JP2701078B2 - Allyl tolan compounds - Google Patents
Allyl tolan compoundsInfo
- Publication number
- JP2701078B2 JP2701078B2 JP31390789A JP31390789A JP2701078B2 JP 2701078 B2 JP2701078 B2 JP 2701078B2 JP 31390789 A JP31390789 A JP 31390789A JP 31390789 A JP31390789 A JP 31390789A JP 2701078 B2 JP2701078 B2 JP 2701078B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- liquid crystal
- compound
- allyl
- tolan compounds
- 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、電気光学的表示材料として有用なトラン化
合物に関し、さらに詳しくは、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を大きくする
のに有用なアリルトラン化合物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a trans compound useful as an electro-optical display material. The present invention relates to an allyl tolan compound useful for increasing anisotropy.
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
薄くする事により、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（Δｎ）の
大きな液晶材料が必要となった。その代表例として低粘
性にして高いΔｎを示す各種トラン化合物が特開昭60−
155142、特開昭61−260031、特開昭63−287737等に開示
されたがまだ不十分であり、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. As a high-speed response, ferroelectric liquid crystals have been studied, but a high-speed response can be expected by making the thickness of the STN-type liquid crystal cell thinner. In that case,
A liquid crystal material having a large refractive index anisotropy (Δn) of the liquid crystal material to be filled in the cell is required. As typical examples, various tolan compounds having a low viscosity and a high Δn are disclosed in
155142, JP-A-61-260031, JP-A-63-287737, etc., are still insufficient, and compounds having higher Δn have 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、X1はハロゲン原子又はシアノ基を示し、X2はハ
ロゲン原子又は水素原子を示す。） 本発明になる上記一般式（Ｉ）で表される化合物にお
いて、X1、X2のハロゲン原子としてフッ素、塩素があげ
られる。 (In the formula, X 1 represents a halogen atom or a cyano group, and X 2 represents a halogen atom or a hydrogen atom.) In the compound represented by the above general formula (I) according to the present invention, X 1 and X 2 Examples of the halogen atom include fluorine and chlorine.
また、上記一般式（Ｉ）で表される化合物は、次の製
造方法に従って製造する事が出来る。The compound represented by the above general formula (I) can be produced according to the following production method.
（１）ジブロムベンゼンとマグネシュウムとの反応によ
り生成するグリニャール試薬に臭化アリルを反応させ、
式（II）の４−ブロモアリルベンゼンを得る。(1) Allyl bromide is reacted with a Grignard reagent produced by the reaction of dibromobenzene and magnesium,
4-bromoallylbenzene of the formula (II) is obtained.
（２）式（II）の化合物をビス（トリフェニルホスフィ
ン）パラジウム（II）クロライドの如き触媒を用いて、
式（III）のメチルブチノールと反応させ、式（IV）の
４−（４−アリルフェニル）−２−メチル−３−ブチン
−２−オールを得る。(2) using a catalyst such as bis (triphenylphosphine) palladium (II) chloride to convert the compound of formula (II)
Reaction with methyl butynol of formula (III) gives 4- (4-allylphenyl) -2-methyl-3-butyn-2-ol of formula (IV).
（３）式（IV）の化合物を水酸化ナトリューム等の触媒
の存在下に、分解し、式（Ｖ）の４−アリルフェニルア
セチレン得る。(3) The compound of formula (IV) is decomposed in the presence of a catalyst such as sodium hydroxide to obtain 4-allylphenylacetylene of formula (V).
（４）式（Ｖ）の４−アリルフェニルアセチレンをビス
（トリフェニルホスフィン）パラジウム（II）クロライ
ドの如き触媒を用いて式（VI）の化合物と反応させて式
（Ｉ）の化合物を製造する。(4) reacting 4-allylphenylacetylene of formula (V) with a compound of formula (VI) using a catalyst such as bis (triphenylphosphine) palladium (II) chloride to produce a compound of formula (I) .
かくして得られる本発明の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 allyltolan compound of the present invention thus obtained is STN
When mixed with a liquid crystal material, it is useful not only for increasing the anisotropy of the refractive index of the liquid crystal material, but also for being excellent in reactivity and thus useful as various synthetic intermediates.
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 3,4−ジフルオロ−４′−アリルトランの合成 （１）４−ブロモアリルベンゼンの合成 ｐ−ジブロモベンゼン141.5gを乾燥したテトラヒドロ
フラン（THF）230mlに溶解し、予め金属マグネシュウム
16.0gとTHF100mlの入ったフラスコへ滴下した。このグ
リニャール試薬にTHF100mlに臭化アリル87.1gを溶解し
た溶液を滴下し、一晩放置した。次に飽和塩化アンモニ
ウム水溶液120mlを加え加水分解した後、上澄みの有機
層をデカンテイションで分離し、乾燥、脱溶媒を後、減
圧蒸留により、目的の４−ブロモアリルベンゼンを63.0
gを得た。Example 1 Synthesis of 3,4-difluoro-4'-allyltran (1) Synthesis of 4-bromoallylbenzene 141.5 g of p-dibromobenzene was dissolved in 230 ml of dry tetrahydrofuran (THF), and metal magnesium was previously dissolved.
