JPS63126844A - Biphenylcarboxylic acid derivative - Google Patents
Biphenylcarboxylic acid derivativeInfo
- Publication number
- JPS63126844A JPS63126844A JP26952486A JP26952486A JPS63126844A JP S63126844 A JPS63126844 A JP S63126844A JP 26952486 A JP26952486 A JP 26952486A JP 26952486 A JP26952486 A JP 26952486A JP S63126844 A JPS63126844 A JP S63126844A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- carboxylate
- reacting
- methylbutyl
- 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
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical class OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 26
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 14
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 abstract description 7
- 239000004990 Smectic liquid crystal Substances 0.000 abstract description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- PHBQSOODLMGROT-UHFFFAOYSA-N methyl 4-(4-hydroxyphenyl)benzoate Chemical compound C1=CC(C(=O)OC)=CC=C1C1=CC=C(O)C=C1 PHBQSOODLMGROT-UHFFFAOYSA-N 0.000 abstract description 3
- IWTBVKIGCDZRPL-UHFFFAOYSA-N (+/-)-3-Methyl-1-pentanol Natural products CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 abstract description 2
- QPRQEDXDYOZYLA-YFKPBYRVSA-N (S)-2-methylbutan-1-ol Chemical compound CC[C@H](C)CO QPRQEDXDYOZYLA-YFKPBYRVSA-N 0.000 abstract description 2
- HFRUPPHPJRZOCM-UHFFFAOYSA-N 4-octoxyphenol Chemical compound CCCCCCCCOC1=CC=C(O)C=C1 HFRUPPHPJRZOCM-UHFFFAOYSA-N 0.000 abstract description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N sec-pentyl alcohol Natural products CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 abstract description 2
- KLXVQCHMFOURGA-UHFFFAOYSA-N 4-[4-(2-methylbutoxy)phenyl]benzoic acid Chemical compound C1=CC(OCC(C)CC)=CC=C1C1=CC=C(C(O)=O)C=C1 KLXVQCHMFOURGA-UHFFFAOYSA-N 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- RUZLIIJDZBWWSA-INIZCTEOSA-N methyl 2-[[(1s)-1-(7-methyl-2-morpholin-4-yl-4-oxopyrido[1,2-a]pyrimidin-9-yl)ethyl]amino]benzoate Chemical group COC(=O)C1=CC=CC=C1N[C@@H](C)C1=CC(C)=CN2C(=O)C=C(N3CCOCC3)N=C12 RUZLIIJDZBWWSA-INIZCTEOSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000010446 mirabilite Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 5
- 150000001555 benzenes Chemical class 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- -1 (S)-2-methylbutyl Chemical group 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 210000003127 knee Anatomy 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- TWDAVWNDGHYAJZ-VIFPVBQESA-N (6s)-1-bromo-6-methyloctane Chemical compound CC[C@H](C)CCCCCBr TWDAVWNDGHYAJZ-VIFPVBQESA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- NGQQUXXTDZADNX-UHFFFAOYSA-N 2,3,4,5-tetrachlorofuran Chemical compound ClC=1OC(Cl)=C(Cl)C=1Cl NGQQUXXTDZADNX-UHFFFAOYSA-N 0.000 description 1
- XIIIHRLCKLSYNH-UHFFFAOYSA-N 4-Hexyloxyphenol Chemical compound CCCCCCOC1=CC=C(O)C=C1 XIIIHRLCKLSYNH-UHFFFAOYSA-N 0.000 description 1
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は新規な液晶性化合物及びこの液晶性化合物の少
なくとも１種を含有する液晶組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel liquid crystal compound and a liquid crystal composition containing at least one of the liquid crystal compounds.
ネマチック液晶化合物を用いた表示素子は、受光型で眼
が疲れ危い、消費電力が極めて少ない、ＩＣとの相性が
良い等の優れた特徴を有してるところから、時計、電卓
等に実用化され、それら商品における液晶表示方式とし
て定着化している。Display elements using nematic liquid crystal compounds have excellent features such as being light-receiving and causing eye fatigue, extremely low power consumption, and good compatibility with ICs, so they have been put into practical use in watches, calculators, etc. It has become established as the liquid crystal display method for these products.
ネマチック液晶化合物を用いた表示素子による表示方式
においては、そのほとんどがツイストネマチック（ＴＮ
）型（特開昭４７−１１７３７参照）であシ、この方式
には、応答が遅い、視角特性が不良である（視る角度に
よって見難い）等の欠点があるため、時計、電卓以外の
用途の拡大が図れていない。Most of the display systems using display elements using nematic liquid crystal compounds are twisted nematic (TN
) type (see Japanese Unexamined Patent Publication No. 47-11737). However, this method has drawbacks such as slow response and poor viewing angle characteristics (difficult to see depending on the viewing angle). The use of the product has not been expanded.
現在、上述の如き欠点を改善し、液晶の優れた特徴を生
かした表示素子を提供することによシ用途開発する目的
で、表示方式の改良及び新しい表示方式の研究が活発に
おこなわれている。Currently, research is being actively conducted to improve display methods and develop new display methods with the aim of improving the above-mentioned drawbacks and developing new applications by providing display elements that take advantage of the excellent characteristics of liquid crystals. .
それらの中で、Ｒ，Ｂ、 Ｍａｙｅｒらにより見い出さ
れた強誘電性液晶（Ｊ、Ｐｈｙｓｉｑｕｅ 、 弱、
Ｌ−６９（１９７５））はネマチック液晶に比べ格段に
高速応答が可能である所から実用化へ向けてのこれを用
いた表示素子（Ｎ、Ａ、 Ｃ１ａｒｋ 、 Ｓ、Ｔ、
Ｌａｇｅｒｗａｌｌ Ａｐｐｌ、Ｐｈｙｓ 。Among them, ferroelectric liquid crystals (J, Physique, weak,
L-69 (1975)) is a display element (N, A, C1ark, S, T,
Lagerwall Appl, Phys.
