JPH0481980B2 - - Google Patents
Info
- Publication number
- JPH0481980B2 JPH0481980B2 JP26137084A JP26137084A JPH0481980B2 JP H0481980 B2 JPH0481980 B2 JP H0481980B2 JP 26137084 A JP26137084 A JP 26137084A JP 26137084 A JP26137084 A JP 26137084A JP H0481980 B2 JPH0481980 B2 JP H0481980B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- liquid crystal
- acid azide
- trans
- present
- 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
Links
- 239000004973 liquid crystal related substance Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 8
- 150000001540 azides Chemical class 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 16
- -1 4-(trans-4 -propylcyclohexyl)benzoic acid azide Chemical compound 0.000 description 13
- 239000012071 phase Substances 0.000 description 6
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- PJHUABJTDFXYRQ-UHFFFAOYSA-N benzoyl azide Chemical compound [N-]=[N+]=NC(=O)C1=CC=CC=C1 PJHUABJTDFXYRQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FURZYCFZFBYJBT-UHFFFAOYSA-N 4-(4-pentylcyclohexyl)benzonitrile Chemical compound C1CC(CCCCC)CCC1C1=CC=C(C#N)C=C1 FURZYCFZFBYJBT-UHFFFAOYSA-N 0.000 description 1
- XXUSEPRYHRDKFV-UHFFFAOYSA-N 4-(4-propylcyclohexyl)benzonitrile Chemical compound C1CC(CCC)CCC1C1=CC=C(C#N)C=C1 XXUSEPRYHRDKFV-UHFFFAOYSA-N 0.000 description 1
- OEABBNGVFWXEJP-JOCQHMNTSA-N C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(C(Cl)=O)C=C1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(C(Cl)=O)C=C1 OEABBNGVFWXEJP-JOCQHMNTSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N Cyclohexanecarboxylic acid Natural products OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Description
（発明の目的）
本発明は新規な液晶化合物である酸アジド誘導
体および該化合物を含有する液晶組成物に関す
る。
液晶を使用した表示素子は時計、電卓などに広
く使用されている。これらの液晶表示素子は液晶
物質の光学異方性および誘導異方性を利用したも
のであり、液晶相にはネマチツク相、スメクチツ
ク相、コレステリツク相があり、そのうちネマチ
ツク液晶を利用したものが最も広く実用化されて
いる。それらには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
型などがあり、それぞれに使用される液晶化合物
に要求される性質は異なる。しかし、いずれにし
てもこれら表示素子に使用される液晶化合物はな
るべく広い温度範囲で液晶相を示すものが望まし
く、また、水分、光、熱、空気等に対しても安定
であることが要求されている。しかし現在のとこ
ろ単一の化合物でそのような条件をすべてみたす
ようなものはなく、数種の液晶化合物または液晶
類似化合物を混合して実用に供しているのが現状
である。
本発明の目的は上記のような目的に使用される
液晶組成物の成分として有用な液晶化合物および
組成物を提供することにある。
（発明の構成）
本発明は、一般式
（（）式中、Ｒは炭素数１〜15のアルキル基、
アルコキシ基またはアルコキシメチル基を示し、
環
(Object of the Invention) The present invention relates to an acid azide derivative, which is a novel liquid crystal compound, and a liquid crystal composition containing the compound. Display elements using liquid crystals are widely used in watches, calculators, etc. These liquid crystal display elements utilize the optical anisotropy and induced anisotropy of liquid crystal materials, and the liquid crystal phases include nematic, smectic, and cholesteric phases, of which nematic liquid crystals are the most widely used. It has been put into practical use. They include TN type (twisted nematic type),
DS type (dynamic scattering type), guest-host type, DAP
