JP2701085B2 - Allyl alkyltran compounds - Google Patents
Allyl alkyltran compoundsInfo
- Publication number
- JP2701085B2 JP2701085B2 JP12753090A JP12753090A JP2701085B2 JP 2701085 B2 JP2701085 B2 JP 2701085B2 JP 12753090 A JP12753090 A JP 12753090A JP 12753090 A JP12753090 A JP 12753090A JP 2701085 B2 JP2701085 B2 JP 2701085B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- allyl
- compound
- alkyl
- alkyltran
- 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、新規なトラン化合物に関し、詳しくは、ST
N型液晶材料に混合することによって、該液晶材料の屈
折率異方性を大きくするのに有用である新規なアルキル
・アリルトラン化合物に関する。The present invention relates to a novel tolan compound, and in particular, to ST
The present invention relates to a novel alkyl allyl tolane compound which is useful for increasing the refractive index anisotropy of a liquid crystal material when mixed with an N-type liquid crystal material.
現在、STN型液晶セルはグリーンまたはブルーモード
より白黒、フルカラー化へ向けて開発が進められてお
り、それと併行して動画対応への高速応答化の検討が進
められている。高速応答としては、従来、強誘電性液晶
が研究されているが、STN型液晶セルの層の厚さをより
薄くすることにより、高速応答が期待される。その場
合、セルに充填される液晶材料の屈折率の異方性（Δ
ｎ）の大きな液晶材料が必要となり、各種の検討が進め
られてきた。たとえば、アルキル・クロチルオキシトラ
ン化合物（特開昭62−277333号公報）、アルキルシクロ
ヘキシル・フルオロトラン化合物（特開昭63−287737号
公報）あるいはアルキル・アルキニルオキシトラン化合
物（特開平２−83346号公報）などが開示されたがまだ
不充分であり、さらに高いΔｎを示す化合物が望まれて
いた。At present, STN-type liquid crystal cells are being developed toward black-and-white and full-color modes from green or blue mode, and at the same time, studies are underway on high-speed response to moving image support. Conventionally, ferroelectric liquid crystal has been studied as a high-speed response, but a high-speed response is expected by making the thickness of the STN-type liquid crystal cell thinner. In that case, the anisotropy of the refractive index of the liquid crystal material filled in the cell (Δ
A liquid crystal material having a large value of n) is required, and various studies have been made. For example, an alkyl crotyl oxytran compound (Japanese Patent Application Laid-Open No. 62-277333), an alkylcyclohexyl fluorotolan compound (Japanese Patent Application Laid-Open No. 63-287737) or an alkyl alkynyl oxytran compound (Japanese Patent Application Laid-Open No. 2-83346). Gazettes) have been disclosed but are still insufficient, and a compound exhibiting a higher Δn has been desired.
本発明者等は、上記現状に鑑み、低粘度にして高いΔ
ｎを示す化合物を見出すべく鋭意検討を重ねた結果、次
の一般式（Ｉ）で表される新規なアリルトラン化合物を
液晶組成物に添加することにより、液晶組成物のΔｎを
著しく改良するとともに、粘度を著しく低下させること
を見出した。In view of the above-mentioned situation, the present inventors have set a low viscosity and a high Δ
As a result of intensive studies to find a compound exhibiting n, the addition of a novel allyltolan compound represented by the following general formula (I) to the liquid crystal composition significantly improved Δn of the liquid crystal composition, It has been found that the viscosity is significantly reduced.
（式中、Ｒは炭素原子数１〜12のアルキル基またはシク
ロアルキル基を示す。） 本発明になる上記一般式（Ｉ）で表される化合物にお
いてＲで示されるアルキル基としては、たとえば、メチ
ル、エチル、プロピル、ブチル、ペンチル、ヘキシル、
シクロヘキシル、ヘプチル、オクチル、ノニル、デシ
ル、ウンデシル、ドデシルなどがあげられる。 (In the formula, R represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group.) In the compound represented by the above general formula (I) according to the present invention, the alkyl group represented by R includes, for example, Methyl, ethyl, propyl, butyl, pentyl, hexyl,
Examples include cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
また、上記一般式（Ｉ）で表される化合物は、たとえ
ば次のスキームに従って容易に製造することができる。The compound represented by the above general formula (I) can be easily produced, for example, according to the following scheme.
