JPH021811B2 - - Google Patents
Info
- Publication number
- JPH021811B2 JPH021811B2 JP8527282A JP8527282A JPH021811B2 JP H021811 B2 JPH021811 B2 JP H021811B2 JP 8527282 A JP8527282 A JP 8527282A JP 8527282 A JP8527282 A JP 8527282A JP H021811 B2 JPH021811 B2 JP H021811B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- trans
- terphenyl
- substituted
- temperature range
- 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
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
本発明は広い温度範囲で液晶相を示す低粘性な
液晶物質及びこれを含有する組成物に関する。
液晶表示素子は液晶物質が有する光学異方性及
び誘電異方性を利用したものであるが、その表示
方式にはTN型、DS型、ゲスト・ホスト型、
DAP型、ホワイト・テイラー型など各種の方式
があり、それぞれの方式により使用される液晶物
質に要求される性質も異る。例えば表示素子の種
類によつて、液晶物質として誘電異方性Δεが正
のものを必要としたり、負のものを必要とした
り、或はその中間的な値のものが適したりする。
しかしいずれにしても使用される液晶物質はでき
るだけ広い温度範囲で液晶相を示し、又水分、
熱、空気、光などに対して安定である必要があ
る。現在のところ単一化合物でこの様な条件をす
べて満たすものはなく、数種の液晶化合物や非液
晶化合物を混合して一応実用に耐えるものを得て
いるのが現状である。
最近、特に広い温度範囲、即ち低温（−20℃）
から高温（80℃位）まで動作する液晶表示素子が
要求されている。その上、更に届析率異方性△ｎ
が大きい組成物が必要な場合があり、従来の化合
物では、粘度が高く要求を満たせない。本発明の
化合物は、広い液晶温度範囲をもち、その上低粘
度で△ｎが大きく、前記の要求をある程度みたす
ものである。
即ち、本発明は一般式
（上式中Ｒは炭素数１〜10のアルキル基、R′は
水素原子又は炭素数１〜10を有するアルキル基を
示す）
で表わされる４−置換−4″−（トランス−４−
アルキルシクロヘキシル）テルフエニルである。
本発明の（）式の化合物は、例えば４−ペン
チル−4″−（トランス−４−エチルシクロヘキ
シル）テルフエニルはＣ−Ｓ点が室温以下、Ｓ−
Ｎ点が281℃、Ｎ−Ｉ点が300℃以上という様に広
い液晶温度範囲を持ちながら低粘度であり、その
上△ｎが大きく、従つて低粘性で広い温度範囲で
ネマチツク液晶相を示す液晶組成物を得るための
構成成分として好適な化合物である。
つぎに本発明の化合物の製造法について述べ
る。まず4′−置換−４−ブロモビフエニルと金属
マグネシウムと反応させ4′−置換ビフエニル−４
−マグネシウムプロミドとし、これを４−（トラ
ンス−4′−アルキルシクロヘキシル）シクロヘキ
サノンと反応させて４−置換−4′−〔4″−（トラン
ス−４−アルキルシクロヘキシル）シクロヘキ
サン−1″−オール〕ビフエニルとする。次にこれ
を硫酸水素カリウムで脱水して４−置換−4′−
〔4″−（トランス−４−アルキルシクロヘキシ
ル）シクロヘキセン−1″−イル〕ビフエニルとす
る。これをクロラニルで脱水素して目的の４−置
換−4″−（トランス−４−アルキルシクロヘキ
シル）テルフエニルを得る。以上を化学式で示す
と、次のようになる。
以下、実施例により本発明の化合物の製法及び
使用例についてさらに詳細に説明する。
実施例 １
〔４−エチル−4″−（トランス−４−エチ
ルシクロヘキシル）テルフエニルの製造〕
削り状マグネシウム1.2ｇ（0.049モル）を３つ
口フラスコに入れ、4′−エチル−４−ブロモビフ
エニル12.8ｇ（0.049モル）をテトラヒドロフラ
ンに溶かした液100mlを、N2気流中還流させなが
らゆつくり滴下していくとマグネシウムは反応し
て均一溶液となり、4′−エチルビフエニル−４−
マグネシウムプロミドを生じる。これに４−（ト
ランス−4′−エチルシクロヘキシル）シクロヘキ
サノンの8.3ｇ（0.040モル）をテトラヒドロフラ
ンに溶かした液50mlを反応温度を30℃以下に保ち
つつなるべく速かに滴下する。滴下後２時間還流
し、ついで3N−塩酸100mlを加える。反応後を分
液漏斗に移し100mlのトルエンで３回抽出後、合
わせたトルエン層を洗液が中性になるまで水洗し
トルエンを減圧留去する。残留物は４−エチル−
4′−〔4″−（トランス−４−エチルシクロヘキシ
ル）シクロヘキサン−1″−オール〕ビフエニルで
あり、これに硫酸水素カリウム40ｇを加え、N2
気流中150℃で１時間脱水する。冷却後、300mlの
トルエンを加え、硫酸水素カリウムを別し、ト
ルエン層を洗液が中性になるまで水洗する。つい
でトルエンを減圧留去し、残る油状物をトルエン
で再結晶して得られるのが４−エチル−4′−
〔4″−（トランス−４−エチルシクロヘキシルシ
クロヘキセン−1″−イル〕ビフエニルである。こ
のもの11ｇ（0.030モル）をキシレン300mlに溶か
しクロラニル16ｇ（0.065モル）を加え20時間還
流する。冷却後トルエン500mlを加え、6N−塩酸
で１回、2N−水酸化ナトリウムで３回洗い、飽
和食塩水で洗液が中性になるまで洗浄する。溶媒
を減圧留去し、トルエンで再結晶させ得られたも
のが目的物である４−エチル−4″−（トランス−
４−エチルシクロヘキシル）テルフエニルであ
る。収量５ｇ。そのＣ−Ｓ点は147.0℃、Ｓ−Ｎ
点は260℃、Ｎ−Ｉ点は300℃以上であつた。
実施例 ２〜６
実施例１と同様の方法で製造した他の（）式
の化合物を実施例１の結果と共に第１表に示す。
