JPH01121247A - Optically active compound - Google Patents
Optically active compoundInfo
- Publication number
- JPH01121247A JPH01121247A JP27840187A JP27840187A JPH01121247A JP H01121247 A JPH01121247 A JP H01121247A JP 27840187 A JP27840187 A JP 27840187A JP 27840187 A JP27840187 A JP 27840187A JP H01121247 A JPH01121247 A JP H01121247A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- optically active
- compound
- acid
- compound shown
- 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 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 6
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000000463 material Substances 0.000 abstract description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 abstract 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 16
- 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
- 239000002253 acid Substances 0.000 description 9
- 239000005711 Benzoic acid Substances 0.000 description 8
- 235000010233 benzoic acid Nutrition 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000004990 Smectic liquid crystal Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PSKIVCBTSGNKBB-UHFFFAOYSA-N 2-propoxypropan-1-ol Chemical compound CCCOC(C)CO PSKIVCBTSGNKBB-UHFFFAOYSA-N 0.000 description 2
- 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 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
- 150000001721 carbon Chemical group 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
- 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
- QIZFUOOPZJHIFV-UHFFFAOYSA-N 1-phenylmethoxynaphthalene-2-carboxylic acid Chemical compound OC(=O)C1=CC=C2C=CC=CC2=C1OCC1=CC=CC=C1 QIZFUOOPZJHIFV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WGKZYJXRTIPTCV-UHFFFAOYSA-N 2-butoxypropan-1-ol Chemical compound CCCCOC(C)CO WGKZYJXRTIPTCV-UHFFFAOYSA-N 0.000 description 1
- UKCFWUCWNZTUPT-UHFFFAOYSA-N 2-dodecoxypropan-1-ol Chemical compound CCCCCCCCCCCCOC(C)CO UKCFWUCWNZTUPT-UHFFFAOYSA-N 0.000 description 1
- DEDUBNVYPMOFDR-UHFFFAOYSA-N 2-ethoxypropan-1-ol Chemical compound CCOC(C)CO DEDUBNVYPMOFDR-UHFFFAOYSA-N 0.000 description 1
- UORWEJLEXRXMJC-UHFFFAOYSA-N 2-hexadecoxypropan-1-ol Chemical compound CCCCCCCCCCCCCCCCOC(C)CO UORWEJLEXRXMJC-UHFFFAOYSA-N 0.000 description 1
- IRZHCXWAHUFSFW-UHFFFAOYSA-N 2-hexoxypropan-1-ol Chemical compound CCCCCCOC(C)CO IRZHCXWAHUFSFW-UHFFFAOYSA-N 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- QFKPJXVBIMDQRJ-UHFFFAOYSA-N 2-nonoxypropan-1-ol Chemical compound CCCCCCCCCOC(C)CO QFKPJXVBIMDQRJ-UHFFFAOYSA-N 0.000 description 1
- VDLKSWBHHFUWOT-UHFFFAOYSA-N 2-octadecoxypropan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCOC(C)CO VDLKSWBHHFUWOT-UHFFFAOYSA-N 0.000 description 1
- FWFAVISHBVXODB-UHFFFAOYSA-N 2-octoxypropan-1-ol Chemical compound CCCCCCCCOC(C)CO FWFAVISHBVXODB-UHFFFAOYSA-N 0.000 description 1
- JTZLOANPENMPIP-UHFFFAOYSA-N 2-pentoxypropan-1-ol Chemical compound CCCCCOC(C)CO JTZLOANPENMPIP-UHFFFAOYSA-N 0.000 description 1
- OZTHFQSNGNJBBB-UHFFFAOYSA-N 2-tetradecoxypropan-1-ol Chemical compound CCCCCCCCCCCCCCOC(C)CO OZTHFQSNGNJBBB-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
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 238000006264 debenzylation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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ＴＮ（Ｔｗｉｓｔ
ｅｄ Ｎｅｍａｔｉｃ ）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, TN (Twist) using nematic liquid crystal
The ED Nematic) 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。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.
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）））。In order to meet the above-mentioned needs, a display device that utilizes the optical switching phenomenon of ferroelectric liquid crystals using optically active smectic liquid crystals has already been proposed (Applied Physics Letters (Appl, Phys, Lett, 1999).
