JPS6355496B2 - - Google Patents
Info
- Publication number
- JPS6355496B2 JPS6355496B2 JP6625281A JP6625281A JPS6355496B2 JP S6355496 B2 JPS6355496 B2 JP S6355496B2 JP 6625281 A JP6625281 A JP 6625281A JP 6625281 A JP6625281 A JP 6625281A JP S6355496 B2 JPS6355496 B2 JP S6355496B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- trans
- present
- biphenyl
- chloro
- 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
- 239000004973 liquid crystal related substance Substances 0.000 claims description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AKCZQKBKWXBJOF-UHFFFAOYSA-N 4-(4-propylcyclohexyl)cyclohexan-1-one Chemical compound C1CC(CCC)CCC1C1CCC(=O)CC1 AKCZQKBKWXBJOF-UHFFFAOYSA-N 0.000 description 1
- XXUSEPRYHRDKFV-CTYIDZIISA-N C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(C#N)C=C1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(C#N)C=C1 XXUSEPRYHRDKFV-CTYIDZIISA-N 0.000 description 1
- FURZYCFZFBYJBT-JCNLHEQBSA-N C1C[C@@H](CCCCC)CC[C@@H]1C1=CC=C(C#N)C=C1 Chemical compound C1C[C@@H](CCCCC)CC[C@@H]1C1=CC=C(C#N)C=C1 FURZYCFZFBYJBT-JCNLHEQBSA-N 0.000 description 1
- CDEMHJCJMMOFMB-UHFFFAOYSA-M ClC1=CC=C([Mg]Br)C=C1 Chemical compound ClC1=CC=C([Mg]Br)C=C1 CDEMHJCJMMOFMB-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- PESJIPUCTXESJH-UHFFFAOYSA-L magnesium chlorobenzene dibromide Chemical compound [Br-].[Mg+2].C1(=CC=CC=C1)Cl.[Br-] PESJIPUCTXESJH-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 propylcyclohexyl Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は正の誘電異方性を有する新規な液晶物
質に関する。
液晶表示素子は液晶物質が持つ光学異方性及び
誘電異方性を利用したものであるが、その表示様
式によつてTN型（ねじれネマチツク型）、DS型
（動的散乱型）、ゲスト・ホスト型、DAP型など
各種の方式に分けられ、夫々の使用に適する液晶
物質の性質は異なる。しかしいずれの液晶物質も
水分、空気、熱、光等に安定であることが必要で
あることは共通しており、又、室温を中心として
出来るだけ広い温度範囲で液晶相を示すものが求
められている。しかし現在のところ単一化合物で
はこの様な条件を満たす物質はなく、数種の液晶
化合物や非液晶化合物を混合して得られる液晶組
成物を使用しているのが現状である。
本発明の目的はこの様な液晶組成物の一成分と
して有用な、特に低粘度で、広い温度範囲で液晶
相を示す新規な液晶化合物を提供することにあ
る。
即ち、本発明は一般式
（上式中、Ｒは炭素数１〜10のアルキル基を示
す）
で表わされる４―クロロ―4′―（トランス―4″―
アルキルシクロヘキシル）ビフエニル及び少くと
もそれを１種含有する液晶組成物である。
本発明の化合物は約80〜190℃の間で液晶相を
示し、又粘度が低いので本発明の化合物を含有す
る液晶組成物は粘度が低くなり、低温での表示特
性を改善することが出来る。又本化合物の誘電異
方性は＋２程度であるにもかかわらず、本化合物
の添加により液晶組成物のしきい電圧、飽和電圧
は同等もしくは低くなる傾向にある。
つぎに本発明の化合物の製造法を示すと、まず
４―ブロモクロロベンゼンと金属マグネシウムを
反応させて４―クロロフエニルマグネシウムブロ
ミドとし、これを４―（トランス―4′―アルキル
シクロヘキシル）シクロヘキサンと反応させて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〕クロロベンゼ
ンとする。次にこれを硫酸水素カリウムで脱水し
て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〕クロロベン
ゼンを得る。ついでクロラニルで脱水素反応して
目的の４―クロロ―4′―（トランス―4″―アルキ
ルシクロヘキシル）ビフエニルを得る。以上を化
学式で示すと、
以下、実施例により本発明の化合物の製法及び
使用例について更に詳細に説明する。
実施例１ 〔４―クロロ―4′―（トランス―4″―
プロピルシクロヘキシル）ビフエニルの製造〕
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―ブロモクロロベンゼン
9.4ｇ（0.049モル）をテトラヒドロフランに溶か
し溶液25mlを、N2気流中で反応温度を30〜35℃
に保ちながらゆつくり滴下して行くと反応して３
時間でマグネシウムは溶けて均一になり４―クロ
ロベンゼンマグネシウムプロミドを生ずる。これ
に４―（トランス―4′―プロピルシクロヘキシ
ル）シクロヘキサノンの9.0ｇ（0.041モル）をテ
トラヒドロフランに溶かして50mlとしたものを、
反応温度を５〜10℃に保ちつつなるべく速かに滴
下する。滴下後、室温まで昇温し１時間撹拌し、
ついで3N塩酸100mlを加える。反応液を分液斗
にとり100mlのトルエンで３回抽出後、合わせた