Ｌｅ ｔｔ、侶へ、８９９（１９８０））の研究がよシ
活発に行われるに至っている。この表示方式は、強誘電
性液晶のカイラルスメクテイツクＣ相（以下８ｍＣ”と
略記する）、カイラルスメクテイツクＨ相（以下、Ｓｍ
Ｈ”と略記する）を利用するものであるが、これに用い
る強誘電性液晶材料として見出されている化合物は未だ
数が少くまた実用に供し得るものが得られていない。Lett., 899 (1980)) is now being actively researched. This display system uses chiral smect C phase (hereinafter abbreviated as 8mC) and chiral smect H phase (hereinafter referred to as SmC) of ferroelectric liquid crystal.
However, the number of compounds that have been discovered as ferroelectric liquid crystal materials for this purpose is still small, and none that can be put to practical use have yet been obtained.
本発明者らは、前述の如き状況下に、実用に供し得る化
学的に安定で広いＳｍＣ”相を有する液晶化合物及び組
成物成分として有用な液晶化合物の開発を目的として鋭
意研究した結果、本発明に係る新規化合物を提供するに
至った。Under the above-mentioned circumstances, the present inventors conducted intensive research with the aim of developing a liquid crystal compound having a chemically stable and wide SmC phase that can be used in practical applications and a liquid crystal compound useful as a composition component. A novel compound according to the invention has now been provided.
すなわち、本発明は、一般式
（式中、Ｒは炭素原子数１〜１８のアルキル基であシ、
ｎは１〜７の整数を表わす）で表わされる化合物並びＫ
この化合物の少くとも１種を含有することを特徴とする
液晶組成物を提供するものである。That is, the present invention provides a method using the general formula (wherein R is an alkyl group having 1 to 18 carbon atoms,
n represents an integer from 1 to 7)
The present invention provides a liquid crystal composition containing at least one of these compounds.
本発明に係る新規な強誘電性液晶化合物は、化学的に安
定であシ、それ自身単独で広い温度範囲でＳｍＣ”相を
有するものであるが、それらの混合物あるいは他の液晶
組成物に添加することによシ得られる混合物によシ、Ｓ
ｍＣ”相の温度範囲を拡張することができ、したがって
、本発明に係る新規なビフェニルカルボン酸誘導体は、
表示素子の動作温度範囲の拡張のために有効に使用され
る物質である。The novel ferroelectric liquid crystal compound according to the present invention is chemically stable and has an SmC'' phase by itself over a wide temperature range, but it can be added to a mixture thereof or to other liquid crystal compositions. The mixture obtained by
The temperature range of the mC” phase can be extended, and therefore the novel biphenylcarboxylic acid derivatives according to the present invention
This material is effectively used to extend the operating temperature range of display elements.
以下に、本発明に係る新規化合物の合成ルートを示し、
そして実施例によりそれら化合物の製造方法例及び使用
例を具体的に説明する。Below, the synthesis route of the new compound according to the present invention is shown,
Examples of manufacturing methods and usage examples of these compounds will be specifically explained using Examples.
図式中に示された（１）〜０４Ｖ）の記号は、いずれも
実施例中の対応する各化合物に符されているものである
。例中で、使用されている略号の意味は以下のとおりで
ある。The symbols (1) to 04V) shown in the diagram are the same as the corresponding compounds in the examples. In the examples, the meanings of the abbreviations used are as follows.
ｍ、ｐ、 ：融点
Ｓｍ：スメクテイツク相
ＳｍＣ” ：カイラルスメクテイツクＣ相ＳｍＡ ：ス
メクテイツク人相
ＳｍＢ ：スメクテイツクＢ相
Ｓｘ：同定できなかったスメクテイック相Ｃｈ：コレス
テリツク相
Ｉｓｏ ：等方性液体
Ｃｒｙｓｔ ：結晶状態
実施例 １
（Ｓ）−ｐ−オクチルオキシフェニル４−［（２’−メ
チルブチル）オキシコピフェニル−４′−カルボキシレ
ート（Ｖ）の合成
（ａ） （Ｓ）−２−メチルブチルｐ−トルエンスル
フォネート（１）の合成
（Ｓ）−２−メチル−１−ブタノール２５Ｃ１’。m, p, : Melting point Sm: Smectic phase SmC" : Chiral smectic C phase SmA : Smectic human phase SmB : Smectic B phase Sx: Unidentified smectic phase Ch: Cholesteric phase Iso : Isotropic liquid Cryst : Crystal Condition Example 1 Synthesis of (S)-p-octyloxyphenyl 4-[(2'-methylbutyl)oxycopyphenyl-4'-carboxylate (V) (a) (S)-2-methylbutyl p-toluenesulfate Synthesis of phonate (1) (S)-2-methyl-1-butanol 25C1'.
ピリジン９００ＣＨの混合物へ、攪拌しなからｐ−トル
エンスルフオニルクロライ’ｔ’５４２１を、１０℃以
下の温度で、徐々に投入した。While stirring, p-toluenesulfonylchloride't'5421 was gradually added to the mixture of pyridine 900CH at a temperature of 10° C. or lower.
同温度で、５時間反応させた後、反応液を水に注加し九
。遊離した有機層をベンゼンで抽出し死後、このベンゼ
ン層を中性になるまで希塩酸で洗浄した。さらにこのベ
ンゼン層を水洗し、芒硝で乾燥させた後、溶媒を留去し
て５２３ＩＩ（７）（Ｓ）−２−メチルブチルｐ−）ル
エンスルフオネート（１）を得た。After reacting at the same temperature for 5 hours, the reaction solution was poured into water. The liberated organic layer was extracted with benzene, and after death, the benzene layer was washed with dilute hydrochloric acid until it became neutral. Further, this benzene layer was washed with water, dried with Glauber's salt, and then the solvent was distilled off to obtain 523II(7)(S)-2-methylbutyl p-)luenesulfonate (1).
