JP3598469B2 - Trifluoromethylbenzene derivatives and liquid crystal compositions containing them - Google Patents

Description

（式中、Ｒ ^１ は炭素原子数１から１４のアルキル基、アルコキシ基あるいはアルコキシアルキル基を表し、Ｒ ^２ は炭素原子数５から１４のアルキル基、アルコキシ基あるいはアルコキシアルキル基を表し、
【化８】

を表し、ｍ並びにｎはそれぞれ独立に０あるいは１を表す。
【００１１】
ただし、ｍとｎとは同時に０であることはなく、ｍとｎとが同時に１であるときは、ＡとＢとはいずれも
【化９】

を表わす）で表されるトリフルオロメチルベンゼン誘導体、並びに、この誘導体の少なくとも１種を含有することを特徴とする液晶組成物を提供するものである。
【００１２】
本発明に係わる新規化合物は、単独ではＳｍＣ相を有しているものと有していないものとがあるが、いずれも強誘電性液晶組成物あるいは、ネマチック液晶組成物を作成する際に使用できる有効な化合物である。
【００１３】
これらの化合物の合成方法の例について合成経路１〜５として概略を説明し、さらに、本発明の実施例を掲げて詳細を説明する。以下に示す合成経路は、その一例であり、これらにより本発明は特定されない。各実施例で合成した化合物の相転移温度の測定結果を表４に掲載する。なお、これらの結果は測定機器、測定方法の違い、あるいは純度により影響されるため、その数値に多少の異同が認められることは理解されよう。
【００１４】
〔合成経路〕
以下の合成経路中、Ｒは炭素原子数１〜１４のアルキル基を表し、Ｊ，ｋ，ｐ，ｑはそれぞれ１〜１３の整数を表し、他の記号は特許請求範囲の項で表されている定義を有する。
【００１５】
【化１０】

【００１６】
経路１（前駆体合成経路−１）
【化１１】

【００１７】
経路２（前駆体合成経路−２）
【化１２】

【００１８】
経路３（標記化合物合成経路−１）
【化１３】

【００１９】
【化１４】

経路４（前駆体合成経路−３）
【化１５】

【００２０】
経路５（標記化合物合成経路−２）
【化１６】

【００２１】
以下に前記合成経路について概略説明する。
経路１について：
一般式（１）〜（５）で表される化合物は市販されており、一般式（６）〜（９）で表される化合物は（６−１），（７−１），（９−１）を出発原料として得ることができる。
【００２２】
化合物（６−１）をＲＯＮａ（ナトリウムアルコキサイド）でエーテル化して得られる化合物（６−２）を臭素を用いて臭素化すれば一般式（６）で表される化合物が得られる。
【００２３】
化合物（７−１）をシアン化カリウムでシアノ化し、次いで酸加水分解して得られる化合物（７−３）をＬｉＡｌＨ_４で還元反応して化合物（７−４）が得られる。これを臭化水素酸で臭素化し、化合物（７−５）が得られる。化合物（７−５）を前記（７−１）に替えて用い、シアノ化、加水分解、還元、臭素化し、得られた臭素化物を用いて一連の反応を繰り返し任意に行うことにより一般式（７−６）で表される化合物が得られる。
【００２４】
一般式（７−６）で表される化合物をＲＯＮａ（ナトリウムアルコキサイド）でエーテル化すれば一般式（７）で表される化合物が得られる。一般式（８）の化合物はｐ−ブロムヨードベンゼンと一般式（７）で表される化合物から誘導されるボロン酸化合物とのカップリング反応により合成することができる。
【００２５】
化合物（９−１）をＬｉＡｌＨ_４で還元して得られる化合物（９−２）を臭化水素酸で臭素化することにより化合物（９−３）が得られる。化合物（９−３）を用いて、前記した化合物（７−１）から化合物（７−６）を得る方法と同様にして一般式（９−８）で表される化合物が得られる。一般式（９−８）で表される化合物を臭素を用いて臭素化し、次いでＲＯＮａ（ナトリウムアルコキサイド）でエーテル化することにより一般式（９）で表される化合物が得られる。
【００２６】
市販の一般式（１）〜（５）で表される化合物並びに前記方法で得られる一般式（６）〜（９）で表される化合物をそれぞれＭｇと反応させてグリニヤール試薬を調製し、これにトリメチルボレート〔Ｂ（ＯＣＨ_３）_３〕を作用させ、次いで加水分解して一般式（Ｐ−１）或いは（Ｐ−２）で表される化合物を得ることができる。
【００２７】
経路２について：
市販の化合物（１０−１）と亜硝酸ソーダを反応させてジアゾニウム塩を調製し、これを硫酸で加熱分解して化合物（１０−２）が、ヨウ化銅（Ｃｕｌ）と反応させて化合物（１１−１）が、又、化合物（１１−１）をシアン化銅〔Ｃｕ（ＣＮ）_２〕と反応させて化合物（１４−１）がそれぞれ得られる。
【００２８】
一般式（１０）で表される化合物は化合物（１０−２）とアルキルブロマイド（ＲＢｒ）との常法によるエーテル化反応により合成することができる。一般式（１１）および（１３）で表される化合物は化合物（１１−１）と経路１に記載の化合物（３）及び（１）のボロン酸とをそれぞれカップリング反応させることにより得られる。
【００２９】
前述の方法で得られる化合物（１４−１）を用い、経路１において化合物（７−１）から一般式（７）及び（８）で表される化合物を得るのと同様の方法で一般式（１４）及び（１５）で表される化合物が得られる。又、この経路中の化合物（１４−３）をトシルクロライドでトシル化し、これにアルキルマグネシウムブロマイド（ＲＭｇＢｒ）を作用させれば一般式（１２）で表される化合物を得ることができる。
このようにして、一般式（Ｐ−３）あるいは（Ｐ−４）で表される化合物が得られる。
【００３０】
経路３について：
経路１並びに経路２で得られる一般式（Ｐ−１）で表される化合物と一般式（Ｐ−４）で表される化合物或いは一般式（Ｐ−２）で表される化合物と一般式（Ｐ−３）で表される化合物をテトラキストリフェニルホスフィンパラジウム〔Ｐｄ（ＰＰｈ_３）_４〕存在下にカップリング反応させることにより、本発明化合物である一般式（Ｉ）で表される化合物が得られる。
【００３１】
経路４について：
一般式（１６−１）で表される化合物を硫酸水素カリウム（ＫＨＳＯ_４）等の酸化剤を用いて酸化反応することにより一般式（１６）で表される化合物を得ることができる。
【００３２】
経路１において一般式（６）で表される化合物から得られるボロン酸誘導体を過酸化水素を用いて酸化反応することにより、一般式（１７−１）で表される化合物が得られる。これをパラジウムカーボン（Ｐｄ／Ｃ）触媒下に核水添して得られる一般式（１７−２）で表される化合物を硫酸水素カリウム（ＫＨＳＯ_４）等の酸化剤を用いて酸化反応することにより、一般式（１７）で表される化合物を得ることができる。
【００３３】
経路５について：
経路２で得られる一般式（Ｐ−３）あるいは（Ｐ−４）で表される化合物とマグネシウムを反応させてグリニヤール試薬を調製し、これらと経路４で得られる一般式（Ｐ−６）あるいは（Ｐ−５）で表される化合物とをそれぞれカップリング反応させることによって得られるシクロヘキセン誘導体をＰｄ／Ｃ存在下に水素添加すれば、本発明化合物である一般式（Ｉ）で表される化合物を得ることができる。
【００３４】
以下に実施例により更に詳しく説明するが、本明細書中に記載の略記号は下記の意味を有する。
ＧＴＯ： ガラスチューブオーブン
ＧＣ： ガスクロマトグラフィー
ＨＰＬＣ： 高速液体クロマトグラフィー
ＩＲ： 赤外線吸収スペクトル
Ｍａｓｓ： 質量スペクトル
ＧＣ−Ｍｓ： ガスクロマトグラフィ−質量スペクトル
ｂ．ｐ．： 沸点
Ｃ： 結晶
Ｓ_ｘ： Ｓｃ，Ｓ_Ａ以外のスメクチック相
ＳｍＣ，Ｓｃ： スメクチックＣ相
Ｓ_Ａ： スメクチックＡ相
Ｃｈ： コレステリック相
Ｎｅ： ネマチック相
Ｉ： 等方性液体
？： 温度不明
【００３５】
【実施例】
実施例１
【化１７】

２−アミノ−５−ブロモベンゾトリフルオリド２０ｇ（８３．３ｍｍｏｌ）に濃硫酸２４ｃｃの水６０ｃｃ溶液を加え、析出物が生じた。この析出物を溶かすためにさらに酢酸６０ｃｃを加えた。この溶液を５℃以下に冷却した後、亜硝酸ナトリウム６．６８ｇ（９６．８ｍｍｏｌ）の水２０ｃｃ溶液を滴下し、氷片、尿素０．５ｇ及び酢酸１２０ｃｃを加え５℃以下にて放置してジアゾニウム塩溶液を放置した。一方、硫酸ナトリウム３１．２ｇ、濃硫酸２４ｃｃ及び水２０ｃｃから成るけん濁液を１３０〜１３５℃に加熱した後、先に調整したジアゾニウム塩溶液を徐々に滴下し生成するフェノール体を水蒸気と一緒に留出させた。この留出液をエーテルで抽出、飽和食塩水で洗浄、硫酸ナトリウムで乾燥後溶媒を留去し、残留物を減圧下、ＧＴＯにて蒸留し２−トリフルオロメチル−４−ブロモフェノール１５．３ｇ（７６．５％）を得た。ｂ．ｐ．１０５℃／３０ｔｏｒｒ、ＧＣ９２．２％、ＧＣ−Ｍｓ２４０（Ｍ−１），２４２（Ｍ＋１）
【００３６】
【化１８】