かくして得られる本発明のアルキル・アリルトラン化
合物はSTN型液晶材料に混合することによって液晶材料
の屈折率の異方性（Δｎ）を大きくするに有用なばかり
でなく、反応性に優れるため、各種の合成中間体として
有用である。 The alkyl / allyl tolane compound of the present invention thus obtained is not only useful for increasing the anisotropy (Δn) of the refractive index of the liquid crystal material by mixing it with the STN type liquid crystal material, but also has excellent reactivity. Useful as a synthetic intermediate.
以下、実施例によって本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１ ４−ｎ−プロピル−４′−アリルトランの合成 ４−ブロモアリルベンゼンの合成 フラスコに金属マグネシウム42.8gと乾燥テトラヒド
ロフラン（THF）270mlを仕込み、そこにｐ−ジブロモベ
ンゼン377.5gを乾燥テトラヒドロフラン（THF）607mlに
溶解して滴下した。さらに臭化アリル232.3gをTHF270ml
に溶解して滴下して、そのまま一夜放置した。次いで飽
和塩化アンモニウム水溶液300mlを加え加水分解した
後、上澄みの有機層をデカンテーションで分離した。乾
燥、脱溶媒をした後、減圧蒸留により、目的の４−ブロ
モアリルベンゼン222.6gを得た。Example 1 Synthesis of 4-n-propyl-4'-allyltran Synthesis of 4-bromoallylbenzene 42.8 g of metallic magnesium and 270 ml of dry tetrahydrofuran (THF) were charged into a flask, and 377.5 g of p-dibromobenzene was dissolved in 607 ml of dry tetrahydrofuran (THF) and added dropwise. Further 232.3 g of allyl bromide in 270 ml of THF
, And added dropwise, and left as it was overnight. Subsequently, 300 ml of a saturated aqueous solution of ammonium chloride was added to hydrolyze, and then the supernatant organic layer was separated by decantation. After drying and removing the solvent, 222.6 g of the desired 4-bromoallylbenzene was obtained by distillation under reduced pressure.
４−（４−アリルフェニル）−２−メチル−３−ブチ
ン−２−オールの合成 で得られた４−ブロモアリルベンゼン222.3g、メチ
ルブチノール126.8g、トリフェニルホスフィン5.3g、ビ
ス（トリフェニルホスフィン）パラジウム（II）クロラ
イド2.1gおよびよう化銅0.8gを1000mlのトリエチルアミ
ンに溶解し、アルゴン雰囲気下に90℃の還流温度にて８
時間反応した。室温まで冷却し、生成したアミン塩を吸
引ろ過で除去した後、脱溶媒をおこなった。トルエンで
抽出後、希塩酸及び蒸留水で洗浄した。乾燥、脱溶媒
後、減圧蒸留によって、目的の４−（４−アリルフェニ
ル）−２−メチル−３−ブチン−２−オール114.0gを得
た。Synthesis of 4- (4-allylphenyl) -2-methyl-3-butyn-2-ol 222.3 g of 4-bromoallylbenzene, 126.8 g of methylbutynol, 5.3 g of triphenylphosphine, bis (triphenyl Dissolve 2.1 g of phosphine) palladium (II) chloride and 0.8 g of copper iodide in 1000 ml of triethylamine and reflux at 90 ° C. under argon atmosphere at 90 ° C.
Reacted for hours. After cooling to room temperature and removing the generated amine salt by suction filtration, the solvent was removed. After extraction with toluene, the extract was washed with diluted hydrochloric acid and distilled water. After drying and removing the solvent, 114.0 g of the desired 4- (4-allylphenyl) -2-methyl-3-butyn-2-ol was obtained by distillation under reduced pressure.