The present invention relates to a low-viscosity liquid crystal material that exhibits a liquid crystal phase over a wide temperature range and a composition containing the same. Liquid crystal display elements utilize the optical anisotropy and dielectric anisotropy of liquid crystal materials, and their display methods include TN type, DS type, guest-host type,
There are various types such as DAP type and White-Taylor type, and each type requires different properties of the liquid crystal material used. For example, depending on the type of display element, a liquid crystal material with a positive dielectric anisotropy Δε may be required, a material with a negative dielectric anisotropy may be required, or a material with an intermediate value may be suitable.
However, in any case, the liquid crystal materials used exhibit a liquid crystal phase over a wide temperature range, and also contain moisture and
It must be stable against heat, air, light, etc. At present, there is no single compound that satisfies all of these conditions, and the current state of affairs is to mix several types of liquid crystal compounds and non-liquid crystal compounds to obtain compounds that can withstand practical use. Recently, especially wide temperature range, i.e. low temperature (-20℃)
There is a need for liquid crystal display elements that can operate from low to high temperatures (approximately 80°C). Moreover, the notification rate anisotropy △n
In some cases, a composition with a high viscosity is required, and conventional compounds cannot meet this requirement due to their high viscosity. The compound of the present invention has a wide liquid crystal temperature range, has a low viscosity and a large Δn, and satisfies the above requirements to some extent. That is, the present invention is based on the general formula (In the above formula, R is an alkyl group having 1 to 10 carbon atoms, and R' is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) 4-substituted-4''-(trans-4-
alkylcyclohexyl)terphenyl. The compound of formula () of the present invention, for example, 4-pentyl-4''-(trans-4-ethylcyclohexyl)terphenyl has a C-S point below room temperature and an S-
It has a wide liquid crystal temperature range, with an N point of 281°C and an N-I point of 300°C or higher, but it also has a low viscosity.In addition, △n is large, so it has a low viscosity and exhibits a nematic liquid crystal phase over a wide temperature range. This compound is suitable as a component for obtaining a liquid crystal composition. Next, a method for producing the compound of the present invention will be described. First, 4'-substituted-4-bromobiphenyl was reacted with metallic magnesium to produce 4'-substituted biphenyl-4.