The solution was dropped into a flask containing 16.0 g and 100 ml of THF. A solution of 87.1 g of allyl bromide in 100 ml of THF was added dropwise to this Grignard reagent, and the mixture was left overnight. Next, 120 ml of a saturated aqueous solution of ammonium chloride was added and hydrolyzed.The organic layer of the supernatant was separated by decantation, dried, and the solvent was removed.
g was obtained.
（２）４−（４−アリルフェニル）−２−メチル−３−
ブチン−２−オールの合成 （１）で得た４−ブロモアリルベンゼン63.0g、メチ
ルブチノール40.4g、トリフェニルホスフィン1.7g、ビ
ス（トリフェニルホスフィン）パラジュウム（II）クロ
ライド0.67g及び沃化銅0.24gを320mlのトリエチルアミ
ンに溶解し、還流下にて８時間反応した。室温まで冷却
し、塩を除去下後、脱溶媒を行い、ジエチルエーテルで
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24.1gを得
た。(2) 4- (4-allylphenyl) -2-methyl-3-
Synthesis of butyn-2-ol 63.0 g of 4-bromoallylbenzene obtained in (1), 40.4 g of methylbutynol, 1.7 g of triphenylphosphine, 0.67 g of bis (triphenylphosphine) palladium (II) chloride and copper iodide 0.24 g was dissolved in 320 ml of triethylamine and reacted under reflux for 8 hours. After cooling to room temperature and removing the salt, the solvent was removed, extracted with diethyl ether, and washed with dilute hydrochloric acid and distilled water. After drying and removing the solvent, 24.1 g of the desired 4- (4-allylphenyl) -2-methyl-3-butyn-2-ol was obtained by distillation under reduced pressure.
（３）４−アリルフェニルアセチレンの合成 （２）で得た４−（４−アリルフェニル）−２−メチ
ル−３−ブチン−２−オール24.1g及び水素化ナトリュ
ウム0.43gを乾燥トルエン220mlに分散し、アルゴン雰囲
気下、最高温度110℃にて反応し、生成したアセトンを
留去した。冷却後、５％塩酸にて洗浄後、更に水洗を行
った。乾燥、脱溶媒を行い、得られた反応生成物を減圧
蒸留により、４−アリルフェニルアセチレン14.9gを得
た。(3) Synthesis of 4-allylphenylacetylene 24.1 g of 4- (4-allylphenyl) -2-methyl-3-butyn-2-ol obtained in (2) and 0.43 g of sodium hydride were dispersed in 220 ml of dry toluene. The reaction was carried out at a maximum temperature of 110 ° C. in an argon atmosphere, and the generated acetone was distilled off. After cooling, the plate was washed with 5% hydrochloric acid, and further washed with water. After drying and solvent removal, the resulting reaction product was distilled under reduced pressure to obtain 14.9 g of 4-allylphenylacetylene.
（４）3,4−ジフルオロ−４′−アリルトランの合成 １−ブロモ−3,4−ジフルオロベンゼン3.2g、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及び沃化銅0.027gをトリエチルアミン10mlに溶
解した。これに、トリエチルアミン4mlに４−アリルフ
ェニルアセチレン2.0gを溶かした溶液を室温で滴下し、
次に95℃まで昇温して８時間反応した。室温まで冷却
後、ジエチルエーテルで抽出し、希塩酸及び水で洗浄し
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た後、減圧蒸留して、目的
物の3,3,4−ジフルオロ−４′−アリルトラン0.5gを得
た。〔融点27.0℃〕 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。(4) Synthesis of 3,4-difluoro-4'-allyltolan 3.2 g of 1-bromo-3,4-difluorobenzene, 0.03 g of bis (triphenylphosphine) palladium (II) chloride and 0.027 g of copper iodide were added to 10 ml of triethylamine. Was dissolved. To this, a solution of 2.0 g of 4-allylphenylacetylene in 4 ml of triethylamine was added dropwise at room temperature.
Next, the temperature was raised to 95 ° C., and the reaction was performed for 8 hours. After cooling to room temperature, the mixture was extracted with diethyl ether and 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. Then, after recrystallization from methanol, distillation under reduced pressure was carried out to obtain 0.5 g of the desired product, 3,3,4-difluoro-4'-allyltran. [Melting point: 27.0 ° C] As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.