（ａ）で得た２−トリフルオロメチル−４−ブロモフェノール５ｇ（２０．７ｍｍｏｌ）、ｎ−オクチルブロマイド４．８ｇ（２４．８ｍｍｏｌ）、炭酸カリウム８．６ｇ（６２．１ｍｍｏｌ）及びメチルエチルケトン５０ｃｃから成る混合物を還流下にて１０時間撹拌した。反応混合物から吸引ろ過により不溶物を除き、そのろ液を濃縮し、ベンゼンで抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分を減圧下、ＧＴＯにて蒸留し２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン５．９ｇ（８０．８％）を得た。ｂ．ｐ．１２５℃／１．５ｔｏｒｒ，ＧＣ９４．４％，ＧＣ−Ｍｓ ３５２（Ｍ−１），３５４（Ｍ＋１）
【００３７】
【化１９】

アルゴン雰囲気下、ヨウ素により活性化したマグネシウム１．８５ｇ（７６．２ｍｍｏｌ）に４−オクチルオキシ−４′−ブロモビフェニル２５ｇ（６９．３ｍｍｏｌ）のテトラヒドロフラン１００ｃｃ溶液の１／５量を加え加熱した。反応開始後、残りの溶液を滴下しさらに還流下で２時間撹拌して、グリニヤール試薬を調整した。一方、アルゴン雰囲気下、ホウ酸トリメチル６ｇ（５７．７ｍｍｏｌ）のテトラヒドロフラン２０ｃｃ溶液を０℃に冷却した後、先に調整したグリニヤール試薬を滴下して、徐々に室温に戻し３時間撹拌した。この反応混合物に氷冷した１０％硫酸水溶液を加えて加水分解を行い、ベンゼンで抽出、水洗、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサンで再結晶して４−オクチルオキシビフェニル−４′−ボロン酸１３，７ｇ（６０．６％）を得た。ＨＰＬＣ９５．９％
【００３８】
【化２０】

アルゴン雰囲気下、Ｐｄ〔ＰＰｈ_３）_４〔テトラキス（トリフェニルホスフィン）パラジウム（０）〕０．２ｇ、（ｂ）で得た２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１，２４ｇ（３．５ｍｍｏｌ）のベンゼン２０ｃｃ溶液、（ｃ）で得た４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇ（３．８ｍｍｏｌ）のエタノール２５ｃｃけん濁液及び２Ｍ炭酸ナトリウム水溶液５ｃｃから成る混合物を還流下で６時間撹拌した。反応混合物を水に注加し、ベンゼンで抽出、水洗、硫酸ナトリウムで乾燥後溶液を留去し、残留分をヘキサン−ベンゼン（１５：１〜５：１）を溶出液としたシリカゲルカラムクロマトグラフィーで精製し次いでアセトンで再結晶を行い３−トリフルオロメチル−４，４″−ジオクチルオキシターフェニル０．８５ｇ（４３．６％）を得た。
【００３９】
この物の純度はＨＰＬＣで９８．９％であり、ＴＬＣで１スポットであった。又ＩＲ測定の結果及びＭａｓｓ分析で５５４に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００４０】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００４１】
実施例２
【化２１】

実施例１−（ｃ）において４−オクチルオキシ−４′−ブロモビフェニル２５ｇに替えて４−ヘプチル−４′−ブロモビフェニル２２．９ｇを用い、他は実施例１−（ｃ）と同様に操作し４−ヘプチルビフェニル−４′−ボロン酸１４ｇ（６８．３％）を得た。ＨＰＬＣ９３．８％
【００４２】
【化２２】

実施例１−（ｄ）において４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇに替えて（ａ）で得られた４−ヘプチルビフェニル−４′−ボロン酸１．１４ｇを用い、他は実施例１−（ｄ）と同様に操作し３−トリフルオロメチル−４−オクチルオキシ−４″−ヘプチルターフェニル１．２５ｇ（６７．９％）を得た。
【００４３】
この物の純度はＨＰＬＣで９９．４％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で５２４に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００４４】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００４５】
実施例３
【化２３】

実施例１−（ｂ）においてｎ−オクチルブロマイド４．８ｇに替えてｎ−ヘキシルブロマイド４．１ｇを用い、他は実施例１−（ｂ）と同様に操作して２−トリフルオロメチル−４−ブロモヘキシルオキシベンゼン５．１ｇ（９２．７％）を得た。ｂ．ｐ．１１０℃／１．５ｔｏｒｒ，ＧＣ９４．７％，ＧＣ−Ｍｓ ３２４（Ｍ−１）３２６（Ｍ＋１）
【００４６】
【化２４】

実施例１−（ｃ）において４−オクチルオキシ−４′−ブロモビフェニル２５ｇに替えて４−ペンチルオキシ−４′−ブロモビフェニル２２．１ｇを用い、他は実施例１−（ｃ）と同様に操作し４−ペンチルオキシビフェニル−４′−ボロン酸１０．５ｇ（５３．３％）を得た。ＨＰＬＣ９６．８％
【００４７】
【化２５】

実施例１−（ｄ）において２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇ並びに４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇに替えて、（ａ）で得た２−トリフルオロメチル−４−ブロモヘキシルオキシベンゼン１．１４ｇ並びに（ｂ）で得た４−ペンチルオキシビフェニル−４′−ボロン酸１．０８ｇを用い、他は実施例１−（ｄ）と同様に操作して３−トリフルオロメチル−４−ヘキシルオキシ−４″−ペンチルオキシターフェニル１．０７ｇ（６２．９％）を得た。
【００４８】
この物の純度はＨＰＬＣで９９．４％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で４８４に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００４９】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００５０】
実施例４
【化２６】

実施例１−（ｃ）において４−オクチルオキシ−４′−ブロモビフェニル２５ｇに替えて４−ペンチル−４′−ブロモビフェニル２１ｇを用い、他は実施例１−（ｃ）と同様に操作し４−ペンチルビフェニル−４′−ボロン酸１０．９ｇ５８．６％）を得た。ＨＰＬＣ ９６．４％
【００５１】
【化２７】

実施例１−（ｄ）において２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇ並びに４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇに替えて、実施例３−（ａ）で得た２−トリフルオロメチル−４−ブロモヘキシルオキシベンゼン１．１４ｇ並びに（ａ）で得た４−ペンチルビフェニル−４′−ボロン酸１．０１ｇを用い、他は実施例１−（ｄ）と同様に操作して３−トリフルオロメチル−４−ヘキシルオキシ−４″−ペンチルターフェニル１．０３ｇ（６２．８％）を得た。
【００５２】
この物の純度はＨＰＬＣで９９．８％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で４６８に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００５３】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００５４】
実施例５
【化２８】

実施例１−（ｄ）において４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇに替えて実施例４−（ａ）で得た４−ペンチルビフェニル−４′−ボロン酸１．０１ｇを用い、他は実施例１−（ｄ）と同様に操作し３−トリフルオロメチル−４−オクチルオキシ−４″−ペンチルターフェニル１．１６ｇ（６７．８％）を得た。
【００５９】
この物の純度はＨＰＬＣで９９．８％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で４９６に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００６０】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００６１】
実施例６
【化２９】

実施例１−（ｃ）において４−オクチルオキシ−４′−ブロモビフェニル２５ｇに替えて４−（トランス−４−ペンチルシクロヘキシル）ブロモベンゼン２１．４ｇを用い、他は実施例１−（ｃ）と同様に操作して４−（トランス−４−ペンチルシクロヘキシル）フェニルボロン酸９．５ｇ（５０．１％）を得た。ＨＰＬＣ９９．７％
【００６２】
【化３０】

実施例１−（ｄ）において４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇに替えて（ａ）で得た４−（トランス−４−ペンチルシクロヘキシル）フェニルボロン酸１．０４ｇを用い、他は実施例１−（ｄ）と同様に操作し４−（トランス−４−ペンチルシクロヘキシル）−３′−トリフルオロメチル−４′−オクチルオキシビフェニル０．９３ｇ（５３．１％）を得た。
【００６３】
この物の純度はＨＰＬＣで９９．２％であり、ＴＬＣで１スポットであった。
又、ＩＲ測定の結果及びＭａＳｓ分析で５０２に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００６４】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００６５】
実施例７
【化３１】

実施例１−（ａ）において２−アミノ−５−ブロモベンゾトリフルオリド２０ｇに替えて５−アミノ−２−ブロモベンゾトリフルオリド２０ｇを用い、他は実施例１−（ａ）と同様に操作し３−トリフルオロメチル−４−ブロモフェノール１４．３ｇ（７１．５％）を得た。ｂ．ｐ．１４０℃／３５ｔｏｒｒ，ＧＣ９８．１％，ＧＣ−Ｍｓ ２４０（Ｍ−１）２４２（Ｍ＋１）
【００６６】
【化３２】

実施例１−（ｂ）において２−トリフルオロメチル−４−ブロモフェノール５ｇに替えて（ａ）で得た３−トリフルオロメチル−４−ブロモフェノール５ｇを用い、他は実施例１−（ｂ）と同様に操作し３−トリフルオロメチル−４−ブロモオクチルオキシベンゼン５．８２ｇ（７９．５％）を得た。ｂ．ｐ．１１５℃／０．９ｔｏｒｒ，ＧＣ９６．１％，ＧＣ−Ｍｓ３５２（Ｍ−１）３５４（Ｍ＋１）
【００６７】
【化３３】

