JPH0269441A - Azulene derivative and liquid crystal composition containing the same - Google Patents
Azulene derivative and liquid crystal composition containing the sameInfo
- Publication number
- JPH0269441A JPH0269441A JP63222127A JP22212788A JPH0269441A JP H0269441 A JPH0269441 A JP H0269441A JP 63222127 A JP63222127 A JP 63222127A JP 22212788 A JP22212788 A JP 22212788A JP H0269441 A JPH0269441 A JP H0269441A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal composition
- azulene derivative
- formula
- composition containing
- 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 36
- 239000000203 mixture Substances 0.000 title claims description 20
- HPJYKMSFRBJOSW-JHSUYXJUSA-N Damsin Chemical compound C[C@H]1CC[C@H]2C(=C)C(=O)O[C@H]2[C@]2(C)C(=O)CC[C@@H]12 HPJYKMSFRBJOSW-JHSUYXJUSA-N 0.000 title claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001545 azulenes Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-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
- 238000001556 precipitation Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 1
- CWYNKKGQJYAHQG-UHFFFAOYSA-N 4-pentylbenzoic acid Chemical compound CCCCCC1=CC=C(C(O)=O)C=C1 CWYNKKGQJYAHQG-UHFFFAOYSA-N 0.000 description 1
- ATZHGRNFEFVDDJ-UHFFFAOYSA-N 4-propylbenzoic acid Chemical compound CCCC1=CC=C(C(O)=O)C=C1 ATZHGRNFEFVDDJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CUFNKYGDVFVPHO-UHFFFAOYSA-N Azulene Natural products C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 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)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は液晶表示等に有用な有色の液晶性を持つアズレ
ン誘導体およびこれを含む有色の液晶組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an azulene derivative having colored liquid crystal properties useful for liquid crystal displays and the like, and a colored liquid crystal composition containing the azulene derivative.
〔従来の技術および発明が解決しようとする課題〕現在
、液晶表示としてはＴＮ型表示の外に、液晶に色素を溶
解して用いるゲストホスト型表示方式が、視野角などの
特徴のために、自動車などの表示装置に広く用いられ始
めている。このため、これに用いる色素はその使用環境
に応じた十分な溶解性を持つ必要がある。しかしながら
、低温で高い溶解性をもつ色素は少なく、高い溶解安定
性を持つ液晶組成物の実現は困難であるという問題点を
有している。[Prior art and problems to be solved by the invention] At present, in addition to the TN type display, there are guest-host type display systems in which dyes are dissolved in liquid crystals, but due to their characteristics such as viewing angle, It is beginning to be widely used in display devices such as automobiles. Therefore, the dye used for this needs to have sufficient solubility depending on the environment in which it is used. However, there is a problem that there are few dyes that have high solubility at low temperatures, and it is difficult to realize a liquid crystal composition that has high dissolution stability.
他方このような難点を持たない表示方式とじて有色の液
晶化合物を用いる方式〔「液晶エレクトロニクスの基礎
と応用」佐々木昭夫編；オーム社、Ｐ２Ｓ５）が知られ
ているが、この方式の場合は有色の液晶化合物が少なく
、このため実現できる色相は極めて限定されているとい
う問題を有している。On the other hand, a method using colored liquid crystal compounds is known as a display method that does not have these difficulties ("Fundamentals and Applications of Liquid Crystal Electronics" edited by Akio Sasaki; Ohmsha, P2S5); The problem is that there are few liquid crystal compounds, and therefore the hues that can be realized are extremely limited.
本発明は上記の問題点を解決するためになされたもので
、液晶表示に有用な新規な有色の液晶化合物であるアズ
レン誘４体およびこれを含む液晶組成物を提供すること
を目的とする。The present invention was made to solve the above-mentioned problems, and an object of the present invention is to provide an azulene derivative, which is a novel colored liquid crystal compound useful for liquid crystal displays, and a liquid crystal composition containing the same.
本発明の目的は、下記−数式
誘導体を少なくとも１種含むことを特徴とする液晶組成
物により達成される。The object of the present invention is achieved by a liquid crystal composition characterized by containing at least one derivative of the following formula.