3040cm-1,2200cm-1,1640cm-1,1590cm-1,1510cm-1,141
0cm-1,1260cm-1,1200cm-1,1100cm-1,990cm-1,910cm-1,8
10cm-1, 実施例２ ４−シアノ−４′−アリルトランの合成 ４−ブロモベンゾニトリル3.1g、ビス（トリェニルホ
スフィン）パラジウム（II）クロライド0.03g及び沃化
銅0.027gをトリエチルアミン10mlに溶解した。これに、
トリエチルアミン4mlに実施例１で得られた４−アリル
フェニルアセチレン2.0gを溶かした溶液を室温で滴下
し、次に95℃まで昇温して３時間反応し、希塩酸及び水
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ｎ−ヘキ
サンにて再結晶を行い、目的物の４−シアノ−４′−ア
リルトランン0.6gを得た。〔融点66.1℃〕 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。 3040cm -1, 2200cm -1, 1640cm -1 , 1590cm -1, 1510cm -1, 141
0cm -1, 1260cm -1, 1200cm -1 , 1100cm -1, 990cm -1, 910cm -1, 8
10 cm -1, Example 2 Synthesis of 4-cyano-4'Arirutoran 3.1 g of 4-bromobenzonitrile, 0.03 g of bis (trienylphosphine) palladium (II) chloride and 0.027 g of copper iodide were dissolved in 10 ml of triethylamine. to this,
A solution prepared by dissolving 2.0 g of 4-allylphenylacetylene obtained in Example 1 in 4 ml of triethylamine was added dropwise at room temperature, then heated to 95 ° C., reacted for 3 hours, and washed with dilute hydrochloric acid and water. After drying and solvent removal, 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, recrystallization was performed with n-hexane to obtain 0.6 g of the desired product, 4-cyano-4'-allyltranne. [Melting point: 66.1 ° C.] As a result of infrared spectroscopy, the obtained product had the following characteristic absorption and was confirmed to be the desired product.
3040cm-1,2200cm-1,1640cm-1,1590cm-1,1510cm-1,141
0cm-1,1260cm-1,1000cm-1,910cm-1,830cm-1,810cm-1, 実施例３ 本発明の新規なアリルトラン化合物を液晶に添加する
ことにより、液晶のΔｎ、誘電率の異方性（Δε）及び
粘度が改良されることを見るために、既存のアルキルシ
クロヘキサンカルボン酸アルコキシフェニルエステル系
液晶組成物に10％のトラン化合物（比較例として、3,4
−ジフルオロ−４′−ｎ−プロピルトラン、比較例２と
して、４−シアノ−４′−ｎ−プロピルトラン）を混合
して それぞれの物性値の変化を測定し、その結果を次
に示した。 3040cm -1, 2200cm -1, 1640cm -1 , 1590cm -1, 1510cm -1, 141
0cm -1, 1260cm -1, 1000cm -1 , 910cm -1, 830cm -1, 810cm -1, by a novel Arirutoran compound of Example 3 the present invention is added to the liquid crystal, the liquid crystal of [Delta] n, the dielectric constant different for In order to see that the anisotropy (Δε) and the viscosity were improved, 10% of a tolan compound (3,4 as a comparative example) was added to an existing alkylcyclohexanecarboxylic acid alkoxyphenyl ester-based liquid crystal composition.
-Difluoro-4'-n-propyl tolane and, as Comparative Example 2, 4-cyano-4'-n-propyl tolane) were mixed, and changes in the respective physical properties were measured. The results are shown below.
〔発明の効果〕 上の結果から明らかなように、本発明の新規なアリル
トラン化合物は、母液晶のΔｎ値を大きくするととも
に、粘度も無添加品に比較し著しく低下せしめ、従来優
れているものより、更に低下せしめる効果が見られる。 [Effects of the Invention] As is clear from the above results, the novel allyltolan compound of the present invention has a large value of Δn of the mother liquid crystal, and also has a significantly reduced viscosity as compared with the non-added product. The effect of further lowering is seen.
Claims (1)
化合物。 （式中、X1はハロゲン原子又はシアノ基を示し、X2はハ
ロゲン原子又は水素原子を示す。）An allyltolan compound represented by the following general formula (I): (In the formula, X 1 represents a halogen atom or a cyano group, and X 2 represents a halogen atom or a hydrogen atom.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31390789A JP2701078B2 (en) | 1989-12-02 | 1989-12-02 | Allyl tolan compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31390789A JP2701078B2 (en) | 1989-12-02 | 1989-12-02 | Allyl tolan compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03176437A JPH03176437A (en) | 1991-07-31 |
| JP2701078B2 true JP2701078B2 (en) | 1998-01-21 |
Family
ID=18046957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31390789A Expired - Lifetime JP2701078B2 (en) | 1989-12-02 | 1989-12-02 | Allyl tolan compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2701078B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100311921B1 (en) * | 1993-10-13 | 2002-10-31 | 스미또모 가가꾸 고오교오 가부시끼가이샤 | Tolan compound, preparation method thereof, liquid crystal composition containing the compound as an active ingredient, and liquid crystal element using the liquid crystal composition |
| WO1998007672A1 (en) * | 1996-08-20 | 1998-02-26 | Chisso Corporation | Liquid-crystal alkenyltolan derivative, liquid-crystal composition, and liquid-crystal display element |
| 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 |
| JP5936947B2 (en) * | 2012-08-09 | 2016-06-22 | 三菱化学株式会社 | Method for producing high-purity vinylene carbonate |
-
1989
- 1989-12-02 JP JP31390789A patent/JP2701078B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03176437A (en) | 1991-07-31 |
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