JPH0813765B2 - Fluorotran compounds - Google Patents
Fluorotran compoundsInfo
- Publication number
- JPH0813765B2 JPH0813765B2 JP12007087A JP12007087A JPH0813765B2 JP H0813765 B2 JPH0813765 B2 JP H0813765B2 JP 12007087 A JP12007087 A JP 12007087A JP 12007087 A JP12007087 A JP 12007087A JP H0813765 B2 JPH0813765 B2 JP H0813765B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- compound
- formula
- substituted
- nematic
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電気光学的表示材料として有用な新規なフル
オロトラン系化合物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel fluorotolan compound useful as an electro-optical display material.
液晶表示セルの中で現在主流をなすものは、電界効果
型セルの一種のTN型セルである。このTN型セルにおいて
は、G.BauerによってMol.Cryat.LIq.Cryst.63 45（198
1）に報告されているように、セル外観を損う原因とな
るセル表面での干渉縞の発生を防止するために、セルに
充填される液晶材料の屈折率の異方性（Δｎ）とセルの
厚さ（ｄ）μｍの積を或る特定の値に設定する必要があ
る。実用的に使用される液晶表示セルでは、Δｎ・ｄの
値が0.5,1.0,1.6又は2.2のいずれかに設定されている。
このようにΔｎ・ｄの値が一定値に設定されるから、Δ
ｎの値の大きな液晶材料を使用すれば、ｄの値を小なら
しめることができる。ｄの値が小となれば、応答時間
（τ）は、よく知られたταd2の関係式に従って小とな
る。従って、Δｎの値の大きな液晶材料は、応答速度が
速く、然も干渉縞のない液晶表示セルを製作するのに極
めて重要な材料である。一方、実用可能な液晶材料の多
くは、通常、室温付近にネマチック相を有する化合物と
室温より高い温度領域にネマチック相を有する化合物か
ら成る数種又はそれ以上の成分を混合することによって
調製される。現在実用的に使用される上記の如き混合液
晶の多くは、少なくとも−30℃〜＋65℃の全温度範囲に
亘ってネマチック相を有することが要求されているが、
液晶表示セルの応用製品の多様化に伴ない、ネマチック
液晶温度範囲を更に高温側に拡張した液晶材料が要望さ
れており、このため、ネマチック相−等方性液体相（Ｎ
−Ｉ）転移温度（以下、Ｎ−Ｉ点という。）の高いネマ
チック液晶化合物が必要とされている。Among the liquid crystal display cells, what is currently the mainstream is a TN cell, which is a kind of field effect cell. In this TN cell, G. Bauer described Mol.Cryat.LIq.Cryst. 63 45 (198
As reported in 1), in order to prevent the generation of interference fringes on the cell surface, which causes deterioration of the cell appearance, the anisotropy (Δn) of the refractive index of the liquid crystal material filled in the cell It is necessary to set the product of the cell thickness (d) μm to a certain value. In a practically used liquid crystal display cell, the value of Δn · d is set to either 0.5, 1.0, 1.6 or 2.2.
Since the value of Δn · d is set to a constant value in this way,
If a liquid crystal material having a large value of n is used, the value of d can be made small. When the value of d becomes small, the response time (τ) becomes small according to the well-known relational expression of ταd 2 . Therefore, a liquid crystal material having a large Δn value is a very important material for producing a liquid crystal display cell having a high response speed and no interference fringes. On the other hand, many practical liquid crystal materials are usually prepared by mixing several or more components consisting of a compound having a nematic phase near room temperature and a compound having a nematic phase in a temperature range higher than room temperature. . Many of the above-mentioned mixed liquid crystals that are practically used at present are required to have a nematic phase at least over the entire temperature range of -30 ° C to + 65 ° C.
Along with the diversification of applied products of liquid crystal display cells, there is a demand for a liquid crystal material in which the nematic liquid crystal temperature range is extended to a higher temperature side. Therefore, a nematic phase-isotropic liquid phase (N
There is a need for a nematic liquid crystal compound having a high -I) transition temperature (hereinafter referred to as NI point).
発明者らはこのような要求に応える大きなΔｎと高い
Ｎ−Ｉ点を有するネマチック液晶化合物として を提案した（特開昭60−152427号）。As a nematic liquid crystal compound having a large Δn and a high N-I point, the inventors of the present invention meet such requirements. Was proposed (Japanese Patent Laid-Open No. 60-152427).
しかし、この化合物は、現在母体液晶として実用的に
汎用されているネマチック混合液晶との相溶性に劣ると
いう欠点がある。However, this compound has a drawback that it is inferior in compatibility with nematic mixed liquid crystals which are practically used as a host liquid crystal at present.