実施例１−（ｄ）において２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇに替えて（ｂ）で得た３−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇを用い、他は実施例１−（ｄ）と同様に操作し２−トリフルオロメチル−４，４″−ジオクチルオキシターフェニル１．６３ｇ（８３．６％）を得た。
【００６８】
この物の純度はＨＰＬＣで９９．６％であり、ＴＬＣで１スポットであった。
又、ＩＲ測定の結果及びＭａｓｓ分析で５５４に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した
【００６９】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００７０】
実施例８
【化３４】

実施例１−（ｄ）において２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇ並びに４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇに替えて、実施例７−（ｂ）で得た３−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇ並びに実施例２−（ａ）で得た４−ヘプチルビフェニル−４′−ボロン酸１．１４ｇを用い、他は実施例１−（ｄ）と同様に操作して２−トリフルオロメチル−４−オクチルオキシ−４″−ヘプチルターフェニル０．９２ｇ（５０％）を得た。
【００７１】
この物の純度はＨＰＬＣで９９．９％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で５２４に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００７２】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００７３】
実施例９
【化３５】

実施例１−（ｃ）において４−オクチルオキシ−４′−ブロモビフェニル２５ｇに替えて４−ブロモオクチルオキシベンゼン１９．８ｇを用い、他は実施例１−（ｃ）と同様に操作し４−オクチルオキシフェニルボロン酸８．９ｇ（５１．１％）を得た。ＨＰＬＣ９３．０％
【００７４】
【化３６】

アルゴン雰囲気下、Ｐｄ〔ＰＰｈ_３）_４０．４ｇ、（ａ）で得た４−オクチルオキシフェニルボロン酸２．９７ｇ（１１．９ｍｍｏｌ）のエタノール３０ｃｃ溶液、２，５−ジブロモベンゾトリフルオリド１．６ｇ（５．４ｍｍｏｌ）のベンゼン３０ｃｃ溶液及び２Ｍ炭酸ナトリウム水溶液１５ｃｃから成る混合物を還流下で１２時間撹拌した。反応混合物を水に注加し、ベンゼンで抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサン−ベンゼン（１０：１〜１：１）を溶出液としたシリカゲルカラムクロマトグラフィーで精製し、次いでアセトンで再結晶を行い２′−トリフルオロメチル−４，４″−ジオクチルオキシターフェニル１．６２ｇ（５５．５％）を得た。
【００７５】
この物の純度はＨＰＬＣで９９．９％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で５５４に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００７６】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００７７】
実施例１０
【化３７】

２−アミノ−５−ブロモベンゾトリフルオリド１５ｇ（６２．５ｍｍｏｌ）に濃硫酸７５ｃｃ及び酢酸１００ｃｃを加え、加熱して析出物を溶かした。この溶液を０℃以下に冷却した後、撹拌下亜硝酸ナトリウム５．２８ｇ（７６．５ｍｍｏｌ）の水３０ｃｃ溶液を滴下し、さらに０℃で３０分間放置してジアゾニウム塩溶液を調製した。
【００７８】
このジアゾニウム塩溶液にシクロヘキサン７５ｃｃ及びヨウ化カリウム２１．５ｇ（１２９．５ｍｍｏｌ）の水７５ｃｃ溶液を順次０℃以下にて滴下し、室温で一昼夜撹拌した。
【００７９】
反応混合物を水に注加し、エーテルにて抽出、ピロ亜硫酸ナトリウム水溶液にて洗浄、次いで水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分を減圧下、ＧＴＯにて蒸留し、５−ブロモ−２−ヨウドベンゾトリフルオリド１８．７ｇ（８５．４％）を得た。ｂ．ｐ．１２０〜１２５℃／１９ｔｏｒｒ、ＧＣ ９５．４％、ＧＣ−Ｍｓ ３５０（Ｍ−１），３５２（Ｍ＋１）
【００８０】
【化３８】

アルゴン雰囲気下、１．６Ｍ ｎ−ブチルリチウム／ヘキサン溶液１０．５ｃｃ（１６．８ｍｍｏｌ）を−１０℃で、１−オクチン１．６４ｇ（１４．９ｍｍｏｌ）のテトラヒドロフラン７ｃｃ溶液に滴下し、同温度で２０分間撹拌した。さらに塩化亜鉛２．２８ｇ（１６．８ｍｍｏｌ）とテトラヒドロフラン１５ｃｃから成るけん濁液を加え−１０℃で３０分間撹拌した後に、（ａ）で得た５−ブロモ−２−ヨウドベンゾトリフルオリド５ｇ（１４．２ｍｍｏｌ）のテトラヒドロフラン１５ｃｃ溶液及びＰｄ〔ＰＰｈ_３〕_４０．８２ｇのテトラヒドロフラン１５ｃｃ溶液を順次滴下した。次いで徐々に室温に戻し、一昼夜撹拌した。
【００８１】
反応混合物を希塩酸水溶液に注加し、エーテルにて抽出、水洗、飽和炭酸水素ナトリウム水溶液にて洗浄、再度水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分を減圧下、ＧＴＯにて蒸留し２−トリフルオロメチル−４−ブロモ−（オクト−１−イニル）ベンゼン３ｇ（６３．３％）を得た。ｂ．ｐ．９５〜１００℃／２ｔｏｒｒ、ＧＣ９６．５％、ＧＣ−Ｍｓ３３２（Ｍ−１），３３４（Ｍ＋１）
【００８２】
【化３９】

実施例１−（ｄ）において２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇに替えて（ｂ）で得た２−トリフルオロメチル−４−ブロモ−（オクト−１−イニル）１．１６ｇを用い、他は実施例１−（ｄ）と同様に操作して３−トリフルオロメチル−４−（オクト−１−イニル）−４′−オクチルオキシターフェニル１．５２ｇ（８１．７％）を得た。ＨＰＬＣ９９．１％、Ｍａｓｓ ５３４（Ｍ）、尚、この物の相変化は下記のようであった。
【００８３】

【化４０】

（ｃ）で得た３−トリフルオロメチル−４−（オクト−１−イニル）−４′−オクチルオキシターフェニル０．５１ｇ（０．９６ｍｍｏｌ）、１０％パラジウムカーボン０．０５ｇ及び酢酸エチル２０ｃｃから成る混合物を２時間水素添加した
【００８４】
反応混合物をろ過してパラジウムカーボンを除き、溶媒を留去した後、残留分をアセトン−メタノール混合溶媒で再結晶し、３−トリフルオロメチル−４−オクチル−４′−オクチルオキシターフェニル０．４８ｇ（９４．１％）を得た。
【００８５】
この物の純度はＨＰＬＣで９９．１％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で５３８に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００８６】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００８７】
実施例１１
【化４１】

実施例１−（ｄ）において２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン１．２４ｇ並びに４−オクチルオキシビフェニル−４′−ボロン酸１．２４ｇに替えて、実施例１０−（ｂ）で得た２−トリフルオロメチル−４−ブロモ−（オクト−１−イニル）ベンゼン１．１６ｇ並びに実施例２−（ａ）で得た４−ヘプチルビフェニル−４′−ボロン酸１．１４ｇを用い、他は実施例１−（ｄ）と同様に操作して３−トリフルオロメチル−４−（オクト−１−イニル）−４′−ヘプチルターフェニル０．８７ｇ（４９．４％）を得た。
ＨＰＬＣ ９９．１％、Ｍａｓｓ ５０４（Ｍ）、尚、この物の相変化は下記のようであった。
【００８８】

【化４２】

実施例１０−（ｄ）において３−トリフルオロメチル−４−（オクト−１−イニル）−４′−オクチルオキシターフェニル０．５１ｇに替えて、（ａ）で得た３−トリフルオロメチル−４−（オクト−１−イニル）−４′−ヘプチルターフェニル０．４８ｇを用い、他は実施例１０−（ｄ）と同様に操作して３−トリフルオロメチル−４−オクチル−４′−ヘプチルターフェニル０．３８ｇ（７９．２％）を得た。
【００８９】
この物の純度はＨＰＬＣで９９．０％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で５０８に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察した。その結果を表４に示す。
【００９０】
参考例１
【化４３】

アルゴン雰囲気下、Ｐｄ（ＰＰｈ_３）_４５ｇ、２−ブロモ−ベンゾトリフルオリド１８．７ｇ（８３．１ｍｍｏｌ）のベンゼン２００ｃｃ溶液及び実施例６−（ａ）で得られる４−（トランス−４−ペンチルシクロヘキシル）フェニルボロン酸２５ｇ（９１．２ｍｍｏｌ）のエタノール２００ｃｃ溶液及び２Ｍ炭酸ナトリウム水溶液９０ｃｃから成る混合物を還流下で２４時間撹拌した。
【００９１】
反応混合物を水に注加し、ベンゼンにて抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサンを溶出液としたシリカゲルカラムクロマトグラフィーで精製し、次いでアセトンで再結晶を行い４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチルビフェニル２７．４ｇ（８８．１％）を得た。ＧＣ９８．９％、Ｍａｓｓ３７４（Ｍ）
【００９２】
【化４４】

氷冷下、臭素９．１ｇ（５６．９ｍｍｏｌ）の塩化メチレン５ｃｃ溶液を（ａ）で得た４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチルビフェニル１９ｇ（５０．８ｍｍｏｌ）硝酸タリウム（ＩＩ）３水和物２．０ｇ及び塩化メチレン１００ｃｃから成る混合物に滴下し、３時間撹拌した。
【００９３】
反応混合物を希水酸化ナトリウム水溶液に注加し、塩化メチレンにて抽出、水洗を行い硫酸ナトリウムで乾燥後溶媒を留去し、残留分をアセトン−メタノール混合溶媒で再結晶し４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ブロモビフェニル１８．１ｇ（７８．７％）を得た。ＧＣ９８．７％、Ｍａｓｓ ４５２（Ｍ−１），４５４（Ｍ＋１）
【００９４】
【化４５】