本発明の一般式（１）で示されるアズレン誘導体におけ
るＲ１およびＲ２としては、水素原子又はメチル基、エ
チル基、分枝状または直鎖状のプロピル基、ブチル基、
ヘキシル基、オクチル基、Ｆデシル基などの炭素数１〜
１８のアルキル基が挙げられる。R1 and R2 in the azulene derivative represented by the general formula (1) of the present invention include a hydrogen atom, a methyl group, an ethyl group, a branched or linear propyl group, a butyl group,
1 or more carbon atoms such as hexyl group, octyl group, F-decyl group, etc.
18 alkyl groups are mentioned.
本発明の一般式（１）で示されるアズレン誘導体は、例
えば、次のようにして製造することができる。すなわち
、Ｔ、Ｍｏｒｉｔａ ｅｔａｌ。The azulene derivative represented by the general formula (1) of the present invention can be produced, for example, as follows. Namely, T, Morita et al.
Ｃｈｅｍ、Ｌｅｔｔ、、１９７７．７５３ （１９７
７）記載の方法によって合成される下記構造式の２．６
−シヒドロキシアズレンと、
（Ｉ）
（式中、Ｒ１およびＲ２は水素原子又はアルキル基を示
す。）
で表されるアズレン誘導体、およびこのアズレン下記−
数式（Ｕ）
（式中、Ｒ１及びＲ２は水素原子またはアルキル基を示
す。）
で示されるカルボン酸から、塩化チオニルなどのクロル
化剤と反応させる公知の方法により合成されるカルボン
酸クロライドとを、ピリジンなどの脱酸剤の存在下に反
応させることにより製造することができる。この場合、
上記カルボン酸クロライドは単離したものを用いてもよ
く、また反応系中に生成させたものをそのまま用いても
よい。Chem, Lett, 1977.753 (197
7) 2.6 of the following structural formula synthesized by the method described
- cyhydroxyazulene, an azulene derivative represented by (I) (wherein R1 and R2 represent a hydrogen atom or an alkyl group), and this azulene shown below -
A carboxylic acid chloride synthesized from a carboxylic acid represented by the formula (U) (wherein R1 and R2 represent a hydrogen atom or an alkyl group) by a known method of reacting with a chlorinating agent such as thionyl chloride. , can be produced by reacting in the presence of a deoxidizing agent such as pyridine. in this case,
The above-mentioned carboxylic acid chloride may be used either in isolation or as it is produced in the reaction system.
反応はベンゼン、クロルベンゼン、ジクロルベンゼンの
ような芳香族系溶媒などの非極性溶媒中で、エーテル、
テトラヒドロフラン、ジオキサンなどのエーテル系溶媒
または酢酸エチルなどの酢酸エステル系溶媒中などで実
施できる。反応温度は一１０℃ないし２００℃で円滑に
実施できる。The reaction is carried out in a nonpolar solvent such as an aromatic solvent such as benzene, chlorobenzene, or dichlorobenzene.
This can be carried out in an ether solvent such as tetrahydrofuran or dioxane or an acetate solvent such as ethyl acetate. The reaction temperature can be smoothly carried out at -10°C to 200°C.
本発明のアズレン誘導体は新規な化合物であり、有色の
液晶性を示す化合物である。このため有色の液晶組成物
の調製のための配合成分としての利用の外、鉱油および
油脂などの着色にも使用しうる。The azulene derivative of the present invention is a novel compound and exhibits colored liquid crystallinity. Therefore, in addition to being used as a compounding component for preparing colored liquid crystal compositions, it can also be used to color mineral oils, fats and oils, and the like.
また、本発明の液晶組成物は前示一般式ＣＩ）で示され
るアズレン誘導体を他の液晶化合物（「液晶の最新技術
」松本昭−２角田市良共著。In addition, the liquid crystal composition of the present invention can be prepared by combining the azulene derivative represented by the general formula CI) with another liquid crystal compound ("Latest Technology of Liquid Crystals" co-authored by Akira Matsumoto and Ichiyoshi Tsunoda).