（ｂ） （Ｓ）−メチル４−［：（２’−メチルブチ
ル）オキシコピフェニル−４′−カルボキシレート（ｌ
ｉ）の合成
反応容器に、メチル４−ヒドロキシピフェニル−４′−
カルボキシレート９０ ｔＩ、 （Ｓ）−２−メチルブ
チルｐ−トルエンスルフオネー） （１）１１１１１無
水炭酸カリウム１１４＃、シクロヘキサノン１１を仕込
み、１３０〜１４０℃で、５時間攪拌した。(b) (S)-Methyl 4-[: (2'-methylbutyl)oxycopyphenyl-4'-carboxylate (l
i) Into the synthesis reaction vessel, methyl 4-hydroxypiphenyl-4'-
Carboxylate 90 tI, (S)-2-methylbutyl p-toluenesulfone) (1) 114 #11111 anhydrous potassium carbonate and 11 cyclohexanone were charged and stirred at 130 to 140°C for 5 hours.
放冷後、反応液を水へあけ、遊離した有機層をベンゼン
で抽出した。このベンゼン層をよく水洗した後、芒硝で
乾燥させた。溶媒を留去し、残留分をアセトンにより精
製し、９４．Ｐの（Ｓ）−メチル４− （（２’−メチ
ルブチル）オキシ〕ビフェニルー４′−カルボキシレー
ト（ＩＩ）１％＆。After cooling, the reaction solution was poured into water, and the liberated organic layer was extracted with benzene. This benzene layer was thoroughly washed with water and then dried with sodium sulfate. The solvent was distilled off and the residue was purified with acetone.94. (S)-Methyl 4-((2'-methylbutyl)oxy)biphenyl-4'-carboxylate (II) of P 1%&.
８ｍ
ｍ、ｐ、 １１８−１２２℃
（ｃ） （ｓ） −４−Ｃ（２’−メチルブチル）オ
キシ〕ビフェニルー４′−カルボン酸（Ｄｉ）の合成反
応容器に、（Ｓ）−メチル４− ［（２’−メチルブチ
ル）オキシコピフェニル−４１−カルボキシレート（ｌ
ｉ） ９４ 、Ｐ Ｃテトラヒドロ７２７２００ＣＨに
溶解）、メタノール２００ＣＣ，９５チ苛性ソーダ３０
Ｉ（水１５０ＣＣに溶解）ヲ仕込ミ、還流下に４時間攪
拌した。次に、この反応液に塩酸を投入して酸性とした
後、析出物を減圧デ過した。ｐ果した結晶を加熱乾燥し
て８５Ｉの（Ｓ）−４−（（２’−メチルブチル）オキ
シコピフェニル−４′−カルボン酸（１ｌｌ）を得た。8 mm, p, 118-122°C (c) (s) -4-C(2'-Methylbutyl)oxy]biphenyl-4'-carboxylic acid (Di) synthesis reaction vessel was charged with (S)-methyl 4-[ (2'-methylbutyl)oxycopyphenyl-41-carboxylate (l
i) 94, dissolved in P C tetrahydro 727,200CH), methanol 200CC, 95CH caustic soda 30
I (dissolved in 150 cc of water) was charged and stirred under reflux for 4 hours. Next, hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was filtered off under reduced pressure. The resulting crystals were dried by heating to obtain 85I (S)-4-((2'-methylbutyl)oxycopyphenyl-4'-carboxylic acid (1 liter)).
（→ （Ｓ） −４−（（２’−メチルブチル）オキシ
フビフェニル−４′−カルボニルクロライ）’ （ｉＶ
）の合成
反応容器に、（Ｓ）−４−（（２’−メチルブチル）オ
キシュビフェニル−４′−カルボン酸（ｉｉｉ） ８５
Ｉｉ。(→ (S) -4-((2'-methylbutyl)oxyfubiphenyl-4'-carbonylchloride)' (iV
) (S)-4-((2'-methylbutyl)oxyubiphenyl-4'-carboxylic acid (iii) 85
Ii.
ベンゼン７０００Ｃ，少量のピリジンを仕込み、還流下
に攪拌しながら塩化チオニル５４Ｎを滴下した。次いで
同温度で１０時間反応させた後、溶媒と過剰の塩化チオ
ニルを留去して（Ｓ） −４−（（２’−メチルブチル
）オキシフビフェニル−４′−カルボニルクロライ￥（
ＩＶ） ９ ｏ ｉを得り。7000C of benzene and a small amount of pyridine were charged, and 54N of thionyl chloride was added dropwise while stirring under reflux. After reacting at the same temperature for 10 hours, the solvent and excess thionyl chloride were distilled off to give (S) -4-((2'-methylbutyl)oxyfubiphenyl-4'-carbonylchloride\(
IV) Obtained 9 o i.
（ｅ）（Ｓ）−ｐ−オクチルオキシフェニル４−（（２
’−メチルブチル）オキシコピフェニル−４′−カルボ
キシレート（Ｖ）の合成
反応容器に、ｐ−オクチルオキシフェノール２．２１％
ぺ７ゼン１０ＣＣ，ピリジ：１０．ＢＩを仕込み、攪拌
しながら室温下、（Ｓ）−４−Ｃ（２’−メチルブチル
）オキシフピフェニル−４′−カルボニルクロライド（
ｌｖ） ３１ （ベンゼン２０ＣＣに溶解させｆｃ）を
滴下した。室温下で２時間、さらに還流下で３時間、反
応させた後、反応液を水に注加した。(e) (S)-p-octyloxyphenyl 4-((2
'-Methylbutyl)oxycopyphenyl-4'-carboxylate (V) In a reaction vessel, 2.21% p-octyloxyphenol was added.
Pe7zen 10CC, Piriji: 10. After charging BI, (S)-4-C(2'-methylbutyl)oxyfupiphenyl-4'-carbonyl chloride (
lv) 31 (fc dissolved in 20 CC of benzene) was added dropwise. After reacting at room temperature for 2 hours and further under reflux for 3 hours, the reaction solution was poured into water.
遊離したベンゼン層をよく水洗し、芒硝で乾燥させた。The liberated benzene layer was thoroughly washed with water and dried with Glauber's salt.