トルエン層を飽和食塩水で洗液が中性になるまで
洗浄してからトルエンを減圧留去する。残留した
油状物は４―〔4′―（トランス―4″―プロピルシ
クロヘキシル）シクロヘキセン―1′―オール〕ク
ロロベンゼンであり、これに硫酸水素カリウム
2.0ｇを加えN2気流中150℃で１時間脱水する。
冷却後200mlのトルエンを加えてから硫酸水素カ
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。次いでトルエンを減圧留去し、残
る油状物をエチルアルコールで再結晶して得られ
るのが４―〔4′―（トランス―4″―プロピルシク
ロヘキシル）シクロヘキセン―1′―イル〕クロロ
ベンゼンである。その4.8ｇをキシレン200mlに溶
解してからクロラニル8.2ｇを加え20時間還流さ
せる。ついでトルエン200mlで抽出し、それを少
量の6N塩酸，2N水酸化ナトリウムで順次洗い、
更に洗液が中性になるまで水洗する。溶媒を減圧
留去し、トルエンで再結晶させて得られる結晶物
が、４―クロロ―4′―（トランス―4″―プロピル
シクロヘキシル）ビフエニルである。収量1.2ｇ，
収率25％，結晶―ネマチツク点（Ｃ―Ｎ点）
155.4〜159.0℃，ネマチツク―透明点（Ｎ―Ｉ
点）196.9〜197.0℃であつた。
実施例 ２，３
実施例１と同様にして他のアルキル基を有する
４―クロロ―4′―（トランス―4″―ペンチルシク
ロヘキシル）ビフエニル，４―クロロ―4′―（ト
ランス―4″―ヘプチルシクロヘキシル）ビフエニ
ルを製造した。その収率，物性値などを実施例１
の結果と共に第１表に示す。
The present invention relates to novel liquid crystal materials with positive dielectric anisotropy. Liquid crystal display elements utilize the optical anisotropy and dielectric anisotropy of liquid crystal materials, and depending on the display format, there are TN type (twisted nematic type), DS type (dynamic scattering type), and guest type. There are various types such as host type and DAP type, and the properties of the liquid crystal materials suitable for each type of use are different. However, all liquid crystal materials have in common that they need to be stable against moisture, air, heat, light, etc., and they are also required to exhibit a liquid crystal phase over as wide a temperature range as possible, centered around room temperature. ing. However, at present, there is no single compound that satisfies these conditions, and the current situation is to use liquid crystal compositions obtained by mixing several types of liquid crystal compounds and non-liquid crystal compounds. An object of the present invention is to provide a novel liquid crystal compound useful as a component of such a liquid crystal composition, which has a particularly low viscosity and exhibits a liquid crystal phase over a wide temperature range. That is, the present invention is based on the general formula (In the above formula, R represents an alkyl group having 1 to 10 carbon atoms) 4-chloro-4′-(trans-4″-
The present invention is a liquid crystal composition containing alkylcyclohexyl)biphenyl and at least one thereof. The compound of the present invention exhibits a liquid crystal phase between about 80 and 190°C and has a low viscosity, so a liquid crystal composition containing the compound of the present invention has a low viscosity and can improve display characteristics at low temperatures. . Furthermore, although the dielectric anisotropy of the present compound is about +2, the addition of the present compound tends to make the threshold voltage and saturation voltage of the liquid crystal composition the same or lower. Next, the method for producing the compound of the present invention will be described. First, 4-bromochlorobenzene and metallic magnesium are reacted to form 4-chlorophenylmagnesium bromide, which is then reacted with 4-(trans-4'-alkylcyclohexyl)cyclohexane. Te4