There are different types, and the properties required of the liquid crystal compound used for each type are different. However, in any case, it is desirable that the liquid crystal compounds used in these display elements exhibit a liquid crystal phase over as wide a temperature range as possible, and they are also required to be stable against moisture, light, heat, air, etc. ing. However, at present, there is no single compound that satisfies all of these conditions, and the current situation is that a mixture of several types of liquid crystal compounds or liquid crystal-like compounds is put into practical use. An object of the present invention is to provide liquid crystal compounds and compositions useful as components of liquid crystal compositions used for the above purposes. (Structure of the invention) The present invention is based on the general formula (() In the formula, R is an alkyl group having 1 to 15 carbon atoms,
Indicates an alkoxy group or an alkoxymethyl group,
ring
【式】または[expression] or
【式】は、互い に独立に[Formula] is mutually independently
【式】または[expression] or
【式】を
示す。）で表わされる酸アジド誘導体および該化
合物を少くとも１種含有する液晶組成物である。
本発明の化合物としては、４−（トランス−４
−プロピルシクロヘキシル）安息香酸アジド、４
−（トランス−４−ペンチルシクロヘキシル）安
息香酸アジド、４−（トランス−４−ヘプチルシ
クロヘキシル）安息香酸アジド、４−（トランス
−４−メトキシメチルシクロヘキシル）安息香酸
アジド、４−（トランス−４−エトキシメチルシ
クロヘキシル）安息香酸アジドなどの４−（トラ
ンス−置換シクロヘキシル）安息香酸アジド、４
−ペンチルビフエニリル−4′−カルボン酸アジ
ド、４−ヘキシルビフエニリル−4′−カルボン酸
アジド、４−ヘプチルビフエニリル−4′−カルボ
ン酸アジドなどの４−（ｐ−置換フエニル）安息
香酸アジド、およびトランス−４−（トランス−
４−置換シクロヘキシル）シクロヘキサンカルボ
ン酸アジド等のほかにトランス−４−（ｐ−置換
フエニル）シクロヘキサンカルボン酸アジドを挙
げることができる。
本発明の化合物の製造法を示すと、目的物に対
応したカルボン酸クロリドに、アセトン、ジオキ
サン、テトラヒドロフラン等の有機溶媒中でアジ
化ナトリウムの水溶液を反応させて目的の酸アジ
ド誘導体とする。これを式で示すと
（上式中、Ｒ、[Formula] is shown. ) and a liquid crystal composition containing at least one kind of the compound. The compounds of the present invention include 4-(trans-4
-propylcyclohexyl)benzoic acid azide, 4
-(trans-4-pentylcyclohexyl)benzoic acid azide, 4-(trans-4-heptylcyclohexyl)benzoic acid azide, 4-(trans-4-methoxymethylcyclohexyl)benzoic acid azide, 4-(trans-4-ethoxy) 4-(trans-substituted cyclohexyl)benzoic acid azide, such as methylcyclohexyl)benzoic acid azide, 4
-4-(p-substituted phenyl) such as pentylbiphenylyl-4'-carboxylic acid azide, 4-hexylbiphenylyl-4'-carboxylic acid azide, 4-heptylbiphenylyl-4'-carboxylic acid azide, etc. benzoic acid azide, and trans-4-(trans-
Trans-4-(p-substituted phenyl)cyclohexanecarboxylic acid azide can be mentioned in addition to 4-substituted cyclohexyl)cyclohexanecarboxylic acid azide. The method for producing the compound of the present invention is to react a carboxylic acid chloride corresponding to the desired product with an aqueous solution of sodium azide in an organic solvent such as acetone, dioxane, or tetrahydrofuran to obtain the desired acid azide derivative. Expressing this in the formula (In the above formula, R,
【式】および[expression] and
【式】は前記に同じ。）と表わされる。
本発明の液晶組成物は（）式で示される本発
明の酸アジド誘導体を、好ましくは１〜30重量
％、より好ましくは５〜20重量％含有することを
特徴とする。
（発明の効果）
本発明の化合物は他の液晶化合物、例えばビフ
エニル系、エステル系、シツフ系、フエニルシク
ロヘキサン系、アゾキシ系、複素環系等の液晶と
の相溶性にすぐれており、また室温付近から高温
まで幅広い液晶温度範囲を有している。さらに本
発明の化合物は粘度が極めて低いために、本発明
の化合物を使用する事により得られた組成物の液
