JPH0764829B2 - Liquid crystal compound - Google Patents
Liquid crystal compoundInfo
- Publication number
- JPH0764829B2 JPH0764829B2 JP60113766A JP11376685A JPH0764829B2 JP H0764829 B2 JPH0764829 B2 JP H0764829B2 JP 60113766 A JP60113766 A JP 60113766A JP 11376685 A JP11376685 A JP 11376685A JP H0764829 B2 JPH0764829 B2 JP H0764829B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal compound
- compound
- configuration
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、強誘電性スメクチツク液晶の電界への応答を
利用した電気光学素子に有用な新規の液晶化合物に関す
る。TECHNICAL FIELD The present invention relates to a novel liquid crystal compound useful for an electro-optical element utilizing the response of a ferroelectric smectic liquid crystal to an electric field.
液晶は、既に種々の電気光学素子として応用され、時計
や電卓などの表示に実用化されてきている。これらに使
用されている液晶化合物は、ネマテイツク液晶や、コレ
ステリツク液晶である。しかし、これら液晶ではコント
ラスト、視角特性の点で大型表示装置の実現は不可能に
近い。Liquid crystals have already been applied as various electro-optical elements and have been put to practical use for displays such as watches and calculators. Liquid crystal compounds used in these are nematic liquid crystals and cholesteric liquid crystals. However, it is almost impossible to realize a large-sized display device with these liquid crystals in terms of contrast and viewing angle characteristics.
こうした中で、クラークらはスメクチツクC*相を持つ液
晶化合物を使つた液晶素子を考案した。このスメクチツ
クC*相を持つ液晶化合物は種々合成されているところ、
最初に合成されたものはＦ−decyloxybenzilidene−
Ｆ′−amino−２−methyl butylcynnamateである。この
化合物と同じ系列の化合物が種々合成され、実用化の検
討を加えられているけれども、この系列の液晶は、室温
以上の比較的高温側でカイラルスメクチツク相を呈する
ため室温では使用できないことや、シツク系化合物であ
るため水分により分解を受け易く化学的安定性に欠ける
などの欠点がある。Under such circumstances, Clark et al. Devised a liquid crystal device using a liquid crystal compound having a smectic C * phase. While various liquid crystal compounds with this smectic C * phase have been synthesized,
The first one synthesized was F-decyloxybenzilidene-
F'-amino-2-methyl butylcynnamate. Although various compounds in the same series as this compound have been synthesized and are being investigated for practical use, liquid crystals of this series exhibit a chiral smectic phase at relatively high temperatures above room temperature and therefore cannot be used at room temperature. In addition, since it is a shock-based compound, it is liable to be decomposed by moisture and lacks chemical stability.
B.I.Ostrovskii らによつて の構造式で表わされる液晶化合物が紹介されている。
又、G.W.Grayら〔Mo1.Cryst.Liq.Cryst.,37（1976）18
9,（1978）37〕によりカイラルスメクチツク液晶相を呈
するビフエニルエステル系材料が報告されている。By BIostrovskii et al. A liquid crystal compound represented by the structural formula is introduced.
Also, GW Gray et al. [Mo1.Cryst.Liq.Cryst., 37 (1976) 18
9, (1978) 37] reported a biphenyl ester material exhibiting a chiral smectic liquid crystal phase.
本発明は、化学的安定性に優れ、室温を含む広い温度範
囲でカイラルスメクチツク液晶性を示す液晶組成物を得
ていくに当つての有力な新規液晶化合物を提供するもの
である。The present invention provides a powerful novel liquid crystal compound for obtaining a liquid crystal composition having excellent chemical stability and exhibiting chiral smectic liquid crystallinity in a wide temperature range including room temperature.
本発明によれば、次式 で示され＊印不斉炭素原子における立体配置がＲ体であ
るところの新規液晶化合物が提供される。According to the invention, , A novel liquid crystal compound having a configuration of R-configuration at the asymmetric carbon atom marked with * is provided.
この目的化合物は次のようにして合成される。This target compound is synthesized as follows.