―[4′-(trans-4″-alkylcyclohexyl)cyclohexane-1′-ol]chlorobenzene. Next, this is dehydrated with potassium hydrogen sulfate to form 4-[4′-(trans-4″-alkylcyclohexyl) ) to obtain cyclohexene-1′-yl]chlorobenzene. Then, the desired 4-chloro-4′-(trans-4″-alkylcyclohexyl)biphenyl is obtained by a dehydrogenation reaction with chloranil.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 [4-chloro-4′-(trans-4″-
Production of propylcyclohexyl)biphenyl] Put 1.2 g (0.049 mol) of magnesium turnings into a three-necked flask, and add 4-bromochlorobenzene.
Dissolve 9.4 g (0.049 mol) in tetrahydrofuran and add 25 ml of the solution to a reaction temperature of 30 to 35°C in a stream of N2 .
If you slowly drop the drops while keeping it at a certain temperature, it will react and 3
Over time, the magnesium dissolves and becomes homogeneous to form 4-chlorobenzene magnesium bromide. To this, 9.0 g (0.041 mol) of 4-(trans-4'-propylcyclohexyl)cyclohexanone was dissolved in tetrahydrofuran to make 50 ml.
Add dropwise as quickly as possible while maintaining the reaction temperature at 5-10°C. After dropping, the temperature was raised to room temperature and stirred for 1 hour.
Then add 100ml of 3N hydrochloric acid. The reaction solution is placed in a separator and extracted three times with 100 ml of toluene. The combined toluene layers are washed with saturated brine until the washings become neutral, and the toluene is distilled off under reduced pressure. The remaining oil is 4-[4'-(trans-4''-propylcyclohexyl)cyclohexene-1'-ol]chlorobenzene, which is treated with potassium hydrogen sulfate.
Add 2.0 g and dehydrate at 150°C in a N2 stream for 1 hour.
After cooling, add 200 ml of toluene, separate the potassium hydrogen sulfate, and wash the toluene layer with water until the washing liquid becomes neutral. Next, toluene is distilled off under reduced pressure, and the remaining oil is recrystallized from ethyl alcohol to obtain 4-[4'-(trans-4''-propylcyclohexyl)cyclohexen-1'-yl]chlorobenzene. Dissolve 4.8 g in 200 ml of xylene, add 8.2 g of chloranil, and reflux for 20 hours. Next, extract with 200 ml of toluene, wash it sequentially with a small amount of 6N hydrochloric acid and 2N sodium hydroxide,
Further wash with water until the washing liquid becomes neutral. The solvent is distilled off under reduced pressure and the crystalline product obtained by recrystallization with toluene is 4-chloro-4'-(trans-4''-propylcyclohexyl)biphenyl. Yield: 1.2 g.
Yield 25%, crystal-nematic point (C-N point)
155.4-159.0℃, nematic-clearing point (N-I
point) It was 196.9 to 197.0°C. Examples 2 and 3 4-chloro-4'-(trans-4''-pentylcyclohexyl)biphenyl, 4-chloro-4'-(trans-4''-heptyl) having other alkyl groups in the same manner as in Example 1 cyclohexyl)biphenyl was produced. Example 1 shows the yield, physical properties, etc.
The results are shown in Table 1.