■工業調査会、第６２頁〜第９１頁に記載のネマチック
液晶又はスメクチック液晶）、例えばビフェニル系、フ
ェニルシクロヘキサン系、フェニルピリミジン系などの
液晶化合物または液晶組成物に公知の方法で混合するこ
とにより容易に有色の液晶組成物を調製することができ
る。■ Nematic liquid crystal or smectic liquid crystal described in Industrial Research Association, pages 62 to 91), such as biphenyl-based, phenylcyclohexane-based, phenylpyrimidine-based liquid crystal compounds or liquid crystal compositions, by mixing with a known method. Colored liquid crystal compositions can be easily prepared.
本発明の液晶組成物は、前示一般弐（１）で示されるア
ズレン誘導体が有色の液晶化合物であるため、色素の析
出などの問題が少ない、温度条件に対し安定な有色の液
晶組成物である。The liquid crystal composition of the present invention is a colored liquid crystal composition that is stable under temperature conditions and has fewer problems such as precipitation of dyes because the azulene derivative shown in General 2 (1) above is a colored liquid crystal compound. be.
本発明のアズレン誘導体は有色の液晶化合物であり、こ
れを用いた本発明の有色の液晶組成物により、色素の析
出などの問題が少ない、温度条件に対して安定な液晶素
子を実現できる。The azulene derivative of the present invention is a colored liquid crystal compound, and by using the colored liquid crystal composition of the present invention using the azulene derivative, it is possible to realize a liquid crystal element that is stable under temperature conditions and has fewer problems such as precipitation of dyes.
次に、本発明を実施例により、具体的に説明するが、本
発明はこれら実施例によって何ら限定されるものではな
い。EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
下記構造式（ＩＩ［）
で表わされる２、６−シヒドロキシアズレン０．０３４
ｇをヘンゼン２ ｍｌに溶解させた溶液を加え、これに
触媒量のピリジンを加えて、室温で１夜間反応させた後
、反応液を０．２Ｎ塩酸および飽和食塩水で洗浄し、無
水硫酸ナトリウムで乾燥脱水し、次いで溶媒を留去して
得られた反応生成物をヘンゼンを用いてカラムクロマト
により精製して下記構造式の化合物０．０８５ ｇを得
た。Example 1 2,6-cyhydroxyazulene 0.034 represented by the following structural formula (II[)
A catalytic amount of pyridine was added to this solution, and the reaction mixture was allowed to react overnight at room temperature. The reaction product obtained by distilling off the solvent was purified by column chromatography using Hensen to obtain 0.085 g of a compound having the following structural formula.
で示されるｐ−ｎ−プロピル安息香酸０．１２５ ｇに
塩化チオニルｌ ｍｅを加え、１１０℃で３時間還流下
で反応させたのち、減圧下で塩化チオニルを留去する。Thionyl chloride lme was added to 0.125 g of p-n-propylbenzoic acid represented by the formula, and the mixture was reacted under reflux at 110°C for 3 hours, and then thionyl chloride was distilled off under reduced pressure.
これに下記構造式
本化合物は１６３．２℃に液晶転移点（結晶一液晶転移
点）を有する青紫色の液晶化合物であり、クロロホルム
中での可視部の極大吸収波長は５３５ｎｍであった。The compound having the following structural formula is a blue-violet liquid crystal compound having a liquid crystal transition point (crystal-liquid crystal transition point) at 163.2° C., and the maximum absorption wavelength in the visible region in chloroform was 535 nm.
本化合物を商品名ＺＬＩ−１１３２（メルク社製品）と
して市販されているフェニルシクロヘキサン系液晶組成
物に１０−ｔ％配合して得られた液晶組成物は赤紫色を
示し、そのネマチック−アイソトロピック転移点は９４
．６℃であった。The liquid crystal composition obtained by blending 10-t% of this compound into a phenylcyclohexane liquid crystal composition commercially available under the trade name ZLI-1132 (product of Merck & Co., Ltd.) exhibits a reddish-purple color and exhibits a nematic-isotropic transition. The score is 94
．． The temperature was 6°C.