即ち （イ）Ｒ体アミルアルコールの合成 O,Schiitz,W,Marckward,Ber.32 1092（1899）及び同29
53（1896）に記載の光学分割の方法に従い（Ｒ）−２−
メチル酪酸を得、これをリチウムアルミニウムハイドラ
イドその他金属水素化物で還元し、（Ｒ）−２−メチル
プタン−オール−１を得る。(B) Synthesis of R-form amyl alcohol O, Schiitz, W, Marckward, Ber. 32 1092 (1899) and 29
53 (1896) according to the optical resolution method (R) -2-
Methylbutyric acid is obtained and reduced with lithium aluminum hydride or other metal hydride to obtain (R) -2-methylputan-ol-1.
かしくて得られた（Ｒ）−２−メチルブタン−オール−
１は、これをハロゲン化し、クリニヤール試薬とし炭酸
ガスを反応させ得られるカルボン酸を金属水素化物で還
元すると炭素原子１個多くなつた（Ｒ）−３−メチルペ
ンタン−オール−１が得られる。また、前記ハロゲン化
物をマロン酸エステルと反応させ、加水分解、脱炭酸し
て、金属水素化物で還元すると炭素原子２個多くなつた
（Ｒ）−４−メチルヘキサン−オール−１が得られる。
これを適宜繰り返し実用すれば炭素数を任意の数に調整
したＲ体アルコールを得ることができる。(R) -2-methylbutan-ol-obtained
In the case of 1, the carboxylic acid obtained by halogenating this and reacting it with carbon dioxide gas using a Clinair reagent is reduced with a metal hydride to obtain (R) -3-methylpentan-ol-1 having one more carbon atom. When the halide is reacted with malonic acid ester, hydrolyzed and decarboxylated, and reduced with a metal hydride, (R) -4-methylhexan-ol-1 having two more carbon atoms is obtained.
By repeating this as appropriate for practical use, an R-alcohol having an adjusted carbon number can be obtained.
（ロ）２−（４−ヒドロキシフエニル）−５−アルキル
ピリミジンの合成 ４−ヒドロキシ（保護されたヒドロキシ基であつてもよ
い）ベンズアミジン若しくはその塩体に、アルキルアセ
トアルデヒドジアルキルアセタールとヴイルスマイヤー
試薬とを反応させて得られるβ−ジメチルアミノ−α−
アルキルアクロレインとをアルコラートの存在下で反応
させる。かくて、式 （Ｙは水素原子又はヒドロキシ基の保護基を示す。） で示される化合物を得る。ここにおいてピリミジン環上
に置換したアルキル基はC5〜C18の直鎖アルキル基を示
す。又保護基Ｙとしてはベンジル，ピラニルなどがあげ
られる。反応は、メタノール，エタノールなどのアルコ
ール溶媒中、ナトリウムメチラート，ナトリウムエチラ
ートを使つて好適に進めることができる。保護基Ｙは水
素添加，酸触媒などによつて取り除かれる。(B) Synthesis of 2- (4-hydroxyphenyl) -5-alkylpyrimidine 4-hydroxy (may be a protected hydroxy group) benzamidine or its salt, alkyl acetaldehyde dialkyl acetal and Weilsmeier reagent Β-dimethylamino-α-obtained by reacting with
Reacting with alkylacrolein in the presence of alcoholate. Thus, the formula (Y represents a hydrogen atom or a hydroxy-protecting group). Here, the alkyl group substituted on the pyrimidine ring represents a C 5 to C 18 linear alkyl group. Examples of the protecting group Y include benzyl and pyranyl. The reaction can be suitably carried out using sodium methylate or sodium ethylate in an alcohol solvent such as methanol or ethanol. The protecting group Y is removed by hydrogenation, acid catalyst or the like.
（ハ）前記（イ），（ロ）に記述したところに従い得ら
れた化合物を反応させて本発明の目的化合物を得る。(C) The target compound of the present invention is obtained by reacting the compound obtained as described in (a) and (b) above.