-magnesium bromide and reacted with 4-(trans-4'-alkylcyclohexyl)cyclohexanone to produce 4-substituted-4'-[4''-(trans-4-alkylcyclohexyl)cyclohexane-1''-ol] Biphenyl. Next, this was dehydrated with potassium hydrogen sulfate to give 4-substituted-4'-
[4″-(trans-4-alkylcyclohexyl)cyclohexen-1″-yl]biphenyl. This is dehydrogenated with chloranil to obtain the desired 4-substituted-4''-(trans-4-alkylcyclohexyl)terphenyl.The chemical formula shown above is as follows. Hereinafter, the production method and usage examples of the compound of the present invention will be explained in more detail with reference to Examples. Example 1 [Production of 4-ethyl-4″-(trans-4-ethylcyclohexyl)terphenyl] 1.2 g (0.049 mol) of magnesium turnings was placed in a three-necked flask, and 12.8 g of 4′-ethyl-4-bromobiphenyl was added. When 100 ml of a solution of (0.049 mol) dissolved in tetrahydrofuran was slowly added dropwise under reflux in a N2 stream, magnesium reacted and became a homogeneous solution, and 4'-ethylbiphenyl-4-
Produces magnesium bromide. To this, 50 ml of a solution of 8.3 g (0.040 mol) of 4-(trans-4'-ethylcyclohexyl)cyclohexanone dissolved in tetrahydrofuran was added dropwise as quickly as possible while keeping the reaction temperature below 30°C. After the dropwise addition, the mixture was refluxed for 2 hours, and then 100 ml of 3N hydrochloric acid was added. After the reaction was transferred to a separatory funnel and extracted three times with 100 ml of toluene, the combined toluene layer was washed with water until the washings became neutral, and the toluene was distilled off under reduced pressure. The residue is 4-ethyl-
4′-[4″-(trans-4-ethylcyclohexyl)cyclohexane-1″-ol]biphenyl, to which 40 g of potassium hydrogen sulfate was added and N 2
Dehydrate for 1 hour at 150°C in a stream of air. After cooling, add 300 ml of toluene, separate the potassium hydrogen sulfate, and wash the toluene layer with water until the washing liquid becomes neutral. Then, the toluene is distilled off under reduced pressure, and the remaining oil is recrystallized with toluene to obtain 4-ethyl-4'-
[4″-(trans-4-ethylcyclohexylcyclohexen-1″-yl]biphenyl). Dissolve 11 g (0.030 mol) of this product in 300 ml of xylene, add 16 g (0.065 mol) of chloranil, and reflux for 20 hours. After cooling, add toluene. Add 500ml, wash once with 6N hydrochloric acid, three times with 2N sodium hydroxide, and wash with saturated saline until the washings become neutral.The solvent is distilled off under reduced pressure, and the solution is recrystallized with toluene. is the target product, 4-ethyl-4″-(trans-
4-ethylcyclohexyl)terphenyl. Yield 5g. Its C-S point is 147.0℃, S-N
The point was 260°C, and the N-I point was 300°C or higher. Examples 2 to 6 Other compounds of formula () produced in the same manner as in Example 1 are shown in Table 1 together with the results of Example 1.
【表】
実施例 ８
（使用例）
トランス−４−プロピル−（4′−シアノフエ
ニル）シクロヘキサン 28％
トランス−４−ペンチル−（4′−シアノフエ
ニル）シクロヘキサン 42％
トランス−４−ヘプチル−（4′−シアノフエ
ニル）シクロヘキサン 30％
なる組成の液晶組成物のネマチツク液晶温度範囲
は−３〜52℃である。この液晶組成物をセル厚
10μmのTNセル（ねじれネマチツクセル）に封
入したものの動作しきい電圧は1.53V、飽和電圧
は2.12Vであつた。又粘度は20℃で23cp、△ｎは
0.120であつた。
上記の液晶組成物95部に本発明の実施例５の４
−エチル−4″−（トランス−４−ペンチルシク
ロヘキシル）テルフエニル５部を加えた液晶組成
物のネマチツク液晶温度範囲は−３〜61.5℃に広
がり、これを上記セルに入れたものの動作しきい
電圧は1.62V、飽和電圧は2.44Vであつた。又粘
度は20℃で24.8cpで、△ｎは0.126と大きくなり、
本発明の化合物は小量の添加で低粘性で広いネマ
チツク温度範囲をもつ組成物をつくるのに有効で
あることがわかる。[Table] Example 8 (Usage example) Trans-4-propyl-(4'-cyanophenyl)cyclohexane 28% Trans-4-pentyl-(4'-cyanophenyl)cyclohexane 42% Trans-4-heptyl-(4'- The nematic liquid crystal temperature range of a liquid crystal composition having a composition of 30% (cyanophenyl)cyclohexane is -3 to 52°C. This liquid crystal composition has a cell thickness of
When sealed in a 10 μm TN cell (twisted nematic cell), the operating threshold voltage was 1.53V and the saturation voltage was 2.12V. Also, the viscosity is 23 cp at 20℃, and △n is
It was 0.120. Example 5-4 of the present invention was added to 95 parts of the above liquid crystal composition.