ベンゼンを留去し、残留分をアセトンより２回再結晶し
て（ｓ）−ｐ−オクチルオキシフェニル４−（（２’−
メチルブチル）オキシフビフェニル−４′−カルボキシ
レート（Ｖ） １．９．９１−得り。Benzene was distilled off, and the residue was recrystallized twice from acetone to give (s)-p-octyloxyphenyl 4-((2'-
Methylbutyl)oxyfubiphenyl-4'-carboxylate (V) 1.9.91-obtained.
このものの純度は液体クロマトグラフィーにて、９９１
以上、薄層クロマトグラフィーにて、１スポツトであっ
た。また、赤外線吸収スペクトル測定によれば、特性値
は２８００〜３０００ｚ−’、１７５０ｃｍ−１，１６
００ｍ−’ 、 １２００ｍ−’であった。またマスス
ペクトル分析では、４８８に分子イオンピーク、２６７
に基準ピークが認められ、このものの化学構造が支持さ
れた。The purity of this product was determined to be 991 by liquid chromatography.
The above results showed 1 spot in thin layer chromatography. Also, according to infrared absorption spectrum measurement, the characteristic values are 2800 to 3000z-', 1750cm-1,16
00m-' and 1200m-'. Also, in mass spectrometry analysis, the molecular ion peak was at 488, and the molecular ion peak was at 267.
A reference peak was observed, supporting the chemical structure of this product.
このものをメトラーホットステージＦＰ−８２にはさみ
、偏光顕微鏡下で相変化を観察したところ、以下のよう
であった。This product was placed on a Mettler hot stage FP-82, and the phase change was observed under a polarizing microscope, and the results were as follows.
Ｇｒｙａ Ｄ、”−５ｍＧ” ”ｍ＝＊ｍｔ＋ ニニｃ
ｎ −ニーＩ ８゜実施例 ２〜５
実施例１に準拠して、同様にして各種の誘導体を合成し
、相転移温度を測定した結果を表１に示す。〔表中、Ｒ
は、前記一般式（１）中における記号Ｒを意味しそれに
より各化合物を示す。〕実施例 ６
（Ｓ） −ｐ−ペンチルオキシフェニル４−［：（４’
−メチルヘキシル）オキシコピフェニル−４′−カルボ
キシレート（１×）の合成
（ａ）（□□□−メチル４−［（４’−メチルヘキシル
）オキシコピフェニル−４′−カルボキシレート（ｖｌ
）の合成
反応容器に、メチル４−ヒドロキシビフェニル−４′−
カルボキシレート６７．５１． （ｓ）−４−）チルヘ
キシルプＯマイト（Ｍｏｔ、 Ｃｒｙｓ ｔ 、Ｌｉｑ
、 Ｃｒｙｓｔ 。Grya D, "-5mG""m=*mt+ Nini c
n-knee I 8° Examples 2 to 5 Based on Example 1, various derivatives were synthesized in the same manner as in Example 1, and the results of measuring the phase transition temperature are shown in Table 1. [In the table, R
represents the symbol R in the general formula (1) and indicates each compound. ] Example 6 (S) -p-pentyloxyphenyl 4-[:(4'
-Methylhexyl)oxycopiphenyl-4'-carboxylate (1x) Synthesis (a) (□□□-Methyl 4-[(4'-methylhexyl)oxycopiphenyl-4'-carboxylate (vl
), methyl 4-hydroxybiphenyl-4'-
Carboxylate 67.51. (s)-4-)TylhexylpOmite (Mot, Cryst, Liq
, Cryst.
ＩＬ４２３７〜２４７１９８４の反応例に従い合成。ｂ
、ｐ。Synthesized according to the reaction example of IL4237-2471984. b
, p.
７１〜ｂ
８２１１、’／クロヘキサノ／７５０ＣＣを仕込み、１
６０〜１４０℃で５時間攪拌した。71~b 8211, '/Clohexano/750CC was prepared, 1
The mixture was stirred at 60-140°C for 5 hours.
放冷後、反応液を水へあけ、遊離した有機層をベンゼン
で抽出した。ベンゼン層をよく水洗した後、芒硝で乾燥
させた。溶媒を留去し、残留分をア七トンよシ再結晶す
ることによシフ５９の（Ｓ）−メチル４− （（４’−
メチルヘキシル）オキシコピフェニル−４′−カルボキ
シレー） （ｖｉ）を得た。このものの相変化を偏光顕
微鏡下で観察したところ以下のようであった。After cooling, the reaction solution was poured into water, and the liberated organic layer was extracted with benzene. After thoroughly washing the benzene layer with water, it was dried with Glauber's salt. The solvent was distilled off and the residue was recrystallized from acetone to give Schiff 59's (S)-methyl 4- ((4'-
Methylhexyl)oxycopyphenyl-4'-carboxylate) (vi) was obtained. When the phase change of this product was observed under a polarizing microscope, it was as follows.
Ｃｒｙ５１ ｔ、」５≧ＳｍＢ 工姐二ＳｍＡ 二ｌ５
Ｏ（ｂ） （ｓ） −４−［（４’−メチルヘキシル
）オキシコピフェニル−４′−カルボン酸（ｖｉｉ）の
合成反応容器に、（Ｓ）−メチル４−［（４’−メチル
ヘキシル）オキシフビフェニル−４′−カルボキシレー
ト（ｖｉ） ７５ ｇ ＜テトラヒドロフラン２００孤
に溶解）、メタノール２００ＣＣ，９５１苛性ソーダ３
０！Ｉ（水１５０ＣＨに溶解）を仕込み、還流下に４時
間攪拌した。次に、この反応液に塩酸を投入して酸性と
した後、析出物を減圧濾過した。炉集した結晶を加熱乾
燥して６７．９の（Ｓ） −４−［（４’−メチルヘキ
シル）オキシフビフェニル−４′−カルボン酸（ｖｔｏ
を得た。Cry51 t,"5≧SmB 工姐二SmA 二l5
(S)-Methyl 4-[(4'-methylhexyl) ) Oxyfubiphenyl-4'-carboxylate (vi) 75 g <dissolved in 200 g of tetrahydrofuran), methanol 200 cc, 951 caustic soda 3
0! I (dissolved in 150 CH of water) was charged and stirred under reflux for 4 hours. Next, hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was filtered under reduced pressure. The collected crystals were dried by heating to obtain 67.9 (S)-4-[(4'-methylhexyl)oxyfubiphenyl-4'-carboxylic acid (vto
I got it.