ここにおいて反応は、前記（イ）記載の方法に従つて得
た化合物を塩化チオニル、三臭化燐などでハロゲン化
し、あるいはメタンスルホニルクロリド,F−トルエンス
ホニルクロリドなどでスルホン酸エステル化合物とした
のち、（ロ）記載の方法に従つて得た２−（４−ヒドロ
キシフエニル）−５−アルキルピリミジンと反応させる
ことによつて行われる。用いられる溶媒は、ジメチルホ
ルムアミド，ジメチルスルホキシド，ジメチルアセタミ
ドなどである。２−（４−ヒドロキシフエニル）−５−
アルキルピリミジンは、これら溶媒中で水素化ナトリウ
ム，金属アルカリを使つて、ヒドロキシ基の水素原子を
置換しておくとよい。In the reaction, the compound obtained according to the method described in (a) above is halogenated with thionyl chloride, phosphorus tribromide or the like, or converted to a sulfonic acid ester compound with methanesulfonyl chloride, F-toluenesulfonyl chloride or the like. Then, it is carried out by reacting with 2- (4-hydroxyphenyl) -5-alkylpyrimidine obtained according to the method described in (b). The solvent used is dimethylformamide, dimethylsulfoxide, dimethylacetamide or the like. 2- (4-hydroxyphenyl) -5-
The alkylpyrimidine is preferably substituted with hydrogen atom of the hydroxy group by using sodium hydride or metal alkali in these solvents.
以下実施例を記述して本発明を更に詳述する。The present invention will be described in more detail with reference to the following examples.
実施例１ （Ｒ）−５−ｎ−ウンデシル−２〔４−（２′−メチル
ブチルオキシ）フエニル〕ピリミジンの合成 50％水素化ナトリウム0.57gを乾燥したジメチルホルム
アミド6mlに懸濁し、２−（４−ハイドロキシフエニ
ル）−５−ｎ−ウンデシルピリミジン3.2gを乾燥ジメチ
ルホルムアミド6mlに溶かして加え、室温で60分間攪拌
後、（Ｒ）−２−メチル−１−（Ｆ−トルエンスホニ
ル）オキシブタン2.9gを乾燥ジメチルホルムアミド5ml
に溶かして加え、混合物を75〜80℃に加温し、８時間攪
拌反応を行い、反応液を氷水に注ぎ、酢酸エチルで抽出
し、食塩水で洗い、硫酸マグネシウム乾燥して、溶媒を
留去後、4.27gの残査を得た。このものをシリカゲルカ
ラムクロマトグラフイー、ついで再結晶により精製し
て、2.0gの（Ｒ）−５−ｎ−ウンデシル−２−〔４−
（２′−メチルブチルオキシ）フエニル〕ピリミジンを
得た ▲〔α〕25 D▼−7.05（Ｃ＝2.0,CHCl3） IRνmax cm-1;1610,1590,1435,1255,1170,850,800 ′Ｈ−NMR（60MHZ,CDCl3） δ（ppm）:0.6〜2.23 （m,30H） 2.53 （t, 2H） 3.72 （d, 2H） 6.88 （d, 2H） 8.24 （d, 2H） 8.43 （s, 2H） この液晶化合物は以下のような転移温度であつた。Example 1 Synthesis of (R) -5-n-undecyl-2 [4- (2'-methylbutyloxy) phenyl] pyrimidine 0.57 g of 50% sodium hydride was suspended in 6 ml of dry dimethylformamide to give 2- ( 3.2 g of 4-hydroxyphenyl) -5-n-undecylpyrimidine was dissolved in 6 ml of dry dimethylformamide and added, and the mixture was stirred at room temperature for 60 minutes, and then (R) -2-methyl-1- (F-toluenesulfonyl) oxybutane2.9. 5 ml of dry dimethylformamide
The mixture was heated to 75-80 ° C and stirred for 8 hours. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with brine, dried over magnesium sulfate and evaporated to remove the solvent. After leaving, 4.27g of residue was obtained. This product was purified by silica gel column chromatography and then recrystallization to obtain 2.0 g of (R) -5-n-undecyl-2- [4-
(2′-Methylbutyloxy) phenyl] pyrimidine was obtained ▲ [α] 25 D ▼ −7.05 (C = 2.0, CHCl 3 ) IRνmax cm −1 ; 1610,1590,1435,1255,1170,850,800 ′ H− NMR (60MHZ, CDCl 3 ) δ (ppm): 0.6 to 2.23 (m, 30H) 2.53 (t, 2H) 3.72 (d, 2H) 6.88 (d, 2H) 8.24 (d, 2H) 8.43 (s, 2H) This liquid crystal compound had the following transition temperatures.