アルゴン雰囲気下、１．６Ｍｎ−ブチルリチウム／ヘキサン溶液４．６ｃｃ（７．３ｍｍｏｌ）を−７０℃で、（ｂ）で得た４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ブロモビフェニル３ｇ（６．６ｍｍｏｌ）のテトラヒドロフラン２０ｃｃ溶液に滴下し同温度で１時間撹拌した。この反応混合物にボロン酸トリメチル１ｃｃを加え、徐々に０℃まで上げて３０分間撹拌した。再度−１０℃以下に冷却し、３０％過酸化水素水５ｃｃを滴下した後徐々に室温に戻し１時間撹拌した。次いでこの反応混合物を−３０℃に冷却し、飽和亜硫酸水素ナトリウム水溶液１０ｃｃを加え、徐々に室温に戻しながら一昼夜撹拌した。
【００９５】
反応混合物を水に注加し、ベンゼンにて抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサン−ベンゼン（２：１〜１：１）を溶出液としたシリカゲルカラムクロマトグラフィーで精製し４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ヒドロキシビフェニル２．４２ｇ（９３．８％）を得た。
ＧＣ９６．６％、ＩＲ（ｎｅａｔ）：３４００ｃｍ^−１（ＯＨ）
【００９６】
【化４６】

氷冷下（ｃ）で得た４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ヒドロキシビフェニル１．０７ｇ（２．７４ｍｍｏ１）のジメチルホルムアミド２０ｃｃ溶液に６０％水素化ナトリウム０．２５ｇを加え、発泡が収まるまで撹拌した。さらにｎ−プロピルブロマイド０．６１ｇ（４．９６ｍｍｏｌ）を加え、室温で２日間撹拌した。
【００９７】
反応混合物を希塩酸水溶液に注加し、ベンゼンにて抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサン−ベンゼン（４：１）を溶出液としたシリカゲルカラムクロマトグラフィーにて精製し、次いでアセトン−メタノール混合溶媒で再結晶を行い４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−プロピルオキシビフェニル０．９５ｇ（７９．８％）を得た。
【００９８】
この物の純度はＨＰＬＣで９９．１％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で４３２に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【００９９】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察したその結果を表４に示す。
【０１００】
実施例１２
【化４７】

参考例１−（ｄ）においてｎ−プロピルブロマイド０．６１ｇ．に替えてｎ−オクチルブロマイド０．９６ｇを用い、他は参考例１−（ｄ）と同様に操作し４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−オクチルオキシビフェニル０．８３ｇ（６０．１％）を得た。
【０１０１】
この物の純度はＨＰＬＣで９７．０％であり、ＴＬＣで１スポットであった。
又、ＩＲ測定の結果及びＭａｓｓ分析で５０２に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【０１０２】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察したその結果を表４に示す。
【０１０３】
参考例２
【化４８】

アルゴン雰囲気下、１．６Ｍｎ−ブチルリチウム／ヘキサン溶液４．６ｃｃ（７．３ｍｍｏｌ）を−７０℃で、参考例１−（ｂ）で得た４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ブロモビフェニル３ｇ（６．６ｍｍｏｌ）のテトラヒドロフラン２０ｃｃ溶液に滴下し、同温度で２時間撹拌した。さらにＮ−ホルミルピペリジン０．９５ｇ（８．４ｍｍｏｌ）を滴下し、徐々に室温まで戻し一昼夜撹拌した。
【０１０４】
反応混合物を希塩酸水溶液に注加し、ベンゼンにて抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し粗４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ホルミルビフェニル２．６９ｇを得た。ＧＣ９３．９％、ＩＲ（ｎｅａｔ）：１７００ｃｍ^−１（ＣＨＯ）
【０１０５】
【化４９】

氷冷下、水素化ホウ素ナトリウム０．５ｇ（１３．２ｍｍｏｌ）を（ａ）で得た粗４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ホルミルビフェニル２．６ｇ（６．５ｍｍｏｌ）のテトラヒドロフラン１０ｃｃ及びエタノール１０ｃｃから成る溶液に加え、３時間還流撹拌した。
【０１０６】
反応混合物を希塩酸水溶液に注加し、ベンゼンにて抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサン−ベンゼン（１：０〜１：１）を溶出液としたシリカゲルカラムクロマトグラフィーにて精製し４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ヒドロキシメチルビフェニル２．２８ｇ（８７．４％）を得た。ＧＣ ９９．４％、ＩＲ（ｎｅａｔ）：３３５０ｃｍ^−１（ＯＨ）
【０１０７】
【化５０】

（ｂ）で得た４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ヒドロキシメチルビフェニル１．１５ｇ（２．８ｍｍｏｌ）のテトラヒドロフラン１５ｃｃ溶液にメチルアイオダイド１．３５ｇ（９．５ｍｍｏｌ）、水酸化カリウム０．４５ｇ（８．０ｍｍｏｌ）及び１８−クラウン−６０．１ｇ（０．３８ｍｍｏｌ）を順次加え、室温で２日間撹拌した。
【０１０８】
反応混合物を水に注加し、ベンゼンにて抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサン−ベンゼン（２：１）を溶出液としたシリカゲルカラムクロマトグラフィーにて精製し、次いでアセトン−メタノール混合溶媒で再結晶を行い４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−メトキシメチルビフェニル０．９１ｇ（７６．５％）を得た。
【０１０９】
この物の純度はＨＰＬＣで９９．４％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で４１８に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【０１１０】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察したその結果を表４に示す。
【０１１１】
実施例１３
【化５１】

参考例２−（ｃ）においてメチルアイオダイド１．３５ｇに替えてｎ−ヘキシルアイオダイド２．０ｇを用い、他は参考例２−（ｃ）と同様に操作し４−（トランス−４−ペンチルシクロヘキシル）−２′−トリフルオロメチル−４′−ヘキシルオキシメチルビフェニル１．０９ｇ（７８．４％）を得た。
【０１１２】
この物の純度はＨＰＬＣで９７．２％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で４８８に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【０１１３】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察したその結果を表４に示す。
【０１１４】
実施例１４
【化５２】

実施例１−（ｄ）において４−オクチルオキシビフェニルー４′−ボロン酸１．２４ｇに替えて実施例９−（ａ）で得られた４−オクチルオキシフェニルボロン酸０．９５ｇを用い、他は実施例１−（ｄ）と同様に操作し３−トリフルオロメチル−４，４′−ジオクチルオキシビフェニル１．３７ｇ（８３．０％）を得た。
【０１１５】
この物の純度はＨＰＬＣで９９．３％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で４７８に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【０１１６】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察したその結果を表４に示す。
【０１１７】
実施例１５
【化５３】

アルゴン雰囲気下、１．６Ｍ ｎ−ブチルリチウム／ヘキサン溶液９．８ｃｃ（１５．６ｍｍｏｌ）を−７０℃で、実施例１−（ｂ）で得られる２−トリフルオロメチル−４−ブロモオクチルオキシベンゼン４ｇ（１１．３ｍｍｏｌ）のテトラヒドロフラン２５ｃｃ溶液に滴下した。同温度で１時間撹拌した後に、ｎ−ペンチルシクロヘキシルシクロヘキサノン３．５５ｇ（１４．２ｍｍｏｌ）のテトラヒドロフラン１０ｃｃ溶液を滴下し、この反応混合物を室温まで徐々に戻した。
【０１１８】
反応混合物を希塩酸水溶液に注加し、トルエン抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分にトルエン２５０ｃｃ及びｐ−トルエンスルホン酸０．５ｇを加え、検水管を用いて２時間還流撹拌した。
【０１１９】
この反応混合物を水に注加し、トルエン抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分を減圧下、ＧＴＯにて蒸留し３−トリフルオロメチル−４−オクチルオキシ−〔４−（トランス−４−ペンチルシクロヘキシル）−１−シクロヘキセン−１−イル〕ベンゼン３．８６ｇ（６７．４％）を得た。ｂ．ｐ．２３５℃／０．１５ｔｏｒｒ）ＨＰＬＣ ９５．３％
【０１２０】
【化５４】

（ａ）で得た３−トリフルオロメチル−４−オクチルオキシ−〔４−（トランス−４−ペンチルシクロヘキシル）−１−シクロヘキセン−１−イル〕ベンゼン３．８６ｇ（７．６ｍｍｏｌ）、１０％パラジウムカーボン０．１ｇ及び酢酸エチル５０ｃｃの混合物を１２時間水素添加した。
【０１２１】
反応混合物をろ過してパラジウムカーボンを除き、溶媒を留去した。アルゴン雰囲気下残留分をジメチルスルホキシド２０ｃｃに溶解し、カリウム−ｔｅｒｔ−ブトキシド１ｇ（８．９ｍｍｏｌ）を加え、８０〜８５℃で３０時間撹拌した。
【０１２２】
この反応混合物を希塩酸水溶液に注加し、ベンゼンにて抽出、水洗を行い、硫酸ナトリウムで乾燥後溶媒を留去し、残留分をヘキサンを溶出液としたシリカゲルカラムクロマトグラフィーにて精製し、次いでアセトン−メタノール混合溶媒で再結晶を行い２−トリフルオロメチル−４−オクチルオキシ−４−〔トランス−４−（トランス−４−ペンチルシクロヘキシル）シクロヘキシル〕ベンゼン１．７１ｇ（４４．３％）を得た。
【０１２３】
この物の純度はＨＰＬＣ９９．３％であり、ＴＬＣで１スポットであった。又、ＩＲ測定の結果及びＭａｓｓ分析で５０８に分子イオンピークが認められたこと並びに用いた原料の関係から得られた物質が標記化合物であることを確認した。
【０１２４】
この物をメトラーホットステージＦＰ−８２を用い、偏光顕微鏡下で相変化を観察したその結果を表４に示す。
【０１２５】
実施例１６
【化５５】