（ｃ） （ｓ） −４−Ｃ（４＃−メチルヘキシル）
オキシコピフェニル−４′−カルボニルクロライド（Ｖ
ｉｉｔ）の合成
反応容器に、（Ｓ） −４−（（４’−メチルヘキシル
）オキシコピフェニル−４′−カルボン酸（Ｖｉｏ ６
７．９、ベンゼン６０００Ｃ１少量のピリジンを仕込み
、還流下に攪拌しながら塩化チオニル５１．９を滴下し
た。次いで同温度で１０時間反応させた後、溶媒と過剰
の塩化チオニルを留去して（Ｓ） −４−（（４’−メ
チルヘキシル）オキシフビフェニル−４′−カルボニル
クロライド（ｖ＋ｉＤ ｙ Ｏ＃を得た。(c) (s) -4-C (4#-methylhexyl)
Oxycopiphenyl-4'-carbonyl chloride (V
(S)-4-((4'-methylhexyl)oxycopiphenyl-4'-carboxylic acid (Vio 6
7.9, benzene 6000C1 A small amount of pyridine was charged, and thionyl chloride 51.9% was added dropwise while stirring under reflux. After reacting at the same temperature for 10 hours, the solvent and excess thionyl chloride were distilled off to give (S) -4-((4'-methylhexyl)oxyfubiphenyl-4'-carbonyl chloride (v+iD y O# I got it.
（ｃｌ）（Ｓ）−ｐ−ペンチルオキシフェニル４−（（
４’−メチルヘキシル）オキシフビフェニル−４′−カ
ルボキシレート（ｌ×）の合成反応容器に、ｐ−ペンチ
ルオキシフェノール２１１ペンゼ／１０ＣＣ１ピリジン
０．８ Ｉｉを仕込み、攪拌しながら、室温下（Ｓ）
−４−（（４’−メチルヘキシル）オキシコピフェニル
−４′−カルボニルクロライド（ｖｉｉｉ） ３ ｇ
（ベンゼン２０ＣＣＫ溶解）を滴下した。室温下で２時
間、さらに還流下で３時間反応させた後、この反応液を
水へ性態した。遊離したベンゼン層をよく水洗し、芒硝
で乾燥させ九。ベンゼンを留去し、残留分をアセト／よ
り２回再結晶して（Ｓ） −ｐ −４ンチルオキシフエ
ニル４− ［（４’−メチルヘキシル）オキシフビフェ
ニル−４′−カルボキシレート（＋Ｘ）１、５１１を得
た。このものの純度は、液体クロマトグラフィーにて一
９９９６以上、薄層クロマトグラフィーにて１スポツト
であった。ま九赤外線吸収スペクトル測定によれば特性
値は、２８００〜３０００α、１７２０ｍ 、１６００
α、１１９０譚であった。(cl)(S)-p-pentyloxyphenyl 4-((
Synthesis of 4'-methylhexyl)oxyfubiphenyl-4'-carboxylate (lx) 0.8 Ii of p-pentyloxyphenol 211penze/10CC1 pyridine was charged into a reaction vessel, and while stirring, the mixture was heated at room temperature (S )
-4-((4'-methylhexyl)oxycopyphenyl-4'-carbonyl chloride (viii) 3 g
(benzene dissolved in 20 CCK) was added dropwise. After reacting at room temperature for 2 hours and further under reflux for 3 hours, the reaction solution was converted into water. Wash the liberated benzene layer thoroughly with water and dry with sodium sulfate. Benzene was distilled off, and the residue was recrystallized twice from acetate to give (S)-p-4-ethyloxyphenyl 4-[(4'-methylhexyl)oxyfubiphenyl-4'-carboxylate ( +X) 1,511 was obtained. The purity of this product was 19996 or higher by liquid chromatography and 1 spot by thin layer chromatography. According to Maku infrared absorption spectrum measurement, the characteristic values are 2800-3000α, 1720m, 1600m.
α, 1190 Tan.
また、マススペクトル分析では４７４に分子イオンピー
ク、２９５に基準ピークが認められ、このものの化学構
造が支持された。このものをメトラーホットステージＦ
Ｐ−８２にはさみ、偏光顕微鏡下で相変化を観察したと
ころ以下のようであった。In addition, mass spectrometry analysis revealed a molecular ion peak at 474 and a reference peak at 295, supporting the chemical structure of this product. This one is Mettler Hot Stage F
When the sample was sandwiched between P-82 and the phase change was observed under a polarizing microscope, the following was observed.