（＊印は過冷却であることを示す。） この液晶化合物を、FVAラビングの一軸配向処理を施し
た基板間に挾持し、液晶層厚を2.5μｍとし、±20Vの電
圧印加で、直交ニコル下で特性を測定した。測定温度は
35℃であつた。 (* Indicates supercooling.) This liquid crystal compound was sandwiched between substrates that had been uniaxially oriented by FVA rubbing, and the liquid crystal layer thickness was 2.5 μm. The properties were measured below. The measurement temperature is
It was 35 ° C.
応答速度 210μｓ 実施例２ （Ｒ）−５−ｎ−オクチル−２−〔４−（４′−メチル
ヘキシルオキシ）フエニル〕ピリミジンの合成 50％水素化ナトリウム0.605gを乾燥ジメチルホルムアミ
ド5mlに懸濁し、２−（４−ハイドロキシフエニル）−
５−ｎ−オクチルピリミジン3.0gを乾燥ジメチルホルム
アミド7mlに溶かして加え、室温で60分間攪拌後、
（Ｒ）−４−メチル−１−（Ｆ−トルエンスルホニル）
オキシヘキサン2.84gを乾燥ジメチルホルムアミド5mlに
溶かして加え、混合物75〜80℃に加温し、８時間攪拌反
応を行つた後、氷水に注ぎ、酢酸エチルで抽出し、食塩
水で洗い、硫酸マグネシウムで乾燥後、溶媒を留去し
て、4.15gの残査を得た。この残査をシリカゲルカラム
クロマトグラフイー、再結晶により精製して、2.5gの
（Ｒ）−５−ｎ−オクチル−２−〔４−（４′−メチル
ヘキシルオキシ）フエニル〕ピリミジンを得た。Response rate 210 μs Example 2 Synthesis of (R) -5-n-octyl-2- [4- (4′-methylhexyloxy) phenyl] pyrimidine 0.605 g of 50% sodium hydride was suspended in 5 ml of dry dimethylformamide, 2- (4-hydroxyphenyl)-
3.0 g of 5-n-octylpyrimidine was dissolved in 7 ml of dry dimethylformamide and added, and after stirring at room temperature for 60 minutes,
(R) -4-methyl-1- (F-toluenesulfonyl)
2.84 g of oxyhexane dissolved in 5 ml of dry dimethylformamide was added and the mixture was heated to 75-80 ° C and stirred for 8 hours. After stirring for 8 hours, the mixture was poured into ice water, extracted with ethyl acetate, washed with brine and washed with magnesium sulfate. After drying at 4, the solvent was distilled off to obtain 4.15 g of a residue. The residue was purified by silica gel column chromatography and recrystallization to obtain 2.5 g of (R) -5-n-octyl-2- [4- (4'-methylhexyloxy) phenyl] pyrimidine.
▲〔α〕25 D▼−5.25○（Ｃ＝2,CHCl3） IRνmax cm-1;1610,1590,1435,1255,1170,850,802 ′Ｈ−NMR（60MHZ,CDCl3） δ（ppm）:0.6〜2.20 （m,28H） 2.55 （t, 2H） 3.97 （t, 2H） 6.91 （d, 2H） 8.25 （d, 2H） 8.48 （s, 2H） この液晶化合物の転移温度は以下のようであつた。▲ [α] 25 D ▼ −5.25 ○ (C = 2, CHCl 3 ) IRνmax cm −1 ; 1610,1590,1435,1255,1170,850,802 ′ H-NMR (60MHZ, CDCl 3 ) δ (ppm): 0.6 ~ 2.20 (m, 28H) 2.55 (t, 2H) 3.97 (t, 2H) 6.91 (d, 2H) 8.25 (d, 2H) 8.48 (s, 2H) The transition temperature of this liquid crystal compound is as follows. .
（＊印は過冷却であることを示す。） この液晶化合物を、FVAラビングの一軸配向処理を施し
た基板間に挾持し、液晶層厚を2.5μｍとし、±20Vの電
圧印加で、直交ニコル下で特性を測定した。測定温度は
27℃であつた。 (* Indicates supercooling.) This liquid crystal compound was sandwiched between substrates that had been uniaxially oriented by FVA rubbing, and the liquid crystal layer thickness was 2.5 μm. The properties were measured below. The measurement temperature is
It was 27 ° C.