上記４種類のフェニルピリミジン化合物から成る母体液晶組成物（Ｂ−１）を調製した。
【０１２６】
母体液晶組成物（Ｂ−１）８０ｗｔ％と実施例１−（ｄ）で得られた３−トリフルオロメチル−４，４″−ジオクチルオキシターフェニル１０ｗｔ％、並びに下記の公知光学活性化合物（Ｄ−１）
【化５６】

を１０ｗｔ％添加し、カイラルＳｃ組成物（Ｍ−１）を作成した。
【０１２７】
同時に、前記実施例１−（ｄ）の化合物を含まない、母体液晶組成物（Ｂ−１）９０ｗｔ％と公知の光学活性化合物（Ｄ−１）１０ｗｔ％とからなるカイラルＳｃ組成物（Ｍ−２）を作成した。
これらの組成物の相転移温度を下記に示す。
【０１２８】

これらの組成物（Ｍ−１）及び組成物（Ｍ−２）を各々市販の液晶セル（ＥＨＣ社製、ポリイミド配向膜、２μｍギャップ）に注入して液晶素子を作成した。
【０１２９】
各々の液晶素子を２枚の偏光板に挟み、±５Ｖ／μｍ、２００Ｈｚの矩形波を印加して透過光強度の変化から応答時間を求めた。又ソーヤー・タワー法にて自発分極を測定し、印加電圧の極性反転時の消光位の移動角度よりチルト角を測定した。
その結果を表１に示す。なお測定温度は２５℃である。
【０１３０】
【表１】

【０１３１】
以上に示したように、本発明化合物は、これを添加することにより、無添加の場合と比べて応答時間の短縮、チルト角の拡大、又カイラルＳｃ上限温度の上昇に有効であり、強誘電性液晶組成物作成の際に、目的とする性質の向上を計るために使用できる有用な化合物である。
【０１３２】
実施例１７
前記実施例１６で調製した母体液晶組成物（Ｂ−１）８７ｗｔ％と実施例１１−（ｂ）で得られた３−トリフルオロメチル−４−オクチルー４″−ヘプチルターフェニル１０ｗｔ％、並びに下記の公知光学活性化合物（Ｄ−２特開平５−２１３９３０）を３ｗｔ％添加し、カイラルＳｃ組成物（Ｍ−３）を作成した。
【０１３３】
【化５７】

【０１３４】
同時に、前記実施例１１−（ｂ）の化合物を含まない、母体液晶組成物（Ｂ−１）９７ｗｔ％と公知の光学活性化合物（Ｄ−２）３ｗｔ％とからなるカイラルＳｃ組成物（Ｍ−４）を作成した。
これらの組成物の相転移温度を下記に示す。
【０１３５】

これらの組成物（Ｍ−３）及び組成物（Ｍ−４）を各々市販の液晶セル（ＥＨＣ社製、ポリイミド配向膜、２μｍギャップ）に注入して液晶素子を作成し、実施例１６と同様に応答時間、自発分極並びにチルト角を測定した。その結果を表２に示す。
【０１３６】
【表２】

【０１３７】
以上に示したように、本発明化合物は、これを添加することにより、無添加の場合と比べて応答時間の短縮及びカイラルＳｃ下限温度を下げるのに有効であり、強誘電性液晶組成物を作成する際に、目的とする性質を向上させるために使用できる有用な化合物である。
【０１３８】
実施例１８
実施例１７において、実施例１１−（ｂ）の化合物に替えて実施例１５−（ｂ）の化合物を用い、実施例１７と同様にカイラルＳｃ組成物（Ｍ−５）を作成し、実施例１１−（ｂ）の化合物を含まない組成物（Ｍ−４）と比較した。その相転移温度を下記に、又、応答時間、自発分極並びにチルト角の測定結果を表３に示す。
【０１３９】

【０１４０】
【表３】

【０１４１】
以上に示したように、本発明化合物は、これを添加することにより、無添加の場合と比べてカイラルＳｃ相温度幅を狭めずにカイラルＳｃ下限温度を下げ、又応答時間の短縮に有効であり、強誘電性液晶組成物を作成する際に、目的とする性質を付与するのに使用できる有用な化合物である。
【０１４２】
実施例１９
実施例１１−（ｂ）で得られた化合物と実施例４−（ｂ）で得られた化合物は下記の相転移温度（℃）を有する化合物である。

上記の実施例１１−（ｂ）と実施例４−（ｂ）の各化合物を３０ｗｔ％と７０ｗｔ％の割合で混合し、Ｓｃ組成物（Ｂ−２）を作成して、その相転移温度（℃）を測定した。その結果を下記に示す。
【０１４３】

以上に示すように、実施例４−（ｂ）化合物のＳｃ相温度幅は１２．３度であるが、これにＳｃ相を持たない実施例１１−（ｂ）化合物を添加することにより、Ｓｃ相温度幅は２０度となり、７．７度拡張された。更に、混合したことにより、それぞれが単品では有していない、実用的に理想とされる相系列、すなわち降温時にＩ→Ｎｅ→Ｓ_Ａ→Ｓｃの相系列を示す組成物が得られた。このようにＳｃ相を持たない化合物も組成物を作成する上で有用である。
【０１４４】
実施例２０
市販のネマチック液晶組成物であるＺＬＩ−１１３２に、液晶相を持たない参考例２−（ｃ）化合物（ｍ．ｐ５８．７℃）を１０ｗｔ％添加（ネマチック組成物Ｍ−６）し、ネマチック相から等方性液体への転移温度（Ｔ_ＮＩ）、屈折率異方性（Δｎ）、並びに、しきい値電圧（Ｖ_ｔｈ）を測定した。又、ＺＬＩ−１１３２自身のそれらについても測定した。その結果を下記に示す。
【０１４５】

【０１４６】
以上に示すように、参考例２−（ｃ）化合物はＴ_ＮＩ下げるものの、Δｎ及びＶ_ｔｈを大幅に低下させる効果があり、ネマチック液晶組成物作成の際、その目的とする特性を調整する材料として有用である。
【０１４７】
【表４】