ｘ
実施例 ７〜１０
実施例６に準拠して、同様にして各種の誘導体を合成し
、相転移温度を測定した結果を表２に示す。〔表中、Ｒ
は前記一般式（１）中における記号Ｒを意味し、それに
よシ各化合物を示す。〕実施例 １１
（Ｓｌｐ−へキシルオキシフェニル４−（（６’−メチ
ルオクチル）オキ７〕ピフェニル−４′−カルボキシレ
ート０４Ｖ）の合成
（ａ）（３１６−メチルオクチルブロマイド（Ｘ）の合
成
反応容器に、粉末臂グネシウム１３．８．９およびテト
ラクロフラン（水素化リチウムアルミニウムで処理した
後に蒸留して精ｍ）ｔ６ｏｃｃを仕込み、これＫ（Ｓ）
−２−メチルブチルブロマイド（Ｍｏｔ、Ｃｒｙｓｔ、
Ｌｉｑ、 Ｃｒｙｓｔ、 ４８３７〜５２１９７８の
反応例に従い合成６ｂ、ｐ、１２５〜１２４℃）７８２
を滴下してグリニヤール試薬を調製した。別に、反応容
器に、１．４−ジブロモブタン１２３ｇ、テトラヒト０
７５７ （ＴＨＦ） ３５０ＣＣ，および０．１ｍｏｖ
ｌのジリチウムテトラクロロキュープレート−’Ｉ’Ｈ
Ｆ溶液（Ｌｉ２ｃｕＣｔ４／ＴＨＦ）１８ｃｃを仕込み
、これに、０℃以下で上記のグリニヤール試薬を滴下し
た。x Examples 7 to 10 Based on Example 6, various derivatives were synthesized in the same manner, and the phase transition temperatures were measured. Table 2 shows the results. [In the table, R
represents the symbol R in the general formula (1), and each compound is represented by it. ] Example 11 Synthesis of (Slp-hexyloxyphenyl 4-((6'-methyloctyl)oxy7)piphenyl-4'-carboxylate 04V) (a) Synthesis reaction of (316-methyloctyl bromide (X)) Powdered magnesium 13.8.9 and tetrachlorofuran (purified by distillation after treatment with lithium aluminum hydride) t6occ were placed in a container, and this was K(S).
-2-methylbutyl bromide (Mot, Cryst,
Synthesis according to the reaction example of Liq, Cryst, 4837-521978 6b, p, 125-124 °C) 782
was added dropwise to prepare a Grignard reagent. Separately, in a reaction vessel, 123 g of 1,4-dibromobutane, 0
757 (THF) 350CC, and 0.1mov
l of dilithium tetrachlorocuprate-'I'H
18 cc of F solution (Li2cuCt4/THF) was charged, and the above-mentioned Grignard reagent was added dropwise thereto at 0°C or lower.
０℃以下で１時間、１０℃で１時間、さらに室温下で１
時間攪拌した後、反応液を希塩酸中に性態した。遊離し
た有機層をベンゼンで抽出し、ベンゼン層を充分に水洗
した。このベンゼン層を芒硝で乾燥させた後、溶媒を留
去し、残留分を減圧蒸留して（Ｓ） −６−メチルオク
チルブロマイド（Ｘ） ６０．９を得た。1 hour at 0℃ or below, 1 hour at 10℃, and 1 hour at room temperature.
After stirring for an hour, the reaction solution was poured into dilute hydrochloric acid. The liberated organic layer was extracted with benzene, and the benzene layer was thoroughly washed with water. After drying this benzene layer with Glauber's salt, the solvent was distilled off and the residue was distilled under reduced pressure to obtain (S)-6-methyloctyl bromide (X) 60.9.
ｂ、ｐ、１０２〜ｂ
（ｂ）（Ｓ）−メチル４−（（６＃−メチルオクチル）
オキシュビフェニル−４′−カルボキシレート（×１）
の合成
反応容器ニ、メチル４−ヒＰロキシビフェニルー４′−
カルボキシレート５Ｂ、９．（Ｓ）−６−メチルオクチ
ルプロマイ）（Ｘ）３Ｂ！ｉ、無水炭酸カリウム５３Ｉ
Ｉ、シクロヘキサノン５０００Ｃを仕込み１３０〜１４
０℃で５時間攪拌した。放冷後、反応液を水へあけ、遊
離した有機層をぺ／−１！＃ンで抽出した。このベンゼ
ン層をよく水洗した後、芒硝で乾燥させた。溶媒を留去
し、残留分をアセトンより再結晶することによ、９．５
０．９の（Ｓ）−メチル４− （（６＃−メチルオクチ
ル）オキシコピフェニル−４′−カルボキシレー） （
ＸＩ） ｔ−得り。b, p, 102~b (b) (S)-Methyl 4-((6#-methyloctyl)
Oxubiphenyl-4'-carboxylate (x1)
Synthesis reaction vessel D, Methyl 4-hydroxybiphenyl-4'-
Carboxylate 5B, 9. (S)-6-methyloctylpromy)(X)3B! i, anhydrous potassium carbonate 53I
I, prepare cyclohexanone 5000C 130-14
The mixture was stirred at 0°C for 5 hours. After cooling, the reaction solution was poured into water, and the free organic layer was diluted with P/-1! Extracted with #n. This benzene layer was thoroughly washed with water and then dried with sodium sulfate. By distilling off the solvent and recrystallizing the residue from acetone, 9.5
0.9 of (S)-methyl 4- ((6#-methyloctyl)oxycopiphenyl-4'-carboxyle) (
XI) t-gain.
ｍ、ｐ、１ １３℃□１２５℃
（ｃ） （Ｓ） −４−（（６’−メチルオクチル）
オキシュビフェニル−４′−カルボン酸（ｘｌｉ）の合
成反応容器に、（Ｓ）−メチル４−（（６“−メチルオ
クチル）オキシフビフェニル−４′−カルボキシレート
（ＸＩ） ５０１ （ｆトラヒｒａ−ｙう：／２００弘
に溶解）、メタノール２００ＣＣ，９５％苛性ソーダ１
５１（水１５０ＣＨに溶解）を仕込み、還流下に４時間
攪拌した。次に、この反応液に塩酸を投入して酸性とし
た後、析出物を減圧濾過した。テ果した結晶を加熱乾燥
して４５ｇの（Ｓ）−４−（（６＃−メチルオクチル）
オキシ５ビフェニル−４′−カルボン酸（ＸｉＤを得た
。m, p, 1 13℃□125℃ (c) (S) -4-((6'-methyloctyl)
In a reaction vessel for the synthesis of oxybiphenyl-4'-carboxylic acid (xli), (S)-methyl 4-((6"-methyloctyl)oxyfubiphenyl-4'-carboxylate (XI) 501 -y u: /200 hiro), methanol 200cc, 95% caustic soda 1
51 (dissolved in 150 CH of water) was charged and stirred under reflux for 4 hours. Next, hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was filtered under reduced pressure. The resulting crystals were heated and dried to give 45 g of (S)-4-((6#-methyloctyl)
Oxy-5biphenyl-4'-carboxylic acid (XiD) was obtained.