本発明が解決しようとする問題点は、Δｎが大きく、
Ｎ−Ｉ点が高く、尚かつ現在母体液晶として実用的に汎
用されているネマチック混合液晶との相溶性の良い新規
なネマチック液晶化合物を提供することにある。The problem to be solved by the present invention is that Δn is large,
It is an object of the present invention to provide a novel nematic liquid crystal compound having a high NI point and having good compatibility with a nematic mixed liquid crystal which is practically widely used as a host liquid crystal at present.
本発明は、上記問題点を解決するために、一般式 〔式中、Ｒは炭素原子数１〜９の直鎖状アルキル基を表
わし、X1はフルオロ基又はメチル基を表わし、X2はフル
オロ基又は炭素原子数１〜９の直鎖状アルキル基を表わ
す。但し、X1とX2の少なくとも一つはフルオロ基を表わ
す。式中のシクロヘキサン環はトランス（エカトリアル
−エカトリアル）配置である。〕で表わされる化合物を
提供するものである。The present invention solves the above problems by using a general formula [In the formula, R represents a linear alkyl group having 1 to 9 carbon atoms, X 1 represents a fluoro group or a methyl group, and X 2 is a fluoro group or a linear alkyl group having 1 to 9 carbon atoms. Represents However, at least one of X 1 and X 2 represents a fluoro group. The cyclohexane ring in the formula is in the trans (equatorial-equatorial) configuration. ] The compound represented by these is provided.
本発明に係る式（Ｉ）の化合物は、次の製造方法に従
って製造することができる。The compound of formula (I) according to the present invention can be produced according to the following production method.
（上記式（II）及び（III）の各式におけるＲ、X1及びX
2は夫々、式（Ｉ）におけるＲ、X1及びX2と同じ意味を
もつ）。 (In each formula of the above formulas (II) and (III), R, X 1 and X
2 has the same meaning as R, X 1 and X 2 in formula (I), respectively.
式（II）の化合物をジエチルアミンの如き塩基の存在
下に、N,N−ジメチルホルムアルデヒドの如き溶媒中
で、ジクロロ−ビス（トリフェニルホスフィン）パラジ
ウム（II）とヨウ化第１銅を触媒として、式（III）の
化合物と反応させて本発明に係る式（Ｉ）の化合物を製
造する。A compound of formula (II) in the presence of a base such as diethylamine in a solvent such as N, N-dimethylformaldehyde, using dichloro-bis (triphenylphosphine) palladium (II) and cuprous iodide as catalysts, Reaction with a compound of formula (III) produces a compound of formula (I) according to the present invention.
斯くして製造される式（Ｉ）の化合物の代表的なもの
の転移温度を第１表に掲げる。The transition temperatures of representatives of the compounds of formula (I) thus prepared are listed in Table 1.
本発明に係る式（Ｉ）の化合物は弱い正又は弱い負の
誘電率異方性を有するネマチック液晶化合物であり、従
って例えば、負の誘電率異方性を有する他のネマチック
液晶化合物との混合物の状態で動的光散乱型表示セルの
材料として使用することができ、また正又は負の誘電率
異方性を有する他のネマチック液晶化合物との混合物の
状態で電界効果型表示セルの材料として使用することが
できる。 The compounds of formula (I) according to the present invention are nematic liquid crystal compounds having a weak positive or weak negative dielectric anisotropy and are therefore, for example, mixtures with other nematic liquid crystal compounds having a negative dielectric anisotropy. Can be used as a material for a dynamic light-scattering display cell in the state of, and as a material for a field-effect display cell in a mixture with another nematic liquid crystal compound having a positive or negative dielectric anisotropy. Can be used.
このように、式（Ｉ）の化合物と混合して使用するこ
とのできる好ましい代表例としては、例えば４−置換安
息香酸４′−置換フェニルエステル、４−置換シクロヘ
キサンカルボン酸４′−置換フェニルエステル、４−置
換シクロヘキサンカルボン酸４′−置換ビフェニルエス
テル、４−（４−置換シクロヘキサンカルボニルオキ
シ）安息香酸４′−置換フェニルエステル、４−（４−
置換シクロヘキシル）安息香酸４′−置換フェニルエス
テル、４−（４−置換シクロヘキシル）安息香酸４′−
置換シクロヘキシルエステル、４−置換４′−置換ビフ
ェニル、４−置換フェニル−４′−置換シクロヘキサ
ン、４−置換４′−置換ターフェニル、４−置換ビフェ
ニル４′−置換シクロヘキサン、２−（４−置換フェニ
ル）−５−置換ピリミジンなどを挙げることができる。Thus, as preferable representative examples which can be used by mixing with the compound of the formula (I), for example, 4-substituted benzoic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted phenyl ester , 4-substituted cyclohexanecarboxylic acid 4'-substituted biphenyl ester, 4- (4-substituted cyclohexanecarbonyloxy) benzoic acid 4'-substituted phenyl ester, 4- (4-
Substituted cyclohexyl) benzoic acid 4′-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4′-
Substituted cyclohexyl ester, 4-substituted 4'-substituted biphenyl, 4-substituted phenyl-4'-substituted cyclohexane, 4-substituted 4'-substituted terphenyl, 4-substituted biphenyl 4'-substituted cyclohexane, 2- (4-substituted Examples thereof include phenyl) -5-substituted pyrimidine.