[0001]
【Technical field】
The present invention relates to a novel liquid crystal compound and a liquid crystal composition containing at least one of these liquid crystal compounds. More specifically, the present invention relates to a ferroelectric liquid crystal composition and a nematic liquid crystal composition, and a liquid crystal compound having a novel trifluoromethylbenzene skeleton which is useful as a composition component thereof and has excellent chemical stability, and a liquid crystal compound thereof. The present invention relates to a liquid crystal composition containing at least one liquid crystal compound having a novel trifluoromethylbenzene skeleton.
[0002]
[Background Art]
Liquid crystal display devices are widely used as display devices for watches, calculators, personal word processors, pocket televisions, and the like. This is because the light-receiving type has excellent characteristics such as not causing eyestrain, low power consumption, and thinness.However, the nematic liquid crystal composition has a low response speed and lacks memory properties. There were limitations in application. In order to expand the application, a super twisted nematic (STN) type display system, which is an improvement of a conventionally used twisted nematic (TN) type display system, has also been found. Further, they are approaching a CRT by being driven using a transistor or a diode such as a TFT or MIM. However, since the response speed is still slow as compared with the CRT and the viewing angle is not sufficient, research on liquid crystal display elements has been actively conducted, and one of them is a ferroelectric liquid crystal [R. B. Meyer et al., Physique, 36 L-69 (1975)]. A. Clark et al .; Applied Phys. lett. , 36, 899 (1980)]. This method has excellent characteristics such as a high-speed response of 100 to 1,000 times as compared with the conventional method and a memory property, so that the use of liquid crystal display devices is expected to be expanded. . Ferroelectric liquid crystal refers to a series of smectic liquid crystals in which the long axis of the liquid crystal molecules has a certain angle with respect to the layer normal direction, but a chiral SmC phase is practically used.
[0003]
A ferroelectric liquid crystal for producing a display element is a liquid crystal composition obtained by mixing (1) compounds having various chiral SmC phases or (2) a compound having various SmC phases and an optically active compound. There are two methods. In the research and development of ferroelectric liquid crystal display devices, the liquid crystal composition obtained by the method (1) was initially used. However, research and development have progressed, and the addition of an optically active compound to a compound having an SmC phase has led to strong research and development. Since it has been found that a dielectric liquid crystal can be obtained, there is a tendency to use the composition obtained by the method (2). In particular, the SmC composition (SmC host) obtained by mixing the SmC compound has one to several kinds of optically active compounds (a compound having a chiral SmC phase is preferable, but a compound which does not necessarily have to have the chiral SmC phase). Research and development of ferroelectric liquid crystal compositions by adding a chiral dopant) have become mainstream.
[0004]
This is because (2) is easier to adjust various characteristics (operating temperature range, response speed, spontaneous polarization, spiral pitch, chemical stability, etc.) required for the display element, or compared to the chiral SmC compound. This is because (2) is considered to be advantageous because the SmC compound can be synthesized at low cost.
[0005]
The response time of a ferroelectric liquid crystal is expressed by the formula τ = η / E · Ps (τ = response time η = viscosity, E = electric field, Ps = spontaneous polarization). can do. However, in practice, in addition to the response time, it is necessary to optimize various characteristics such as the operating temperature range, the viewing angle, and the contrast. Therefore, a large number of compounds are mixed and each compound has Attempts have been made to optimize by taking advantage of the features that are available. Most of the ferroelectric liquid crystal composition in the method (2) is an SmC host component, and the SmC host component has a large effect on the characteristics of the ferroelectric liquid crystal composition.
[0006]
Therefore, in order to optimize a ferroelectric liquid crystal composition for a display element, an excellent SmC host is required. For example, a wide SmC temperature range, low viscosity, and a tilt angle of 22. 5 ° and the layer structure is a bookshelf or chevron type. However, it has not yet been put to practical use, and there is a demand for the development of various compounds that can be useful components when preparing a ferroelectric liquid crystal composition.
[0007]
The present inventors have focused on the liquid crystal compound necessary for preparing an SmC host from the above viewpoint, and aimed to obtain an effective liquid crystal compound when preparing a ferroelectric liquid crystal composition. The usefulness as a material for improving various physical properties when preparing a nematic liquid crystal composition was also examined.
[0008]
By introducing a trifluoromethyl group with a strong electron-withdrawing property on the side of the molecular long axis, a compound whose permittivity in the direction perpendicular to the molecular long axis is designed and synthesized.
[0009]
As a result, a ferroelectric liquid crystal display (JM Geary, SID'85, Digest (1985) that can increase the tilt angle, shorten the response time, and achieve a high viewing angle and a high contrast display by a high frequency superposition method. ) 128, as a material for Y. Sato, et al, SID '86, Digest (1986) 348) and at the time of preparing a nematic liquid crystal composition,_th), A novel trifluoromethylbenzene derivative useful as a material for adjusting the refractive index anisotropy (Δn) was successfully synthesized.
[0010]
DISCLOSURE OF THE INVENTION
The present invention provides a compound represented by the general formula (I):
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(WhereR ¹ IsRepresents an alkyl group having 1 to 14 carbon atoms, an alkoxy group or an alkoxyalkyl group,R ² Represents an alkyl group having 5 to 14 carbon atoms, an alkoxy group or an alkoxyalkyl group,
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And m and n each independently represent 0 or 1.
[0011]
However, m and n are not 0 at the same time, and when m and n are 1 at the same time, neither A nor B
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A) a trifluoromethylbenzene derivative represented by the formula: and a liquid crystal composition comprising at least one of the derivatives.
[0012]
The novel compounds according to the present invention include those having an SmC phase alone and those having no SmC phase, but each of them can be used for preparing a ferroelectric liquid crystal composition or a nematic liquid crystal composition. It is an effective compound.
[0013]
Examples of the methods for synthesizing these compounds will be briefly described as synthesis routes 1 to 5, and further details will be described with reference to examples of the present invention. The following synthetic routes are merely examples, and do not specify the present invention. Table 4 shows the measurement results of the phase transition temperatures of the compounds synthesized in the examples. It is to be understood that these results are affected by differences in measuring instruments and measuring methods, or by purity, and that there are some differences in the numerical values.
[0014]
(Synthetic route)
In the following synthetic routes, R represents an alkyl group having 1 to 14 carbon atoms, J, k, p, and q each represent an integer of 1 to 13, and other symbols are represented by claims. Have a definition.
[0015]
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[0016]
Route 1 (Precursor synthesis route-1)
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[0017]
Route 2 (Precursor synthesis route-2)
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[0018]
Route 3 (Synthesis route of the title compound-1)
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[0019]
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Route 4 (Precursor synthesis route-3)
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[0020]
Route 5 (Synthesis route of the title compound-2)
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[0021]
Hereinafter, the synthesis route will be schematically described.
For Route 1:
The compounds represented by the general formulas (1) to (5) are commercially available, and the compounds represented by the general formulas (6) to (9) are (6-1), (7-1), and (9- 1) can be obtained as a starting material.
[0022]
If the compound (6-1) obtained by etherifying the compound (6-1) with RONa (sodium alkoxide) is brominated with bromine, the compound represented by the general formula (6) is obtained.
[0023]
Compound (7-1) is cyanated with potassium cyanide, and then the compound (7-3) obtained by acid hydrolysis is converted to LiAlH₄To give a compound (7-4). This is brominated with hydrobromic acid to obtain compound (7-5). Using the compound (7-5) in place of the above (7-1), cyanation, hydrolysis, reduction, and bromination, and a series of reactions repeatedly and arbitrarily performed using the obtained bromide to form a compound represented by the general formula ( The compound represented by 7-6) is obtained.
[0024]
If the compound represented by the general formula (7-6) is etherified with RONa (sodium alkoxide), the compound represented by the general formula (7) is obtained. The compound of the general formula (8) can be synthesized by a coupling reaction between p-bromoiodobenzene and a boronic acid compound derived from the compound represented by the general formula (7).
[0025]
Compound (9-1) was converted to LiAlH₄The compound (9-2) obtained by reduction with the above is brominated with hydrobromic acid to give the compound (9-3). Using the compound (9-3), the compound represented by the general formula (9-8) is obtained in the same manner as in the method for obtaining the compound (7-6) from the compound (7-1). The compound represented by the general formula (9-8) is obtained by brominating the compound represented by the general formula (9-8) with bromine and then etherifying the compound with RONa (sodium alkoxide).
[0026]
The compounds represented by the general formulas (1) to (5) and the compounds represented by the general formulas (6) to (9) obtained by the above method are respectively reacted with Mg to prepare a Grignard reagent. Trimethyl borate [B (OCH₃)₃And then hydrolysis to give a compound represented by the general formula (P-1) or (P-2).
[0027]
For Route 2:
A commercially available compound (10-1) is reacted with sodium nitrite to prepare a diazonium salt, which is thermally decomposed with sulfuric acid, and the compound (10-2) is reacted with copper iodide (Cul) to form a compound ( 11-1) further converts compound (11-1) to copper cyanide [Cu (CN)₂To give each of the compounds (14-1).
[0028]
The compound represented by the general formula (10) can be synthesized by a conventional etherification reaction of the compound (10-2) with an alkyl bromide (RBr). The compounds represented by the general formulas (11) and (13) are obtained by performing a coupling reaction between the compound (11-1) and the boronic acid of the compounds (3) and (1) described in the route 1, respectively.
[0029]
Using the compound (14-1) obtained by the above-mentioned method, the compound of the general formula (7) and the compound represented by the general formula (7) and (8) are obtained from the compound (7-1) in the route 1 by the same method. The compounds represented by 14) and (15) are obtained. Further, the compound represented by the general formula (12) can be obtained by tosylating the compound (14-3) in this route with tosyl chloride and reacting it with alkylmagnesium bromide (RMgBr).
Thus, the compound represented by the general formula (P-3) or (P-4) is obtained.
[0030]
For Route 3:
The compound represented by the general formula (P-1) obtained by the route 1 and the route 2 and the compound represented by the general formula (P-4) or the compound represented by the general formula (P-2) and the general formula ( The compound represented by P-3) is converted to tetrakistriphenylphosphine palladium [Pd (PPh₃)₄By performing the coupling reaction in the presence of the compound, the compound of the present invention represented by the general formula (I) can be obtained.
[0031]
For Route 4:
Compounds represented by the general formula (16-1) were converted to potassium hydrogen sulfate (KHSO₄The compound represented by the general formula (16) can be obtained by an oxidation reaction using an oxidizing agent such as
[0032]
By oxidizing a boronic acid derivative obtained from the compound represented by the general formula (6) using hydrogen peroxide in the route 1, the compound represented by the general formula (17-1) is obtained. This is subjected to nucleus hydrogenation under a palladium carbon (Pd / C) catalyst to obtain a compound represented by the general formula (17-2), which is converted to potassium hydrogen sulfate (KHSO).₄The compound represented by the general formula (17) can be obtained by performing an oxidation reaction using an oxidizing agent such as
[0033]
For Route 5:
A compound represented by the general formula (P-3) or (P-4) obtained in Route 2 is reacted with magnesium to prepare a Grignard reagent, and a Grignard reagent obtained therefrom is reacted with the general formula (P-6) or When a cyclohexene derivative obtained by performing a coupling reaction with the compound represented by (P-5) is hydrogenated in the presence of Pd / C, the compound represented by the general formula (I), which is the compound of the present invention, is obtained. Can be obtained.
[0034]
Hereinafter, the present invention will be described in more detail with reference to Examples, but the abbreviations described herein have the following meanings.
GTO: Glass tube oven
GC: Gas chromatography
HPLC: High Performance Liquid Chromatography
IR: infrared absorption spectrum
Mass: mass spectrum
GC-Ms: Gas chromatography-mass spectrum
b. p. : Boiling point
C: Crystal
S_x: Sc, S_ASmectic phase other than
SmC, Sc: smectic C phase
S_A: Smectic A phase
Ch: Cholesteric phase
Ne: Nematic phase
I: Isotropic liquid
? : Temperature unknown
[0035]
【Example】
Example 1
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A solution of 24 cc of concentrated sulfuric acid in 60 cc of water was added to 20 g (83.3 mmol) of 2-amino-5-bromobenzotrifluoride to produce a precipitate. An additional 60 cc of acetic acid was added to dissolve the precipitate. After the solution was cooled to 5 ° C. or lower, a solution of 6.68 g (96.8 mmol) of sodium nitrite in 20 cc of water was added dropwise, and ice chips, 0.5 g of urea and 120 cc of acetic acid were added, and the mixture was left at 5 ° C. or lower. The diazonium salt solution was left. On the other hand, a suspension composed of 31.2 g of sodium sulfate, 24 cc of concentrated sulfuric acid and 20 cc of water was heated to 130 to 135 ° C., and the diazonium salt solution prepared above was gradually dropped to form a phenol compound together with steam. Distilled. The distillate was extracted with ether, washed with saturated saline, dried over sodium sulfate, and the solvent was distilled off. The residue was distilled under reduced pressure using GTO to obtain 15.3 g of 2-trifluoromethyl-4-bromophenol. (76.5%). b. p. 105 ° C./30 torr, GC 92.2%, GC-Ms 240 (M−1), 242 (M + 1)
[0036]
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From 5 g (20.7 mmol) of 2-trifluoromethyl-4-bromophenol obtained in (a), 4.8 g (24.8 mmol) of n-octyl bromide, 8.6 g (62.1 mmol) of potassium carbonate and 50 cc of methyl ethyl ketone The resulting mixture was stirred at reflux for 10 hours. The reaction mixture was filtered to remove insolubles by suction filtration, the filtrate was concentrated, extracted with benzene, washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue was distilled under reduced pressure using GTO to give 2- 5.9 g (80.8%) of trifluoromethyl-4-bromooctyloxybenzene were obtained. b. p. 125 ° C./1.5 torr, GC 94.4%, GC-Ms 352 (M-1), 354 (M + 1)
[0037]
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Under an argon atmosphere, 1/5 of a solution of 25 g (69.3 mmol) of 4-octyloxy-4'-bromobiphenyl in 100 cc of tetrahydrofuran was added to 1.85 g (76.2 mmol) of magnesium activated by iodine, and the mixture was heated. After the start of the reaction, the remaining solution was added dropwise, and the mixture was further stirred under reflux for 2 hours to prepare a Grignard reagent. On the other hand, under an argon atmosphere, a solution of 6 g (57.7 mmol) of trimethyl borate in 20 cc of tetrahydrofuran was cooled to 0 ° C., and the Grignard reagent prepared above was added dropwise, and the mixture was gradually returned to room temperature and stirred for 3 hours. The reaction mixture was hydrolyzed by adding an ice-cooled 10% aqueous sulfuric acid solution, extracted with benzene, washed with water, dried over sodium sulfate, evaporated, and the residue was recrystallized from hexane to give 4-octyloxybiphenyl. 13.7 g (60.6%) of -4'-boronic acid were obtained. HPLC 95.9%
[0038]
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Under an argon atmosphere, Pd [PPh₃)₄[Tetrakis (triphenylphosphine) palladium (0)] 0.2 g, 2-trifluoromethyl-4-bromooctyloxybenzene obtained in (b), 24 g (3.5 mmol) in 20 cc benzene solution, (c) A mixture of 1.24 g (3.8 mmol) of 4-octyloxybiphenyl-4'-boronic acid obtained in the above and a suspension of 25 cc of ethanol and 5 cc of a 2 M aqueous sodium carbonate solution was stirred under reflux for 6 hours. The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, and the solution was distilled off. The residue was subjected to silica gel column chromatography using hexane-benzene (15: 1 to 5: 1) as an eluent. And then recrystallized from acetone to obtain 0.85 g (43.6%) of 3-trifluoromethyl-4,4 "-dioctyloxyterphenyl.
[0039]
The purity of this product was 98.9% by HPLC and one spot by TLC. It was also confirmed by IR measurement and Mass analysis that a molecular ion peak was observed at 554, and that the substance obtained was the title compound from the relationship between the raw materials used.
[0040]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0041]
Example 2
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In the same manner as in Example 1- (c), except that 22.9 g of 4-heptyl-4'-bromobiphenyl was used instead of 25 g of 4-octyloxy-4'-bromobiphenyl in Example 1- (c). Thus, 14 g (68.3%) of 4-heptylbiphenyl-4'-boronic acid was obtained. HPLC 93.8%
[0042]
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In Example 1- (d), 1.14 g of 4-heptylbiphenyl-4'-boronic acid obtained in (a) was used instead of 1.24 g of 4-octyloxybiphenyl-4'-boronic acid. By operating in the same manner as in Example 1- (d), 1.25 g (67.9%) of 3-trifluoromethyl-4-octyloxy-4 ″ -heptylterphenyl was obtained.
[0043]
The purity of this product was 99.4% by HPLC and one spot by TLC. It was also confirmed by IR measurement and Mass analysis that a molecular ion peak was observed at 524, and that the substance obtained was the title compound from the relationship between the raw materials used.
[0044]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0045]
Example 3
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In Example 1- (b), 4.1 g of n-hexyl bromide was used instead of 4.8 g of n-octyl bromide, and the others were operated in the same manner as in Example 1- (b) to obtain 2-trifluoromethyl-4. 5.1 g (92.7%) of -bromohexyloxybenzene were obtained. b. p. 110 ° C./1.5 torr, GC 94.7%, GC-Ms 324 (M−1) 326 (M + 1)
[0046]
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In Example 1- (c), 2-pentyloxy-4'-bromobiphenyl was replaced with 22.1 g of 4-octyloxy-4'-bromobiphenyl in place of 25 g, and the other conditions were the same as in Example 1- (c). By operation, 10.5 g (53.3%) of 4-pentyloxybiphenyl-4'-boronic acid was obtained. HPLC 96.8%
[0047]
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In Example 1- (d), instead of 1.24 g of 2-trifluoromethyl-4-bromooctyloxybenzene and 1.24 g of 4-octyloxybiphenyl-4'-boronic acid, 2- Using 1.14 g of trifluoromethyl-4-bromohexyloxybenzene and 1.08 g of 4-pentyloxybiphenyl-4'-boronic acid obtained in (b), operating in the same manner as in Example 1- (d), except that As a result, 1.07 g (62.9%) of 3-trifluoromethyl-4-hexyloxy-4 ″ -pentyloxyterphenyl was obtained.
[0048]
The purity of this product was 99.4% by HPLC and one spot by TLC. In addition, it was confirmed from the results of IR measurement and mass analysis that a molecular ion peak was observed at 484, and that the substance obtained was the title compound from the relationship between the raw materials used.
[0049]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0050]
Example 4
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The procedure of Example 1- (c) was repeated except that 25 g of 4-octyloxy-4'-bromobiphenyl was replaced by 21 g of 4-pentyl-4'-bromobiphenyl. -Pentylbiphenyl-4'-boronic acid (10.9 g, 58.6%). HPLC 96.4%
[0051]
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In Example 3- (a), instead of 1.24 g of 2-trifluoromethyl-4-bromooctyloxybenzene and 1.24 g of 4-octyloxybiphenyl-4'-boronic acid in Example 1- (d), Using 1.14 g of the obtained 2-trifluoromethyl-4-bromohexyloxybenzene and 1.01 g of 4-pentylbiphenyl-4'-boronic acid obtained in (a), the others were the same as in Example 1- (d). The same operation was performed to obtain 1.03 g (62.8%) of 3-trifluoromethyl-4-hexyloxy-4 ″ -pentyl terphenyl.
[0052]
The purity of this product was 99.8% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound based on the result of IR measurement and the fact that a molecular ion peak was observed at 468 by Mass analysis, and the relationship between the raw materials used.
[0053]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0054]
Example 5
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Using 1.01 g of 4-pentylbiphenyl-4'-boronic acid obtained in Example 4- (a) instead of 1.24 g of 4-octyloxybiphenyl-4'-boronic acid in Example 1- (d). Otherwise by operating in the same manner as in Example 1- (d), 1.16 g (67.8%) of 3-trifluoromethyl-4-octyloxy-4 ″ -pentylterphenyl was obtained.
[0059]
The purity of this product was 99.8% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound based on the result of IR measurement and the fact that a molecular ion peak was observed at 496 by Mass analysis and the relationship between the raw materials used.
[0060]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0061]
Example 6
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In Example 1- (c), 21.4 g of 4- (trans-4-pentylcyclohexyl) bromobenzene was used in place of 25 g of 4-octyloxy-4′-bromobiphenyl, and the others were the same as in Example 1- (c). The same operation was performed to obtain 9.5 g (50.1%) of 4- (trans-4-pentylcyclohexyl) phenylboronic acid. HPLC 99.7%
[0062]
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Using 1.04 g of 4- (trans-4-pentylcyclohexyl) phenylboronic acid obtained in (a) instead of 1.24 g of 4-octyloxybiphenyl-4′-boronic acid in Example 1- (d), Otherwise, operating as in Example 1- (d), 4- (trans-4-pentylcyclohexyl) -3'-trifluoromethyl-4'-octyloxybiphenyl 0.93 g (53.1%) was obtained. .
[0063]
The purity of this product was 99.2% by HPLC and one spot by TLC.
In addition, it was confirmed that the substance obtained from the IR measurement and the MaSs analysis showed a molecular ion peak at 502, and the obtained substance was the title compound based on the relationship between the raw materials used.
[0064]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0065]
Example 7
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The procedure of Example 1- (a) was repeated, except that 20 g of 5-amino-2-bromobenzotrifluoride was used instead of 20 g of 2-amino-5-bromobenzotrifluoride in Example 1- (a). 14.3 g (71.5%) of 3-trifluoromethyl-4-bromophenol were obtained. b. p. 140 ° C./35 torr, GC 98.1%, GC-Ms 240 (M−1) 242 (M + 1)
[0066]
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In Example 1- (b), 5 g of 3-trifluoromethyl-4-bromophenol obtained in (a) was used instead of 5 g of 2-trifluoromethyl-4-bromophenol, and the others were the same as in Example 1- (b). ) To give 5.82 g (79.5%) of 3-trifluoromethyl-4-bromooctyloxybenzene. b. p. 115 ° C./0.9 torr, GC 96.1%, GC-Ms 352 (M−1) 354 (M + 1)
[0067]
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Using 1.24 g of 3-trifluoromethyl-4-bromooctyloxybenzene obtained in (b) instead of 1.24 g of 2-trifluoromethyl-4-bromooctyloxybenzene in Example 1- (d), Others were the same as those in Example 1- (d) to obtain 1.63 g (83.6%) of 2-trifluoromethyl-4,4 "-dioctyloxyterphenyl.
[0068]
The purity of this product was 99.6% by HPLC and one spot by TLC.
In addition, it was confirmed that the substance obtained from the relationship between the raw material used and the molecular ion peak at 554 as a result of IR measurement and Mass analysis was the title compound.
[0069]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0070]
Example 8
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Example 7- (b) in place of 1.24 g of 2-trifluoromethyl-4-bromooctyloxybenzene and 1.24 g of 4-octyloxybiphenyl-4'-boronic acid in Example 1- (d). Using 1.24 g of the obtained 3-trifluoromethyl-4-bromooctyloxybenzene and 1.14 g of 4-heptylbiphenyl-4'-boronic acid obtained in Example 2- (a), Operating in the same manner as in (d), 0.92 g (50%) of 2-trifluoromethyl-4-octyloxy-4 ″ -heptyl terphenyl was obtained.
[0071]
The purity of this product was 99.9% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound based on the result of IR measurement and the fact that a molecular ion peak was observed at 524 by Mass analysis, and the relationship between the raw materials used.
[0072]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0073]
Example 9
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The procedure of Example 1- (c) was repeated, except that 19.8 g of 4-bromooctyloxybenzene was used instead of 25 g of 4-octyloxy-4'-bromobiphenyl. 8.9 g (51.1%) of octyloxyphenylboronic acid were obtained. HPLC 93.0%
[0074]
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Under an argon atmosphere, Pd [PPh₃)₄0.4 g, a solution of 2.97 g (11.9 mmol) of 4-octyloxyphenylboronic acid obtained in (a) in 30 cc of ethanol, and a solution of 1.6 g (5.4 mmol) of 2,5-dibromobenzotrifluoride in 30 cc of benzene And 15 cc of a 2M aqueous solution of sodium carbonate were stirred under reflux for 12 hours. The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was subjected to silica gel column elution with hexane-benzene (10: 1 to 1: 1). Purification by chromatography and recrystallization from acetone gave 1.62 g (55.5%) of 2'-trifluoromethyl-4,4 "-dioctyloxyterphenyl.
[0075]
The purity of this product was 99.9% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 554 in Mass analysis, and the relationship between the raw materials used.
[0076]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0077]
Example 10
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75 cc of concentrated sulfuric acid and 100 cc of acetic acid were added to 15 g (62.5 mmol) of 2-amino-5-bromobenzotrifluoride, and the precipitate was dissolved by heating. After the solution was cooled to 0 ° C. or lower, a solution of 5.28 g (76.5 mmol) of sodium nitrite in 30 cc of water was added dropwise with stirring, and the solution was allowed to stand at 0 ° C. for 30 minutes to prepare a diazonium salt solution.
[0078]
To this diazonium salt solution, a 75 cc solution of cyclohexane and 21.5 g (129.5 mmol) of potassium iodide in 75 cc of water were sequentially added dropwise at 0 ° C. or lower, and the mixture was stirred at room temperature for 24 hours.
[0079]
The reaction mixture was poured into water, extracted with ether, washed with an aqueous solution of sodium pyrosulfite, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was distilled with GTO under reduced pressure. 18.7 g (85.4%) of 5-bromo-2-iodobenzotrifluoride were obtained. b. p. 120-125 ° C / 19 torr, GC 95.4%, GC-Ms 350 (M-1), 352 (M + 1)
[0080]
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Under an argon atmosphere, 10.5 cc (16.8 mmol) of a 1.6 M n-butyl lithium / hexane solution was added dropwise at −10 ° C. to a 7-cc solution of 1.64 g (14.9 mmol) of 1-octyne in tetrahydrofuran. Stirred for 20 minutes. Further, a suspension composed of 2.28 g (16.8 mmol) of zinc chloride and 15 cc of tetrahydrofuran was added, and the mixture was stirred at −10 ° C. for 30 minutes. .2 mmol) in 15 cc of tetrahydrofuran and Pd [PPh₃]₄0.82 g of a 15 cc solution of tetrahydrofuran was sequentially added dropwise. Then, the temperature was gradually returned to room temperature, and the mixture was stirred overnight.
[0081]
The reaction mixture was poured into a dilute hydrochloric acid aqueous solution, extracted with ether, washed with water, washed with a saturated aqueous solution of sodium hydrogen carbonate, washed again with water, dried over sodium sulfate, and the solvent was distilled off. Then, 3 g (63.3%) of 2-trifluoromethyl-4-bromo- (oct-1-ynyl) benzene was obtained. b. p. 95-100 ° C / 2 torr, GC 96.5%, GC-Ms332 (M-1), 334 (M + 1)
[0082]
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2-trifluoromethyl-4-bromo- (oct-1-ynyl) 1 obtained in (b) instead of 1.24 g of 2-trifluoromethyl-4-bromooctyloxybenzene in Example 1- (d) The same operation as in Example 1- (d) was conducted except that 1.52 g (81.7 g) of 3-trifluoromethyl-4- (oct-1-ynyl) -4'-octyloxyterphenyl was used. %). HPLC 99.1%, Mass 534 (M). The phase change of this product was as follows.
[0083]