（ｄ） （Ｓ） −４−（（６Ｎ−メチルオクチル）
オキシュビフェニル−４′−カルボニルクロライド（Ｘ
ｉｉｌ ）の合成
反応容器に、（Ｓ）−４−［（６’−メチルオクチル）
オキシコピフェニル−４′−カルボン酸αｉ＋） ４５
１、ベンゼン５００ＣＣ，少量のピリジ／を仕込み、還
流下に攪拌しながら塩化チオニル３２ｇを滴下した。次
いで同温度で１０時間反応させた後溶媒と過剰の塩化チ
オニルを留去して４７ｇの（Ｓ） −４−（（６’−メ
チルオクチル）オキシュビフェニル−４′−カルボニル
クロライド（Ｘｉｊｉ）を得た。(d) (S) -4-((6N-methyloctyl)
Oxubiphenyl-4'-carbonyl chloride (X
(S)-4-[(6'-methyloctyl)
Oxycopyphenyl-4'-carboxylic acid αi+) 45
1. 500 cc of benzene and a small amount of pyridine were charged, and 32 g of thionyl chloride was added dropwise while stirring under reflux. After reacting at the same temperature for 10 hours, the solvent and excess thionyl chloride were distilled off to obtain 47 g of (S)-4-((6'-methyloctyl)oxyubiphenyl-4'-carbonyl chloride (Xiji). Obtained.
（ｅ）（Ｅｌ）−ｐ−ヘキシルオキシフェニル４−［（
６’−メチルオクチル）オキシフビフェニル−４′−カ
ルボキシレート（文■）の合成反応容器に、ｐ−へキシ
ルオキシフェノール１．６ｇ、（７−に’７１ＱＣＣ，
ｋ’リジ：／ ０．７．９を仕込み、攪拌しながら・室
温下（Ｓ）−４−［（６’−メチルオクチル）オキシュ
ビフェニル−４′−カルボニルクロライド（Ｘｉｉｌ）
３．９ （イｙゼｙ２０ｃｃに溶解）を滴下した。室温
下で２時間、さらに還流下で３時間反応させた後、反応
液を水に性態した。(e) (El)-p-hexyloxyphenyl 4-[(
Synthesis of 6'-methyloctyl)oxyfubiphenyl-4'-carboxylate (text) Into a reaction vessel, 1.6 g of p-hexyloxyphenol, (7- to '71QCC,
k'lidi:/0.7.9 was added, and while stirring, at room temperature, (S)-4-[(6'-methyloctyl)oxyubiphenyl-4'-carbonyl chloride (Xiil)
3.9 (dissolved in 20 cc of sugar) was added dropwise. After reacting at room temperature for 2 hours and further under reflux for 3 hours, the reaction solution was dissolved in water.
遊離したベンゼン層をよく水洗し、芒硝で乾燥させた。The liberated benzene layer was thoroughly washed with water and dried with Glauber's salt.
ベンゼンを留去し、残留分をア七トンより２回再結晶し
て（Ｓ） −ｐ−ヘキシルオキシフェニル４−（（６’
−メチルオクチル）オキシコピフェニル−４′−カルボ
キシレー）（％Ｖ）ｉ、１．ｆｔ−得九。このものの純
度は、液体クロマトグラフィーにて９９１以上、薄層ク
ロマトグラフィーにて１スポツトであった。また、赤外
線吸収スペクトル測定によれば特性値は、２８００〜３
０００ｉ’、１７３０ｚ−’、１６００３−’、１２０
０ｃｍ−’ であった。また、マススペクトル分析では
、５１６に分子イオンビーク、３２３に基準ピークが認
められ、このものの化学構造が支持された。Benzene was distilled off, and the residue was recrystallized twice from a7ton to give (S) -p-hexyloxyphenyl 4-((6'
-methyloctyl)oxycopyphenyl-4'-carboxylate) (%V)i, 1. ft-9. The purity of this product was 991 or higher by liquid chromatography and 1 spot by thin layer chromatography. Also, according to infrared absorption spectrum measurement, the characteristic value is 2800 to 3
000i', 1730z-', 16003-', 120
It was 0 cm-'. Furthermore, mass spectrometry analysis revealed a molecular ion peak at 516 and a reference peak at 323, supporting the chemical structure of this product.
このものをメトラーホットステージＦＰ−８２にはさみ
、偏光顕微鏡下で相変化を観察したところ、以下のよう
であった。This product was placed on a Mettler hot stage FP-82, and the phase change was observed under a polarizing microscope, and the results were as follows.
。ｒｙｓｔ二。ニー？邊！８０゜本 １７４．５ ８
ニー３コ３１−ｏ、１８５．５ エ。。. ryst2. knee? Nearby! 80° book 174.5 8
Knee 3 ko 31-o, 185.5 d. .
実施例 １２〜１６
実施例１１に準拠して、同様にして各種の誘導体を合成
し、相転移温度を測定した結果を表３に示す。〔表中、
Ｒは前記一般式（１）中における記号Ｒを意味し、それ
により各化合物を示す。〕
実施例 １７
表面にデリイミＰ系高分子膜を塗布し、ラビング処理し
た２枚の透明電極を有するガラス基板に、マイラーフィ
ルムをはさんで、液晶セルを組立てた。なお、２枚の基
板は、そのラビング方向は平行になるようにされ、セル
間隔は、９℃ｗｔｓとした。この液晶セルに前記各実施
例で得られたＳｍＣ”相を有する化合物を封入し、等方
性液体からＳｍＣ”相まで徐冷した。Examples 12 to 16 Various derivatives were synthesized in the same manner as in Example 11, and the phase transition temperatures were measured. Table 3 shows the results. [In the table,
R means the symbol R in the general formula (1) and indicates each compound. Example 17 A liquid crystal cell was assembled by sandwiching a Mylar film between two glass substrates having two transparent electrodes, the surface of which was coated with a Deliimi P polymer film and rubbed. Note that the rubbing directions of the two substrates were parallel to each other, and the cell spacing was 9° C.wts. The compound having the SmC'' phase obtained in each of the above Examples was sealed in this liquid crystal cell, and slowly cooled from an isotropic liquid to a SmC'' phase.