４−アリルフェニルアセチレンの合成 で得られた４−（４−アリルフェニル）−２−メチ
ル−３−ブチン−２−オール114.0gおよび水素化ナトリ
ウム0.43gを乾燥トルエン912mlに分散し、アルゴン雰囲
気下に生成するアセトンを除去しながら加温し、最高温
度110℃まで反応した。室温まで冷却し、希塩酸および
蒸留水で洗浄した。乾燥、脱溶媒後、減圧蒸留によっ
て、目的の４−アリルフェニルアセチレン62.9gを得
た。114.0 g of 4- (4-allylphenyl) -2-methyl-3-butyn-2-ol and 0.43 g of sodium hydride obtained in the synthesis of 4-allylphenylacetylene were dispersed in 912 ml of dry toluene, and the mixture was dispersed under an argon atmosphere. The reaction was heated up to a maximum temperature of 110 ° C. while removing acetone generated in the reaction. It was cooled to room temperature and washed with dilute hydrochloric acid and distilled water. After drying and removing the solvent, 62.9 g of the desired 4-allylphenylacetylene was obtained by distillation under reduced pressure.
４−ｎ−プロピル−４′−アリルトランの合成 ｐ−ｎ−プロピルモードベンゼン1.7g、ビス（トリフ
ェニルホスフィン）パラジウム（II）クロライド0.015
g、よう化銅0.013gおよびジエチルアミン2.05gをN,N′
−ジメチルホルムアミド5mlに溶解した。これに、トリ
エチルアミン2mlにで得られた４−アリルフェニルア
セチレン1.2gを溶かした溶液を室温で滴下し、そのまま
室温で７時間撹拌した。トルエンで抽出した後、希塩酸
および水で洗浄した。乾燥、脱溶媒を行い、反応生成物
をｎ−ヘキサンを展開溶媒として、シリカゲルカラム処
理を行った。次いでメタノールで再結晶を行って目的の
４−ｎ−プロピル−４′−アリルトラン0.8gを得た。融
点28.0℃ 赤外分光分析の結果、得られた生成物は次の特性吸収
を有しており、目的物であることを確認した。Synthesis of 4-n-propyl-4'-allyltran 1.7 g of pn-propylmodebenzene, bis (triphenylphosphine) palladium (II) chloride 0.015
g, copper iodide 0.013 g and diethylamine 2.05 g were N, N ′
-Dissolved in 5 ml of dimethylformamide. To this was added dropwise a solution of 1.2 g of 4-allylphenylacetylene obtained in 2 ml of triethylamine at room temperature, and the mixture was stirred at room temperature for 7 hours. After extraction with toluene, the extract was washed with dilute hydrochloric acid and water. After drying and removing the solvent, the reaction product was subjected to silica gel column treatment using n-hexane as a developing solvent. Next, the product was recrystallized from methanol to obtain 0.8 g of the desired 4-n-propyl-4'-allyltran. Melting point: 28.0 ° C. As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.
3040cm-1, 2930cm-1, 2210cm-1, 1910cm-1, 1640cm-1, 1510cm-1, 1410cm-1, 990cm-1, 910cm-1, 820cm-1, 540cm-1 実施例２ ４−ブチル−４′−アリルトランの合成 ｐ−ｎ−ブチルヨードベンゼン3.6g、ビス（トリフェ
ニルホスフィン）パラジウム（II）クロライド0.03g、
よう化銅0.027gおよびジエチルアミン4.10gをN,N′−ジ
メチルホルムアミド12ml Ｈに溶解した。ここに、トリ
エチルアミン2mlに実施例１ので得られた４−アリル
フェニルアセチレン2.3gを溶かした溶液を室温で滴下
し、そのまま室温で６時間撹拌した。トルエンで抽出
し、希塩酸および水で洗浄した。乾燥、脱溶媒を行い、
反応生成物をｎ−ヘキサンに５％の酢酸エチルを混合し
たものを展開溶媒として、シリカゲルカラム処理を行っ
た。次いで減圧蒸留を行ない、目的の４−ｎ−ブチル−
４′−アリルトラン0.6gを得た。 3040cm -1, 2930cm -1, 2210cm -1 , 1910cm -1, 1640cm -1, 1510cm -1, 1410cm -1, 990cm -1, 910cm -1, 820cm -1, 540cm -1 Example 2 4-butyl - Synthesis of 4'-allyltran 3.6 g of pn-butyl iodobenzene, 0.03 g of bis (triphenylphosphine) palladium (II) chloride,
0.027 g of copper iodide and 4.10 g of diethylamine were dissolved in 12 ml of N, N'-dimethylformamide. A solution of 2.3 g of 4-allylphenylacetylene obtained in Example 1 in 2 ml of triethylamine was added dropwise at room temperature, and the mixture was stirred at room temperature for 6 hours. Extracted with toluene and washed with dilute hydrochloric acid and water. After drying and desolvation,
The reaction product was subjected to silica gel column treatment using a mixture of n-hexane and 5% ethyl acetate as a developing solvent. Then, distillation under reduced pressure was performed to obtain the desired 4-n-butyl-
0.6 g of 4'-allyltran was obtained.