晶温度範囲を広げかつ粘度を低下させる効果は大
である。
酸アジドは次の反応式で示されるクリチウス反
応により、アミンを生成することが知られている
（P.A.S.Smith；Org.React.，３，337（1946））。
本発明の酸アジド誘導体から液晶材料の中間体
として有用なアニリン誘導体を得ることもでき
る。
（実施例）
以下に実施例により、本発明をさらに詳しく説
明するが、本発明はこれらの例に限定されるもの
ではない。
実施例 １
４−（トランス−４−プロピルシクロヘキシル）
安息香酸アジドの製造
公知の方法で得られた４−（トランス−４−プ
ロピルシクロヘキシル）安息香酸クロリド６ｇ
（22.6ミルモル）をアセトン30c.c.に５〜10℃にて
撹拌懸濁させているところへ、アジ化ナトリウム
1.8ｇ（27.0ミリモル）を水10c.c.に溶解した溶液
を10℃以下で加え、10〜15℃で５時間撹拌し、反
応させた後に反応液を水200c.c.に加えた。ここで
析出した結晶を過し、水洗後、乾燥した。これ
をエチルアルコール20c.c.から再結晶を行い、目的
物である４−（トランス−４−プロピルシクロヘ
キシル）安息香酸アジド4.2ｇを得た（収率68.5
％）。この物は液晶相を示し、結晶−ネマチツク
相転移点（Ｃ−Ｎ点と略す）は43.5℃、ネマチツ
ク相−等方性液相転移点（Ｎ−Ｉ点と略す）は
103.2℃であつた。
実施例 ２、３
実施例１に準じて、それぞれ対応するカルボン
酸クロリドから目的の酸アジドを製造した。これ
らの相転移温度を次に記す。
４−（トランス−４−メトキシメチルシクロヘキ
シル）安息香酸アジド
Ｃ−Ｎ点：46.5℃
Ｎ−Ｉ点：93.7℃
４−ペンチルビフエニル−4′−カルボン酸アジド
Ｃ−Ｎ点：90.1℃
Ｎ−Ｉ点：101.6℃
実施例 ４
トランス−４−プロピル−（４−シアノフエニル）
シクロヘキサン 30重量％
トランス−４−ペンチル−（４−シアノフエニル）
シクロヘキサン 40重量％
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重量％
なる液晶組成物(A)のＮ−Ｉ点は52℃、誘電率の異
方性△εは11.2、20℃における粘度は23.4epであ
つた。この液晶組成物(A)85重量％に実施例１で製
造した４−（トランス−４−プロピルシクロヘキ
シル）安息香酸アジド15重量％を加えた液晶組成
物のＮ−Ｉ点は60.0℃、△εは12.1であつた。ま
た20℃における粘度は20.7epと低下した。
この様に本発明の化合物を使用する事により得
られた液晶組成物の液晶温度範囲を広げかつ組成
物の粘度を低下させる効果は著しい。[Formula] is the same as above. ). The liquid crystal composition of the present invention is characterized in that it contains preferably 1 to 30% by weight, more preferably 5 to 20% by weight of the acid azide derivative of the present invention represented by formula (). (Effects of the Invention) The compound of the present invention has excellent compatibility with other liquid crystal compounds, such as biphenyl-based, ester-based, Schiff-based, phenylcyclohexane-based, azoxy-based, and heterocyclic-based liquid crystals, and also at room temperature. It has a wide liquid crystal temperature range from near to high temperatures. Further, since the compound of the present invention has an extremely low viscosity, the use of the compound of the present invention has a great effect of widening the liquid crystal temperature range and lowering the viscosity of the composition obtained. It is known that acid azides produce amines through the Critius reaction represented by the following reaction formula (PASSmith; Org. React., 3 , 337 (1946)). Aniline derivatives useful as intermediates for liquid crystal materials can also be obtained from the acid azide derivatives of the present invention. (Examples) The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. Example 1 4-(trans-4-propylcyclohexyl)
Production of benzoic acid azide 6 g of 4-(trans-4-propylcyclohexyl)benzoic acid chloride obtained by a known method
Sodium azide
A solution of 1.8 g (27.0 mmol) dissolved in 10 c.c. of water was added below 10°C, stirred at 10-15°C for 5 hours, allowed to react, and then the reaction solution was added to 200 c.c. of water. The precipitated crystals were filtered, washed with water, and then dried. This was recrystallized from 20 c.c. of ethyl alcohol to obtain 4.2 g of 4-(trans-4-propylcyclohexyl)benzoic acid azide (yield 68.5).