実施例２
実施例１の構造式（ＩＩＩ）で示される化合物の代わり
に下記構造式
で示されるｐ−ｎ−ペンチル安息香酸０．１５ ｇを用
い、他は実施例１と同様にして下記構造式の化合物０．
０８７ｇを得た。Example 2 The following structure was prepared in the same manner as in Example 1 except that 0.15 g of p-n-pentylbenzoic acid shown by the following structural formula was used instead of the compound shown by the structural formula (III) of Example 1. A compound of formula 0.
087g was obtained.
１（ｎ） ｎｍであった。1(n) It was nm.
本化合物を商品名ＺＬＩ−１１３’２（メルク社製品）
として市販されているフェニルシクロヘキサン系液晶組
成物に１０ｗｔ％配合して得られた液晶組成物は赤紫色
を示し、そのネマチック−アイソトロピック転移点は９
１．２℃であった。This compound is used under the trade name ZLI-113'2 (product of Merck & Co., Ltd.)
The liquid crystal composition obtained by blending 10 wt% into a phenylcyclohexane liquid crystal composition commercially available as 10% exhibits a reddish-purple color, and its nematic-isotropic transition point is 9.
The temperature was 1.2°C.
実施例３
実施例１．２に準じた方法により合成した第１表に示さ
れる本発明のアズレン誘導体のクロロホルム中での可視
部の極大吸収波長（λｍａｘ）および商品名ＺＬＩ−１
１３２（メルク社製品）として市販されているフェニル
シクロヘキサン系液晶組成物に１０−ｔ％配合して得ら
れた液晶組成物の色相、ネマチック−アイソトロピック
転移点（ＴＮＩ）を第１表に示す。Example 3 Maximum absorption wavelength (λmax) in the visible region in chloroform of the azulene derivatives of the present invention shown in Table 1 synthesized by a method according to Example 1.2 and product name ZLI-1
Table 1 shows the hue and nematic-isotropic transition point (TNI) of a liquid crystal composition obtained by adding 10-t% to a phenylcyclohexane-based liquid crystal composition commercially available as 132 (Merck & Co., Ltd. product).
Claims (2)
を示す。） で表されるアズレン誘導体。(1) An azulene derivative represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [I] (In the formula, R^1 and R^2 represent a hydrogen atom or an alkyl group.)
を示す。） で表されるアズレン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。(2) Contain at least one azulene derivative represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 and R^2 represent a hydrogen atom or an alkyl group.) A liquid crystal composition characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63222127A JPH0768174B2 (en) | 1988-09-05 | 1988-09-05 | Azulene derivative and liquid crystal composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63222127A JPH0768174B2 (en) | 1988-09-05 | 1988-09-05 | Azulene derivative and liquid crystal composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0269441A true JPH0269441A (en) | 1990-03-08 |
| JPH0768174B2 JPH0768174B2 (en) | 1995-07-26 |
Family
ID=16777588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63222127A Expired - Lifetime JPH0768174B2 (en) | 1988-09-05 | 1988-09-05 | Azulene derivative and liquid crystal composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768174B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1318185A1 (en) * | 2001-12-10 | 2003-06-11 | MERCK PATENT GmbH | Reactive mesogenic azulenes |
| WO2006136345A1 (en) * | 2005-06-23 | 2006-12-28 | Tetragon-Chemie Ag | Liquid crystal molecules comprising hydroazulene structures |
-
1988
- 1988-09-05 JP JP63222127A patent/JPH0768174B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1318185A1 (en) * | 2001-12-10 | 2003-06-11 | MERCK PATENT GmbH | Reactive mesogenic azulenes |
| WO2006136345A1 (en) * | 2005-06-23 | 2006-12-28 | Tetragon-Chemie Ag | Liquid crystal molecules comprising hydroazulene structures |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0768174B2 (en) | 1995-07-26 |
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