第２表はネマチック液晶材料として現在母体液晶とし
て実用的に汎用されている混合液晶（Ａ）の85重量％と
第１表に示した式（Ｉ）の化合物No.1〜５の各々の15重
量％とから成る各混合液晶について測定されたＮ−Ｉ点
と屈折率の異方性（Δｎ）を掲示し、比較のために混合
液晶（Ａ）自体について測定されたＮ−Ｉ点とΔｎを掲
示したものである。尚、混合液晶（Ａ）は、 20重量％の 16重量％の 16重量％の ８重量％の ８重量％の ８重量％の ８重量％の ８重量％の 及び ８重量％の から成るものである。Table 2 shows 85% by weight of the mixed liquid crystal (A) which is practically widely used as a matrix liquid crystal as a nematic liquid crystal material and 15 of each of the compounds Nos. 1 to 5 of the formula (I) shown in Table 1. The measured NI point and the anisotropy (Δn) of the refractive index are shown for each mixed liquid crystal composed of 10% by weight, and the NI point and Δn measured for the mixed liquid crystal (A) itself are shown for comparison. Is posted. In addition, the mixed liquid crystal (A) contained 20% by weight. 16% by weight 16% by weight 8% by weight 8% by weight 8% by weight 8% by weight 8% by weight And 8% by weight It consists of
第２表に掲示したデータから、式（Ｉ）の化合物は混
合液晶（Ａ）のＮ−Ｉ点を実用上充分なまでに上昇さ
せ、而もΔｎを大幅に上昇せしめ得ることが理解でき
る。 From the data shown in Table 2, it can be understood that the compound of formula (I) can raise the NI point of the mixed liquid crystal (A) to a practically sufficient level, and can also significantly increase Δn.
本発明の効果は、下記の比較実験によっても明らかに
される。化学構造が本発明に係る式（Ｉ）の化合物に類
似しており、且つ混合液晶のＮ−Ｉ点及びΔｎを高める
目的で開発された式 の公知化合物を前記の混合液晶（Ａ）に添加したとこ
ろ、混合液晶（Ａ）に対する−30℃での溶解度は６％で
あった。この時の混合液晶のＮ−Ｉ点は62.1℃でΔｎは
0.101であった。The effect of the present invention is also clarified by the following comparative experiment. A compound having a chemical structure similar to that of the compound of formula (I) according to the present invention and a compound developed for the purpose of increasing the NI point and Δn of the mixed liquid crystal. When the known compound (1) was added to the mixed liquid crystal (A), the solubility in the mixed liquid crystal (A) at -30 ° C was 6%. The NI point of the mixed liquid crystal at this time is 62.1 ° C and Δn is
It was 0.101.
これに対し本発明に係る化合物の１つ、即ち式 の化合物の混合液晶（Ａ）に対する−30℃での溶解度は
14％であった。この時の混合液晶のＮ−Ｉ点は70.8℃で
Δｎは0.113であった。On the other hand, one of the compounds according to the invention, namely the formula The solubility of the compound in the mixed liquid crystal (A) at -30 ° C is
14%. The NI point of the mixed liquid crystal at this time was 70.8 ° C. and Δn was 0.113.
これらの事実から本発明に係る式（Ｉ）の化合物は代
表的な公知の類似化合物に比べて、現在母体液晶として
実用的に汎用されているネマチック混合液晶に多量に添
加し得るため、その結果Ｎ−Ｉ点とΔｎを大幅に上昇さ
せ得ることが理解できるであろう。From these facts, the compound of the formula (I) according to the present invention can be added in a large amount to the nematic mixed liquid crystal which is practically used as a host liquid crystal at present, as compared with a typical known similar compound. It will be appreciated that the NI point and Δn can be significantly increased.