%). This substance exhibits a liquid crystal phase, with a crystalline-nematic phase transition point (abbreviated as the C-N point) at 43.5°C and a nematic phase-isotropic liquid phase transition point (abbreviated as the N-I point).
It was 103.2℃. Examples 2 and 3 According to Example 1, target acid azides were produced from the corresponding carboxylic acid chlorides. These phase transition temperatures are described below. 4-(trans-4-methoxymethylcyclohexyl)benzoic acid azide C-N point: 46.5℃ N-I point: 93.7℃ 4-Pentylbiphenyl-4'-carboxylic acid azide C-N point: 90.1℃ N-I Point: 101.6°C Example 4 Trans-4-propyl-(4-cyanophenyl)
Cyclohexane 30% by weight trans-4-pentyl-(4-cyanophenyl)
Cyclohexane 40% by weight trans-4-heptyl-(4-cyanophenyl)
The liquid crystal composition (A) containing 30% by weight of cyclohexane had an N-I point of 52°C, an anisotropy of dielectric constant Δε of 11.2, and a viscosity at 20°C of 23.4ep. The N-I point of a liquid crystal composition prepared by adding 15% by weight of 4-(trans-4-propylcyclohexyl)benzoic acid azide produced in Example 1 to 85% by weight of this liquid crystal composition (A) was 60.0°C, Δε was 12.1. In addition, the viscosity at 20°C decreased to 20.7ep. As described above, the use of the compound of the present invention has a remarkable effect of widening the liquid crystal temperature range of the obtained liquid crystal composition and lowering the viscosity of the composition.
Claims (1)
キシ基またはアルコキシメチル基を示し、環
【式】または【式】は、互いに 独立に【式】または【式】を示 す）で表される酸アジド誘導体。 ２ 一般式 （式中、Ｒは炭素数１〜15のアルキル基、アルコ
キシ基またはアルコキシメチル基を示し、環
【式】または【式】は互いに独 立に【式】または【式】を示 す）で表される酸アジド誘導体を少なくとも１種
含有することを特徴とする液晶組成物。[Claims] 1. General formula (In the formula, R represents an alkyl group, alkoxy group, or alkoxymethyl group having 1 to 15 carbon atoms, and the ring [formula] or [formula] independently represents [formula] or [formula]) Acid azide derivatives. 2 General formula (In the formula, R represents an alkyl group, alkoxy group, or alkoxymethyl group having 1 to 15 carbon atoms, and the ring [formula] or [formula] independently represents [formula] or [formula]) A liquid crystal composition comprising at least one acid azide derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26137084A JPS61140558A (en) | 1984-12-11 | 1984-12-11 | Acid azide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26137084A JPS61140558A (en) | 1984-12-11 | 1984-12-11 | Acid azide derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61140558A JPS61140558A (en) | 1986-06-27 |
| JPH0481980B2 true JPH0481980B2 (en) | 1992-12-25 |
Family
ID=17360894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26137084A Granted JPS61140558A (en) | 1984-12-11 | 1984-12-11 | Acid azide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61140558A (en) |
-
1984
- 1984-12-11 JP JP26137084A patent/JPS61140558A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61140558A (en) | 1986-06-27 |
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