応答速度 245μｓ 以上、実施例で示したように、本発明の化合物は、室温
近辺で、SC *相を有し、かつ応答速度の速い材料として
極めて有用である。又、本発明の化合物は、不斉炭素原
子まわりの立体配置がＲ体であるため、Ｓ体とは、逆ま
わりの立体配置がＲ体であるため、Ｓ体とは、逆まわり
の施光能を有する。よつて、Ｓ体と混合することによつ
て、SC *相のカイラルピツチを自由に変化させることが
出来、所望のカイラルピツチを有する強誘電性液晶組成
物を得る上で、有用な液晶化合物てある。Response speed 245 μs or more, as shown in the examples, the compound of the present invention is extremely useful as a material having an S C * phase near room temperature and having a high response speed. Further, since the compound of the present invention has an R configuration in the configuration around the asymmetric carbon atom, it has an R configuration in the opposite configuration with respect to the S configuration, and therefore has a configuration in the opposite configuration with respect to the S configuration. Have the ability. Therefore, by mixing with the S-form, the chiral pitch of the S C * phase can be freely changed, and it is a useful liquid crystal compound in obtaining a ferroelectric liquid crystal composition having a desired chiral pitch. .
Claims (1)
って、カイラルスメクチック液晶相（SC*）のスパイラ
ルピッチ調整能を有する強誘電性カイラルスメクチック
液晶化合物。 （式中ｍは１〜８、ｎは５〜18の整数を示す）1. A formula The ferroelectric chiral smectic liquid crystal compound having the R configuration in the configuration around the asymmetric carbon atom and having the ability to adjust the spiral pitch of the chiral smectic liquid crystal phase (SC * ). (In the formula, m represents an integer of 1 to 8 and n represents an integer of 5 to 18)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60113766A JPH0764829B2 (en) | 1985-05-27 | 1985-05-27 | Liquid crystal compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60113766A JPH0764829B2 (en) | 1985-05-27 | 1985-05-27 | Liquid crystal compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61271279A JPS61271279A (en) | 1986-12-01 |
| JPH0764829B2 true JPH0764829B2 (en) | 1995-07-12 |
Family
ID=14620597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60113766A Expired - Lifetime JPH0764829B2 (en) | 1985-05-27 | 1985-05-27 | Liquid crystal compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764829B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3577211D1 (en) * | 1984-06-07 | 1990-05-23 | Seiko Instr Inc | LIQUID CRYSTAL CONNECTION. |
| DE3515373A1 (en) * | 1985-04-27 | 1986-11-06 | Merck Patent Gmbh, 6100 Darmstadt | NITROGENIC HETEROCYCLES |
| JPH0794446B2 (en) * | 1986-06-25 | 1995-10-11 | 帝国化学産業株式会社 | 2-phenylpyrimidine derivative |
| JPH0684356B2 (en) * | 1986-12-26 | 1994-10-26 | 旭電化工業株式会社 | Pyrimidine compound |
| JPS63165370A (en) * | 1986-12-26 | 1988-07-08 | Adeka Argus Chem Co Ltd | Pyrimidine compound |
| US4804759A (en) * | 1987-05-27 | 1989-02-14 | Adeka Argus Chemical Co., Ltd. | Pyrimidine compound |
| US4824597A (en) * | 1987-06-23 | 1989-04-25 | Alps Electric Co., Ltd. | Liquid crystal composition |
| JP2691405B2 (en) * | 1987-11-06 | 1997-12-17 | チッソ株式会社 | Ferroelectric liquid crystal composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60260564A (en) * | 1984-06-07 | 1985-12-23 | Seiko Instr & Electronics Ltd | Liquid crystal compound |
| JPS6122072A (en) * | 1984-07-09 | 1986-01-30 | Seiko Instr & Electronics Ltd | Liquid crystal compound |
-
1985
- 1985-05-27 JP JP60113766A patent/JPH0764829B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60260564A (en) * | 1984-06-07 | 1985-12-23 | Seiko Instr & Electronics Ltd | Liquid crystal compound |
| JPS6122072A (en) * | 1984-07-09 | 1986-01-30 | Seiko Instr & Electronics Ltd | Liquid crystal compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61271279A (en) | 1986-12-01 |
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