沸点 145℃/0.8mmHg 赤外分光分析の結果、得られた生成物は次の特性吸収
を有しており、目的物であることを確認した。As a result of infrared spectroscopy at a boiling point of 145 ° C./0.8 mmHg, the obtained product had the following characteristic absorption and was confirmed to be the desired product.
3040cm-1, 2920cm-1, 2210cm-1, 1910cm-1, 1640cm-1, 1520cm-1, 1410cm-1, 990cm-1, 910cm-1, 830cm-1, 540cm-1 参考例 本発明になる新規な４−アルキル−４′−アリルトラ
ン化合物を液晶材料混合物に添加することにより、該液
晶材料のΔｎを改良することができる。その効果をみる
ために、次の化合物の1:1:1の液晶混合物に４−アルキ
ル−４′−アリルトラン化合物を10％混合して20℃にお
けるΔｎの値の変化を測定した。その結果を次に示し
た。また、類似構造の既存の下記化合物についてもΔｎ
を外挿法により求め、その値との比較を行なった。 3040cm -1, 2920cm -1, 2210cm -1 , 1910cm -1, 1640cm -1, 1520cm -1, 1410cm -1, 990cm -1, 910cm -1, novel becomes 830 cm -1, 540 cm -1 Reference Example present invention By adding such a 4-alkyl-4'-allyltrane compound to a liquid crystal material mixture, the Δn of the liquid crystal material can be improved. To see the effect, 10% of a 4-alkyl-4'-allyltran compound was mixed with a 1: 1: 1 liquid crystal mixture of the following compounds, and the change in Δn value at 20 ° C. was measured. The results are shown below. In addition, the following compound having a similar structure also has Δn
Was determined by extrapolation and compared with that value.
〔発明の効果〕 上の結果から明らかなように、本発明になる新規なア
ルキル・アリルトラン化合物は、母液晶および既存のジ
アルキルトラン化合物に比べて、Δｎの値を大きくする
効果があり、液晶材料の視角依存性を改良する材料とし
て有効であることが明らかである。 [Effects of the Invention] As is clear from the above results, the novel alkyl allyl tolan compound according to the present invention has an effect of increasing the value of Δn as compared with the mother liquid crystal and the existing dialkyl tolan compound, and the liquid crystal material It is clear that the material is effective as a material for improving the viewing angle dependency of.
Claims (1)
リルトラン化合物。 （式中、Ｒは炭素原子数１〜12のアルキル基またはシク
ロアルキル基を示す。）1. An alkyl / allyl tolane compound represented by the following general formula (I). (In the formula, R represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12753090A JP2701085B2 (en) | 1990-05-17 | 1990-05-17 | Allyl alkyltran compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12753090A JP2701085B2 (en) | 1990-05-17 | 1990-05-17 | Allyl alkyltran compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0421640A JPH0421640A (en) | 1992-01-24 |
| JP2701085B2 true JP2701085B2 (en) | 1998-01-21 |
Family
ID=14962301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12753090A Expired - Lifetime JP2701085B2 (en) | 1990-05-17 | 1990-05-17 | Allyl alkyltran compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2701085B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63319299A (en) * | 1987-06-20 | 1988-12-27 | Agency Of Ind Science & Technol | Aluminum borate whisker and production thereof |
| JP4186133B2 (en) * | 1997-09-29 | 2008-11-26 | Ｄｉｃ株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
| WO2011024917A1 (en) * | 2009-08-27 | 2011-03-03 | 旭硝子株式会社 | Hot melt adhesive composition |
| JP6121074B1 (en) | 2015-09-16 | 2017-04-26 | 大日精化工業株式会社 | Alumina-based thermally conductive oxide and method for producing the same |
-
1990
- 1990-05-17 JP JP12753090A patent/JP2701085B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0421640A (en) | 1992-01-24 |
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