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From 0.51 g (0.96 mmol) of 3-trifluoromethyl-4- (oct-1-ynyl) -4'-octyloxyterphenyl obtained in (c), 0.05 g of 10% palladium carbon and 20 cc of ethyl acetate. The resulting mixture was hydrogenated for 2 hours
[0084]
The reaction mixture was filtered to remove palladium carbon, the solvent was distilled off, and the residue was recrystallized with an acetone-methanol mixed solvent to give 3-trifluoromethyl-4-octyl-4'-octyloxyterphenyl 0.1. 48 g (94.1%) were obtained.
[0085]
The purity of the product was 99.1% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound based on the result of IR measurement and the fact that a molecular ion peak was observed at 538 by Mass analysis and the relationship between the raw materials used.
[0086]
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0087]
Example 11
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Example 10- (b) in place of 1.24 g of 2-trifluoromethyl-4-bromooctyloxybenzene and 1.24 g of 4-octyloxybiphenyl-4'-boronic acid in Example 1- (d). Using 1.16 g of the obtained 2-trifluoromethyl-4-bromo- (oct-1-ynyl) benzene and 1.14 g of 4-heptylbiphenyl-4'-boronic acid obtained in Example 2- (a), Otherwise by operating in the same manner as in Example 1- (d), 0.87 g (49.4%) of 3-trifluoromethyl-4- (oct-1-ynyl) -4'-heptylterphenyl was obtained.
HPLC 99.1%, Mass 504 (M). The phase change of this product was as follows.
[0088]