実施例１ 式 の化合物3.28g（0.0100モル）をジエチルアミン4.1mlに
溶解し、この溶液にジクロロ−ビス（トリフェニルホス
フィン）パラジウム（II）7mg（0.010ミリモル）とヨウ
化第１銅19mg（0.10ミリモル）を加え、これらを室温で
撹拌しながら、４−ｎ−ブチル−２−フルオロフェニル
アセチレン1.76g（0.0100モル）をN,N−ジメチルホルム
アミド5mlに溶かした溶液を滴下した後、室温で24時間
放置した。この反応液を冷希塩酸水溶液中に撹拌しなが
ら加えて酸性とした後、反応生成物をトルエンで抽出
し、抽出液を水洗、乾燥後、この液からトルエンを留去
して、反応生成物を得た。Example 1 Formula 3.28 g (0.0100 mol) of the compound of Example 1 was dissolved in 4.1 ml of diethylamine, and 7 mg (0.010 mmol) of dichloro-bis (triphenylphosphine) palladium (II) and 19 mg (0.10 mmol) of cuprous iodide were added to this solution, While stirring these at room temperature, a solution of 1.76 g (0.0100 mol) of 4-n-butyl-2-fluorophenylacetylene dissolved in 5 ml of N, N-dimethylformamide was added dropwise, and the mixture was allowed to stand at room temperature for 24 hours. This reaction solution was added to cold dilute hydrochloric acid aqueous solution with stirring to make it acidic, the reaction product was extracted with toluene, the extract solution was washed with water and dried, and then toluene was distilled off from this solution to obtain a reaction product. Obtained.
得られた反応生成物を、シリカゲルカラムクロマトグ
ラフィーによって分離精製した後、ｎ−ヘキサンから再
結晶させて精製し、下記化合物1.43g（0.00380モル）を
得た。The obtained reaction product was separated and purified by silica gel column chromatography, and then purified by recrystallization from n-hexane to obtain 1.43 g (0.00380 mol) of the following compound.
実施例２ 実施例１と同様にして下記化合物を得た。 Example 2 The following compound was obtained in the same manner as in Example 1.
実施例３ 実施例１と同様にして下記化合物を得た。 Example 3 In the same manner as in Example 1, the following compound was obtained.
実施例４ 実施例１と同様にして下記化合物を得た。 Example 4 In the same manner as in Example 1, the following compound was obtained.
実施例５ 実施例１と同様にして下記化合物を得た。 Example 5 The following compound was obtained in the same manner as in Example 1.
〔発明の効果〕 本発明の新規ネマチック液晶化合物はＮ−Ｉ転移温度
が高く、しかもΔｎの大きいものであり、現在母体液晶
として実用的に汎用されているネマチック混合液晶に混
合することによってＮ−Ｉ点とΔｎを引き上げることが
できる。更に公知の構造類似化合物と比べ、現在母体液
晶として実用的に汎用されているネマチック混合液晶に
対する低温での溶解度が大きいため、より高いＮ−Ｉ点
とΔｎを有する混合液晶を作製することができる。 EFFECTS OF THE INVENTION The novel nematic liquid crystal compound of the present invention has a high NI transition temperature and a large Δn, and when mixed with a nematic mixed liquid crystal which is currently practically used as a host liquid crystal, N- The point I and Δn can be raised. Further, compared to known structurally similar compounds, the solubility at low temperature in the nematic mixed liquid crystal that is practically widely used as the host liquid crystal at the present time is large, so that a mixed liquid crystal having a higher NI point and Δn can be prepared. .
Claims (1)
わし、X1はフルオロ基又はメチル基を表わし、X2はフル
オロ基又は炭素原子数１〜９の直鎖状アルキル基を表わ
す。但し、X1とX2の少なくとも一つはフルオロ基を表わ
す。式中のシクロヘキサン環はトランス（エカトリアル
−エカトリアル）配置である〕 で表わされる化合物。1. A general formula [In the formula, R represents a linear alkyl group having 1 to 9 carbon atoms, X 1 represents a fluoro group or a methyl group, and X 2 is a fluoro group or a linear alkyl group having 1 to 9 carbon atoms. Represents However, at least one of X 1 and X 2 represents a fluoro group. The cyclohexane ring in the formula has a trans (equatorial-equatorial) configuration].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12007087A JPH0813765B2 (en) | 1987-05-19 | 1987-05-19 | Fluorotran compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12007087A JPH0813765B2 (en) | 1987-05-19 | 1987-05-19 | Fluorotran compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63287737A JPS63287737A (en) | 1988-11-24 |
| JPH0813765B2 true JPH0813765B2 (en) | 1996-02-14 |
Family
ID=14777149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12007087A Expired - Lifetime JPH0813765B2 (en) | 1987-05-19 | 1987-05-19 | Fluorotran compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813765B2 (en) |
-
1987
- 1987-05-19 JP JP12007087A patent/JPH0813765B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63287737A (en) | 1988-11-24 |
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