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有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 is free of such unstable elements, has photochemical and chemical stability, and is useful as an intermediate for a ferroelectric liquid crystal 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、Ｒは炭素数１〜２０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 relates to an optically active compound represented by the general formula (I) (wherein R represents an alkyl group having 1 to 20 carbon atoms, and the mark * represents an asymmetric carbon atom).
（１）式の化合物は種々の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。Although the compound of formula (1) can be produced by various methods, it can typically be produced by the following synthetic route.
（ａ）
（ｂ）
（Ｃ）
（ｄ）
（但し、Ｒ１＊印は前記に同じ、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ポン酸（
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) (C) (d) (However, the R1* mark is the same as above, and Bz represents a benzyl group.) That is, 2,6-hydroxynaphthalenecarboxylic acid (
After a) is benzylated to form a compound (b), thionyl chloride, oxalate chloride or the like is further used to form an acid chloride derivative (c).
そして（Ｃ）と種々の光学活性２−アルコキシプロパツ
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。Then, (C) is reacted with various optically active 2-alkoxypropertools to form an ester (d). Thereafter, compound (I) can be produced by debenzylation with hydrogen in the presence of palladium/carbon.
本発明の化合物（１）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、、
１９５４ 、６７８）に記載の通り公知の物質である。The 2,6-hydroxynaphthalenecarboxylic acid used in the production of the compound (1) of the present invention is described, for example, in the Journal of the Chemical Society (J, Chem, Soc.
1954, 678), it is a known substance.
また光学活性２−アルコキシプロパツールとしては、具
体的には光学活性２−メトキシプロパツール、光学活性
２−エトキシプロパノール、光学活性２−プロポキシプ
ロパノール、光学活性２−ブトキシプロパノール、光学
活性２−ペンチルオキシプロパノール、光学活性２−へ
キシルオキシプロパノール、光学活性２−へブチルオキ
シプロパノール、光学活性２−オクチルオキシプロパツ
ール、光学活性２−ノニルオキシプロパノール、光学活
性２−デシルオキシブロバノール、光学活性２−ドデシ
ルオキシプロパノール、光学活性２−テトラデシルオキ
シプロバノール、光学活性２−ヘキサデシルオキシプロ
パノール、光学活性２−オクタデシルオキシプロパノー
ル、光学活性２−（２“−メチルプロポキシ）プロパツ
ール、光学活性２− （３’−メチルブトキシ）プロパ
ツール等を挙げることができる。Further, examples of the optically active 2-alkoxypropanol include optically active 2-methoxypropanol, optically active 2-ethoxypropanol, optically active 2-propoxypropanol, optically active 2-butoxypropanol, optically active 2-pentyloxy Propanol, optically active 2-hexyloxypropanol, optically active 2-hebutyloxypropanol, optically active 2-octyloxypropanol, optically active 2-nonyloxypropanol, optically active 2-decyloxybrobanol, optically active 2- Dodecyloxypropanol, optically active 2-tetradecyloxypropanol, optically active 2-hexadecyloxypropanol, optically active 2-octadecyloxypropanol, optically active 2-(2"-methylpropoxy)propanol, optically active 2-( Examples include 3'-methylbutoxy) propatool.