【表】
実施例４ （応用例）
トランス―４―プロピル―（4′―シアノフエニ
ル）シクロヘキサン 26％
トランス―４―ペンチル―（4′―シアノフエニ
ル）シクロヘキサン 35％
トランス―４―ヘプチル―（4′―シアノフエニ
ル）シクロヘキサン 26％
トランス―４―ペンチル―（4″―シアノビフエ
ニル）シクロヘキサン 13％
なる割合の液晶組成物のネマチツク液晶温度範囲
は−６〜72.3℃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1.69V，飽和電圧
は2.31Vであつた。又粘度は20℃で27.6cpであつ
た。
上記の液晶組成物92.5部に本発明の化合物の１
つである４―クロロ―4′―（トランス―4″―プロ
ピルシクロヘキシル）ビフエニル7.5部を加えた
液晶組成物のネマチツク液晶温度範囲は−５〜
58.6℃になり、これを先と同じ10μｍのセル厚の
TNセルに封入したものの動作しきい電圧は
1.54V，飽和電圧は2.16V，20℃での粘度は23.8cp
であつた。このように本発明の化合物を成分とし
て加えることにより駆動電圧を低くし、さらに低
温での表示特性を改善することが出来た。[Table] Example 4 (Application example) Trans-4-propyl-(4'-cyanophenyl)cyclohexane 26% Trans-4-pentyl-(4'-cyanophenyl)cyclohexane 35% Trans-4-heptyl-(4'- The nematic liquid crystal temperature range of a liquid crystal composition containing 26% of cyanophenyl)cyclohexane and 13% of trans-4-pentyl-(4″-cyanobiphenyl)cyclohexane is -6 to 72.3°C.
When sealed in a 10 μm TN cell (twisted nematic cell), the operating threshold voltage was 1.69V and the saturation voltage was 2.31V. The viscosity was 27.6 cp at 20°C. 92.5 parts of the above liquid crystal composition and 1 part of the compound of the present invention.
The nematic liquid crystal temperature range of the liquid crystal composition containing 7.5 parts of 4-chloro-4′-(trans-4″-propylcyclohexyl)biphenyl is −5 to
The temperature reached 58.6℃, and this temperature was changed to the same cell thickness of 10μm as before.
The operating threshold voltage of the TN cell sealed is
1.54V, saturation voltage is 2.16V, viscosity at 20℃ is 23.8cp
It was hot. By adding the compound of the present invention as a component in this way, it was possible to lower the driving voltage and further improve the display characteristics at low temperatures.
Claims (1)
基を示す） で表わされる４―クロロ―4′―（トランス―4″―
アルキルシクロヘキシル）ビフエニル。 ２ 一般式 （上式中、Ｒは炭素数１〜10を有するアルキル
基を示す） で表わされる４―クロロ―4′―（トランス―4″―
アルキルシクロヘキシル）ビ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 represents an alkyl group having 1 to 10 carbon atoms) 4-chloro-4′-(trans-4″-
alkylcyclohexyl)biphenyl. 2 General formula (In the above formula, R represents an alkyl group having 1 to 10 carbon atoms) 4-chloro-4′-(trans-4″-
A liquid crystal composition containing at least one type of alkylcyclohexyl)biphenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6625281A JPS57183727A (en) | 1981-05-01 | 1981-05-01 | 4-chloro-4'-(trans-4"-alkylcyclohexyl)biphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6625281A JPS57183727A (en) | 1981-05-01 | 1981-05-01 | 4-chloro-4'-(trans-4"-alkylcyclohexyl)biphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57183727A JPS57183727A (en) | 1982-11-12 |
| JPS6355496B2 true JPS6355496B2 (en) | 1988-11-02 |
Family
ID=13310479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6625281A Granted JPS57183727A (en) | 1981-05-01 | 1981-05-01 | 4-chloro-4'-(trans-4"-alkylcyclohexyl)biphenyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57183727A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0334298U (en) * | 1989-08-11 | 1991-04-04 |
-
1981
- 1981-05-01 JP JP6625281A patent/JPS57183727A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0334298U (en) * | 1989-08-11 | 1991-04-04 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57183727A (en) | 1982-11-12 |
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