この液晶セルを２枚の偏光板にはさみ、電圧を印加し、
極性を反転させると表示状態が変化した。このように、
各実施例で得られた各化合物のＳｍＣ”相は、強誘電性
を示し、電気光学素子として使用し得るものである。This liquid crystal cell is sandwiched between two polarizing plates and a voltage is applied.
When the polarity was reversed, the display status changed. in this way,
The SmC'' phase of each compound obtained in each example exhibits ferroelectricity and can be used as an electro-optical element.
実施例 １８
既存の強誘電性液晶化合物（Ｓ）−ｐ−オクチルオキシ
フェニル４−（（２’−メチルブチル）〕〕ピフェニル
ー４′−カルボキシレートＯＡＯム０ｒｙｓｔｒＬｉｑ
、 Ｃｒｙｓｔ、 ３７１８９１９７６ ）と実施例１
で得られた（Ｓｉｐ−オクチルオキシフェニル４−（（
２’−メチルブチル）オキシコピフェニル−４〃−カル
ボキシレートとを重量比８０：２０及び６７：３３で混
合したものの各ＳｍＣ“相の温度範囲を表４に示した。Example 18 Existing ferroelectric liquid crystal compound (S)-p-octyloxyphenyl 4-((2'-methylbutyl)]]piphenyl-4'-carboxylate OAO)
, Cryst, 371891976) and Example 1
(Sip-octyloxyphenyl 4-((
Table 4 shows the temperature range of each SmC phase when mixed with 2'-methylbutyl)oxycopiphenyl-4-carboxylate at a weight ratio of 80:20 and 67:33.
この表から明らかなように（Ｓ） −ｐ−オクチルオキ
シフェニル４−（（２’−メチルブチル）〕〕ビアユニ
ルー４′−カルボキシレーは、単独ではＳｍＣ”相の温
度範囲が７６〜８８．６℃すなわち、巾が１２．６℃で
あるのに対し、（８）−ｐ−オクチルオキシフェニル４
−ＣＣ２’−メチルブチル）オキシコピフェニル−４′
−カルボキンレートを添加スル（ｚｏｔｓ）ことに！り
、７２〜９７℃スナワチ巾が２５℃となっていることが
判る。同様に３３重量−の場合は、６８〜１０１℃すな
わち巾が３３℃と拡張されている。As is clear from this table, when (S)-p-octyloxyphenyl 4-((2'-methylbutyl)]]viauniru-4'-carboxylene is used alone, the temperature range of the SmC'' phase is 76 to 88.6°C. That is, while the width is 12.6°C, (8)-p-octyloxyphenyl 4
-CC2'-methylbutyl)oxycopyphenyl-4'
-I decided to add carboquinlate! It can be seen that the width between 72 and 97°C is 25°C. Similarly, in the case of 33 weight -, the width is expanded to 68 to 101°C, that is, 33°C.
このように、本発明に係る化合物は、強誘電性液晶組成
物の温度範囲を拡張する成分として有用なものである。As described above, the compound according to the present invention is useful as a component for extending the temperature range of a ferroelectric liquid crystal composition.
特許出顯人 関東化学株式会社Patent issuer Kanto Chemical Co., Ltd.
Claims (1)
ｎは１〜７の整数を表わす）で表わされるビフェニルカ
ルボン酸誘導体。 ２）一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは炭素原子数１〜１８のアルキル基であり、
ｎは１〜７の整数を表わす）で表わされるビフェニルカ
ルボン酸誘導体の少くとも１種を含有することを特徴と
する液晶組成物。[Claims] 1) General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an alkyl group having 1 to 18 carbon atoms,
n represents an integer of 1 to 7). 2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an alkyl group having 1 to 18 carbon atoms,
1. A liquid crystal composition comprising at least one biphenylcarboxylic acid derivative represented by (n represents an integer of 1 to 7).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61269524A JPH0774182B2 (en) | 1986-11-14 | 1986-11-14 | Biphenylcarboxylic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61269524A JPH0774182B2 (en) | 1986-11-14 | 1986-11-14 | Biphenylcarboxylic acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63126844A true JPS63126844A (en) | 1988-05-30 |
| JPH0774182B2 JPH0774182B2 (en) | 1995-08-09 |
Family
ID=17473589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61269524A Expired - Lifetime JPH0774182B2 (en) | 1986-11-14 | 1986-11-14 | Biphenylcarboxylic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774182B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5323883A (en) * | 1976-08-16 | 1978-03-04 | Gray George William | Photooactive thermoocoloring mixture and liquid crystal electrooptical apparatus or thermoocoloring apparatus and surface temperature measuring method utilizing same |
| JPS60235885A (en) * | 1984-05-10 | 1985-11-22 | Alps Electric Co Ltd | Liquid crystal composition |
| JPS6281483A (en) * | 1985-10-04 | 1987-04-14 | Alps Electric Co Ltd | Liquid crystal composition |
| JPS63146985A (en) * | 1986-04-17 | 1988-06-18 | Seiko Epson Corp | Chiral smectic liquid crystal composition |
-
1986
- 1986-11-14 JP JP61269524A patent/JPH0774182B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5323883A (en) * | 1976-08-16 | 1978-03-04 | Gray George William | Photooactive thermoocoloring mixture and liquid crystal electrooptical apparatus or thermoocoloring apparatus and surface temperature measuring method utilizing same |
| JPS60235885A (en) * | 1984-05-10 | 1985-11-22 | Alps Electric Co Ltd | Liquid crystal composition |
| JPS6281483A (en) * | 1985-10-04 | 1987-04-14 | Alps Electric Co Ltd | Liquid crystal composition |
| JPS63146985A (en) * | 1986-04-17 | 1988-06-18 | Seiko Epson Corp | Chiral smectic liquid crystal composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774182B2 (en) | 1995-08-09 |
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