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（Ｉ）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り
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）安息香酸、４−（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）シクロへキシ
ルカルボン酸、トランス−４−（４’−アルコキシフェ
ニル）シクロへキシルカルボン酸、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）
シクロへキシルカルボン酸、４−（）ランス−４゛−ア
ルキルシクロへキシル）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−１’、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 (I) can be used, for example, as an alkylcarboxylic acid, an alkoxycarboxylic acid, 4-alkylbenzoic acid, 4-alkoxybenzoic acid, 4-alkylcarbonyloxybenzoic acid, or 4-alkoxycarbonylbenzoic acid. , 4-alkoxycarbonyloxybenzoic acid, 6-
Alkylnaphthalene-2-carboxylic acid, 6-alkoxynaphthalene-2-carboxylic acid, 6-alkylcarbonyloxy-naphthalene-2-carboxylic acid, 6-alkoxycarbonyl-naphthalene-2-carboxylic acid, 6-alkoxycarbonyloxy- naphthalene-2-carboxylic acid,
4-(4′-alkylphenyl)benzoic acid, 4-(4”
-alkoxyphenyl)benzoic acid, 4-(4'-alkylcarbonyloxyphenyl)benzoic acid, 4-(4'-
alkoxycarbonylphenyl)benzoic acid, 4-(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-()lanse-4'-alkylcyclohexyl)benzoic acid, 4-(5'-alkylpyrimidin-2'-yl)benzoic acid, 4-(5'-alkoxypyrimidine-2) '-yl)benzoic acid, 4-(trans-5"-alkyl-1', 3"-dioxane-
2'-yl)benzoic acid, 4-(trans-5'-alkyl-1',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
酸あるいは４−（４“−アルコキシフェニル）安息香酸
から製造される一般式（Ｕ）で示される化合物
（式中、ＲＩは炭素数１〜２０のアルキル基、ｍは１ま
たは２の整数を示し、Ｒ２は炭素数１〜２０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クＣ相を示
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非常に重要である。For example, a compound represented by the general formula (U) produced from the compound (1) of the present invention and 4-alkoxybenzoic acid or 4-(4"-alkoxyphenyl)benzoic acid (where RI is a carbon number of 1 to 20 alkyl groups, m represents an integer of 1 or 2, R2 represents an alkyl group having 1 to 20 carbon atoms, and the * mark represents an asymmetric carbon atom) are shown in the specific examples in Table 2. It exhibits a chiral smectic C phase and is very important as a constituent in preparing ferroelectric liquid crystal mixtures that operate near room temperature.
第２表中、Ｃは結晶相、ＳＣ９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 represents the crystalline phase, SC9 represents the chiral smectic C phase, SA represents the smectic A phase, and ■ represents the isotropic liquid. indicates the transition temperature of
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。Further, 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.
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。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.
１０一
実施例１
６−ヒトロキシナフタレンー２−カルボン酸＝（２°−
プロポキシ）プロピルエステル（式（１）においてＲ”
”Ｃｓ１（ｙの化合物）の製造（ｉ）６−ベンジルオキ
シナフタレン−２−カルボン酸の製造。101 Example 1 6-hydroxynaphthalene-2-carboxylic acid = (2°-
propoxy) propyl ester (R” in formula (1)
``Production of Cs1 (compound y) (i) 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、８
５％水酸化カリウム７０ｇを水１００ｒｄ、エタノール
７００ｄ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３５ｇの
水酸化カリウムを加え５時間加熱還流を続けた。2.6-Hydroxinaphthalenecarboxylic acid 100g, 8
70 g of 5% potassium hydroxide was dissolved in 100 d of water and 700 d of ethanol, 110 g of benzyl bromide was added thereto, and the mixture was heated under reflux for 8 hours. Thereafter, 35 g of potassium hydroxide was further 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−ベンジルオキシナフタレン−２
−カルボン酸６５ｇを５０ｍ１のトルエン中３０ｄ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
ルエンを減圧下留去し、酸塩化物を得た。この粗生成物
は次の反応に精製することなく用いた。(ii) Production of 6-benzyloxynaphthalene-2-carboxylic acid chloride Compound 6-benzyloxynaphthalene-2 obtained in (i)
- 65 g of carboxylic acid was heated under reflux with 30 d of thionyl chloride in 50 ml of toluene for 3 hours, and excess thionyl chloride and toluene were distilled off under reduced pressure to obtain an acid chloride. This crude product was used in the next reaction without purification.
（ｉｉ） （ｓ） ６−ベンジルオキシナフタレン
−２−カルボン酸−（２°−プロポキシ）プロピルエス
テルの製造
（ｉｉ ）で得た酸塩化物を１００ｄのトルエンに溶解
させ、この溶液に（ｓ）−２−プロポキシプロパノール
２７ｇをピリジン３０ｆｆｉｌ！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。(ii) (s) Production of 6-benzyloxynaphthalene-2-carboxylic acid-(2°-propoxy)propyl ester. Dissolve the acid chloride obtained in (ii) in 100 d of toluene, and add (s) to this solution. -27g of 2-propoxypropanol and 30ffil of pyridine! A solution dissolved in was added and left at room temperature for 8 hours. After the precipitated pyridine hydrochloride was filtered off, 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、トルエンを減圧下留去し目的物を６５
ｇ得た。The organic layer was separated, and the toluene was distilled off under reduced pressure to obtain the desired product.
