloride for 3 hours, and excess thionyl chloride and toluene were distilled off under reduced pressure to obtain an acid chloride.
この粗生成物は次の反応に精製することなく用いた。This crude product was used in the next reaction without purification.
（ｆｉｔ） （ｓ） −６−ベンジルオキシナフタレ
ン−２−カルボン酸−３’、 ？’−ジメチルオクチル
エステルの製造
（ｉｉ）で得た酸塩化物を１００−のトルエンに溶解さ
せこの溶液に（ｓ）−３，７−シメチルオクタノール３
８ｇをピリジン３０１１ｉ！に溶解した溶液を加え、室
温で８時間放置した。析出したピリジン塩酸塩を濾別し
た後、有機層・を２Ｎ−塩酸で洗浄し、さらに２Ｎ−水
酸化ナトリウム水溶液で洗い、さらに中性になるまで水
洗した。(fit) (s) -6-benzyloxynaphthalene-2-carboxylic acid-3', ? The acid chloride obtained in step (ii) of production of '-dimethyloctyl ester was dissolved in 100-dimethyloctyl toluene, and (s)-3,7-dimethyloctanol 3
8g of pyridine 3011i! A solution dissolved in was added and left at room temperature for 8 hours. After filtering off the precipitated pyridine hydrochloride, the organic layer was washed with 2N hydrochloric acid, further washed with 2N aqueous sodium hydroxide solution, and further washed with water until neutral.
有機層を分離し、トルエンを減圧上留去した後、残渣を
エタノールより再結晶し、無色板状晶の結晶として目的
物を７０ｇ得た。After separating the organic layer and distilling off toluene under reduced pressure, the residue was recrystallized from ethanol to obtain 70 g of the desired product as colorless plate-like crystals.
融点 ５１．５〜５３．０’Ｃ
（ｉｖ） （ｉｉｉ）で得た（ｓ） −５−ベンジル
オキシナフタレン−２−カルボン酸−３”、７′−ジメ
チルオクチルエステル７０ｇを２００ｄのエタノールに
溶解し、５％パラジウム／炭素４ｇの存在下、常圧４０
”Ｃで水素化した。Melting point 51.5-53.0'C (iv) Dissolve 70 g of (s)-5-benzyloxynaphthalene-2-carboxylic acid-3'',7'-dimethyloctyl ester obtained in (iii) in 200 d of ethanol. and in the presence of 4 g of 5% palladium/carbon at normal pressure of 40
"Hydrogenated with C.
パラジウム／炭素を濾別後、溶媒を減圧下に留去した後
、残渣をエタノール−ｎ−ヘキサンより再結晶し無色針
状晶の結晶として目的とする（Ｓ）−６−ヒトロキシナ
フタレンー２−カルボン酸−３’、 ７’−ジメチルオ
クチルエステルを５０ｇ得た。After the palladium/carbon was filtered off, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol-n-hexane to give the desired colorless needle-shaped crystals (S)-6-hydroxynaphthalene-2. 50 g of -carboxylic acid-3',7'-dimethyloctyl ester was obtained.
融点 ８６．５〜８８．２°に
の化合物の元素分析値は表３に示すように理論値とよく
一致した。The elemental analysis values of the compound with a melting point of 86.5-88.2° were in good agreement with the theoretical values as shown in Table 3.
実施例２〜１５
実施例１の（ｉｉｉ）において、（ｓ）−３，７−シメ
チルオクタノールの代わりに種々の光学活性アルコール
を使用した以外は、実施例１の（ｉｌ）第３表
に記載した方法に従い種々の光学活性６−ベンジルオキ
シナフタレン−２−カルボン酸−アルキルエステルを製
造した。Examples 2 to 15 Table 3 in (il) of Example 1 except that in (iii) of Example 1, various optically active alcohols were used in place of (s)-3,7-dimethyloctanol. Various optically active 6-benzyloxynaphthalene-2-carboxylic acid alkyl esters were prepared according to the described method.
さらに実施例１゛の（ｉｖ）において（Ｓ）−６−ベン
ジルオキシナフタレン−２−カルボン酸−３′１７”−
ジメチルオクチルエステルの代わりに種々の光学活性６
−ベンジルオキシナフタレン−２−カルボン酸−アルキ
ルエステルを使用した以外は実施例１の（ｉｖ）に記載
した方法に従い、種々の光学活性６−ヒトロキシナフタ
レンー２−カルボン酸−アルキルエステルを製造した。Furthermore, in (iv) of Example 1, (S)-6-benzyloxynaphthalene-2-carboxylic acid-3'17''-
Various optically active substances 6 can be used instead of dimethyloctyl ester.
Various optically active 6-hydroxynaphthalene-2-carboxylic acid-alkyl esters were produced according to the method described in Example 1 (iv), except that -benzyloxynaphthalene-2-carboxylic acid-alkyl ester was used. .
これらの化合物の元素分析値は第３表に示すように理論
値とよ（一致した。The elemental analysis values of these compounds were in agreement with the theoretical values as shown in Table 3.
本発明の化合物を中間体として用いて製造した化合物は
非常に優れた強誘電性液晶となり、しかも光化学的、化
学的に非常に安定である。A compound produced using the compound of the present invention as an intermediate becomes an excellent ferroelectric liquid crystal and is photochemically and chemically very stable.
出願人 三井東圧化学株式会社Applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
のアルキル基を示し、＊印は不斉炭素原子を示す。）で
表わされる光学活性化合物。[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, m is an integer of 1 to 3, and R is a carbon number of 4 to 10
represents an alkyl group, and the * mark represents an asymmetric carbon atom. ) An optically active compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27937887A JPH0796531B2 (en) | 1987-11-06 | 1987-11-06 | Optically active compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27937887A JPH0796531B2 (en) | 1987-11-06 | 1987-11-06 | Optically active compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01121248A true JPH01121248A (en) | 1989-05-12 |
| JPH0796531B2 JPH0796531B2 (en) | 1995-10-18 |
Family
ID=17610309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27937887A Expired - Fee Related JPH0796531B2 (en) | 1987-11-06 | 1987-11-06 | Optically active compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796531B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194665A (en) * | 1988-06-30 | 1993-03-16 | Hoechst Ag | Surfactants based on hydroxynaphthoic esters and preparation and use thereof |
-
1987
- 1987-11-06 JP JP27937887A patent/JPH0796531B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194665A (en) * | 1988-06-30 | 1993-03-16 | Hoechst Ag | Surfactants based on hydroxynaphthoic esters and preparation and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0796531B2 (en) | 1995-10-18 |
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