The nematic liquid crystal temperature range of the liquid crystal composition containing 5 parts of -ethyl-4''-(trans-4-pentylcyclohexyl)terphenyl expands from -3 to 61.5°C, and when this is placed in the above cell, the operating threshold voltage is 1.62V, the saturation voltage was 2.44V.The viscosity was 24.8cp at 20°C, and △n was as large as 0.126.
It can be seen that the compounds of the present invention are effective in producing compositions with low viscosity and a wide nematic temperature range when added in small amounts.
Claims (1)
R′は水素原子又は炭素数１〜10を有するアルキ
ル基を示す） で表わされる４−置換−4″−（トランス−４−
アルキルシクロヘキシル）テルフエニル。 ２ 一般式 （上式中Ｒは炭素数１〜10を有するアルキル基、
R′は水素原子又は炭素数１〜10を有するアルキ
ル基を示す） で表わされる４−置換−4″−（トランス−４−
アルキルシクロヘキシル）テルフエニルを少なく
とも一種含有することを特徴とする液晶組成物。[Claims] 1. General formula (In the above formula, R is an alkyl group having 1 to 10 carbon atoms,
4-substituted-4″-(trans-4-
alkylcyclohexyl)terphenyl. 2 General formula (In the above formula, R is an alkyl group having 1 to 10 carbon atoms,
4-substituted-4″-(trans-4-
A liquid crystal composition containing at least one type of alkylcyclohexyl)terphenyl.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8527282A JPS58203922A (en) | 1982-05-20 | 1982-05-20 | 4-substituted-4"-(trans-4'''-alkylcyclohexyl)terphenyl |
| US06/460,071 US4477369A (en) | 1982-01-22 | 1983-01-21 | New high temperature liquid-crystalline substances consisting of 4 or 5 six-member-rings and liquid-crystalline compositions containing same |
| DE8383300354T DE3362745D1 (en) | 1982-01-22 | 1983-01-24 | Carbocyclic compounds with liquid-crystal properties |
| EP19830300354 EP0084974B1 (en) | 1982-01-22 | 1983-01-24 | Carbocyclic compounds with liquid-crystal properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8527282A JPS58203922A (en) | 1982-05-20 | 1982-05-20 | 4-substituted-4"-(trans-4'''-alkylcyclohexyl)terphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58203922A JPS58203922A (en) | 1983-11-28 |
| JPH021811B2 true JPH021811B2 (en) | 1990-01-12 |
Family
ID=13853923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8527282A Granted JPS58203922A (en) | 1982-01-22 | 1982-05-20 | 4-substituted-4"-(trans-4'''-alkylcyclohexyl)terphenyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58203922A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4526605B2 (en) | 1996-08-28 | 2010-08-18 | チッソ株式会社 | Tetracyclic compound having lateral halogen substituent and liquid crystal composition |
-
1982
- 1982-05-20 JP JP8527282A patent/JPS58203922A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58203922A (en) | 1983-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6239136B2 (en) | ||
| US4477369A (en) | New high temperature liquid-crystalline substances consisting of 4 or 5 six-member-rings and liquid-crystalline compositions containing same | |
| JPS644497B2 (en) | ||
| JPS6313411B2 (en) | ||
| JPS6344132B2 (en) | ||
| JPH0244290B2 (en) | ||
| JPH021811B2 (en) | ||
| JPS6353177B2 (en) | ||
| JPS5942329A (en) | 3-fluorophenylcyclohexane derivative | |
| JP2897397B2 (en) | Difluorobenzonitrile derivative, liquid crystal composition containing the same, and liquid crystal display using the same | |
| JPH0331184B2 (en) | ||
| JPS644496B2 (en) | ||
| JP2829436B2 (en) | Cyclobutane derivative | |
| JP2822079B2 (en) | Cyclopropane derivative | |
| JPH0229055B2 (en) | JISHIKUROHEKISHIRUBENZENJUDOTAI | |
| JP2822083B2 (en) | Alkyneoxyphenylbicyclohexanes compounds | |
| JPH0216737B2 (en) | ||
| JPS6261017B2 (en) | ||
| JPS6355496B2 (en) | ||
| JPH0220615B2 (en) | ||
| JPH033650B2 (en) | ||
| JPH0158168B2 (en) | ||
| JPS6361292B2 (en) | ||
| JPH0247455B2 (en) | 44ARUFUA * ARUFUA * ARUFUAATORIFURUOROMECHIRUANSOKUKOSANN44 * TORANSUU4 ** ARUKIRUSHIKUROHEKISHIRU * FUENIRUESUTERU | |
| JPS597149A (en) | 4-(trans-4'-(trans-4"-alkylcyclohexyl)cyclohexyl)phenyl 4-cyanobenzoate |