I got g.
’Ｈ−ＮＭＲ（ｉｎ ＣＤＣ１３）
δ（ｐｐｍ） ０．９〜１．８（８１（） 、３．４
〜４．４（５Ｆ＋）５．２（２８） 、７．２〜８．５
（１１８）（ｉｖ） （ｉｉｉ）で得た（ｓ）−６−
ベンジルオキシナフタレン−２−カルボン酸−（２“−
プロポキシ）プロピルエステル６０ｇを２００１ｄ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。パラジウム／炭素を濾
別後、溶媒を減圧下に留去し、目的とする（ｓ）−６−
ヒトロキシナフタレンー２−カルボン酸−（２°−プロ
ポキシ）プロピルエステル４４ｇを得た。'H-NMR (in CDC13) δ (ppm) 0.9-1.8 (81(), 3.4
~4.4 (5F+) 5.2 (28), 7.2 ~ 8.5
(118) (iv) (s)-6- obtained in (iii)
Benzyloxynaphthalene-2-carboxylic acid-(2“-
60 g of propoxy)propyl ester was dissolved in 2001d ethanol and hydrogenated in the presence of 4 g of 5% palladium on carbon at normal pressure and 40°C. After filtering off the palladium/carbon, the solvent was distilled off under reduced pressure to obtain the desired (s)-6-
44 g of human roxinaphthalene-2-carboxylic acid-(2°-propoxy)propyl ester was obtained.
’ＨＮＭＲ（ｉｎ ＣＤＣｌ５）
δ （ｐｐｍ） ０．９〜１．８（８Ｈ） 、３．４
〜４．４（５Ｈ）７．２〜８．５（７Ｈ）
また、こ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。'HNMR (in CDCl5) δ (ppm) 0.9-1.8 (8H), 3.4
~4.4 (5H) 7.2~8.5 (7H) Furthermore, the elemental analysis values of this compound were in good agreement with the theoretical values as shown in Table 3.
実施例２〜９
実施例１の（ｉｎ）において、（ｓ）−２−プロポキシ
プロパノールの代わりに種々の光学活性２−アルコキシ
プロパツールを使用した以外は、実施例１の（ｉｉｉ）
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−カルボン第３表
酸−（２”−アルコキシ）プロピルエステルを製造した
。Examples 2-9 (iii) of Example 1, except that in (in) of Example 1, various optically active 2-alkoxypropanols were used in place of (s)-2-propoxypropanol.
Various optically active 6-benzyloxynaphthalene-2-carboxylic acid-(2''-alkoxy)propyl esters were prepared according to the method described in .
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−（２“−プロ
ポキシ）プロピ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−（２”
−アルコキシ）プロピ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−（２’
−アルコキシ）プロピルエステルを製造した。Further, in (iv) of Example 1, various optically active 6
-Benzyloxynaphthalene-2-carboxylic acid-(2”
Various optically active 6-hydroxynaphthalene-2-carboxylic acids-(2'
-alkoxy)propyl ester was prepared.
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
値とよく一致した。The elemental analysis values of these compounds were in good 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)
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) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R represents an alkyl group having 1 to 20 carbon atoms, and the * mark represents an asymmetric carbon atom. An optically active compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27840187A JPH0796530B2 (en) | 1987-11-05 | 1987-11-05 | Optically active compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27840187A JPH0796530B2 (en) | 1987-11-05 | 1987-11-05 | Optically active compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01121247A true JPH01121247A (en) | 1989-05-12 |
| JPH0796530B2 JPH0796530B2 (en) | 1995-10-18 |
Family
ID=17596833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27840187A Expired - Fee Related JPH0796530B2 (en) | 1987-11-05 | 1987-11-05 | Optically active compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796530B2 (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
- 1987-11-05 JP JP27840187A patent/JPH0796530B2/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 |
|---|---|
| JPH0796530B2 (en) | 1995-10-18 |
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