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3-trifluoromethyl- obtained in (a) in place of 0.51 g of 3-trifluoromethyl-4- (oct-1-ynyl) -4'-octyloxyterphenyl in Example 10- (d). Using 4-8- (oct-1-ynyl) -4'-heptyl terphenyl in the same manner as in Example 10- (d), but using 0.48 g of 3-trifluoromethyl-4-octyl-4'- 0.38 g (79.2%) of heptyl terphenyl was obtained.
[0089]
The purity of this product was 99.0% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 508 by Mass analysis, and the relationship between the raw materials used.
This product was observed for phase change under a polarizing microscope using a Mettler hot stage FP-82. Table 4 shows the results.
[0090]
Reference Example 1
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Under an argon atmosphere, Pd (PPh₃)₄5 g, 18.7 g (83.1 mmol) of 2-bromo-benzotrifluoride in 200 cc of benzene and 25 g (91.2 mmol) of 4- (trans-4-pentylcyclohexyl) phenylboronic acid obtained in Example 6- (a) ) In 90 ml of a 2M aqueous solution of sodium carbonate was stirred under reflux for 24 hours.
[0091]
The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, and the solvent was distilled off.The residue was purified by silica gel column chromatography using hexane as an eluent, and then re-used with acetone. The crystals were crystallized to obtain 27.4 g (88.1%) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethylbiphenyl. GC 98.9%, Mass 374 (M)
[0092]
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Under ice cooling, a solution of 9.1 g (56.9 mmol) of bromine in 5 cc of methylene chloride was obtained in (a). 19 g (50.8 mmol) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethylbiphenyl nitric acid The mixture was added dropwise to a mixture consisting of 2.0 g of thallium (II) trihydrate and 100 cc of methylene chloride, and stirred for 3 hours.
[0093]
The reaction mixture was poured into a dilute aqueous sodium hydroxide solution, extracted with methylene chloride, washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue was recrystallized from an acetone-methanol mixed solvent to give 4- (trans- 18.1 g (78.7%) of 4-pentylcyclohexyl) -2'-trifluoromethyl-4'-bromobiphenyl were obtained. GC 98.7%, Mass 452 (M-1), 454 (M + 1)
[0094]
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Under an argon atmosphere, 4.6 cc (7.3 mmol) of a 1.6 Mn-butyllithium / hexane solution was obtained at -70 ° C at the temperature of-(trans-4-pentylcyclohexyl) -2'-trifluoromethyl obtained in (b). The solution was added dropwise to a solution of 3 g (6.6 mmol) of 4'-bromobiphenyl in 20 cc of tetrahydrofuran and stirred at the same temperature for 1 hour. 1 cc of trimethyl boronate was added to the reaction mixture, which was gradually heated to 0 ° C. and stirred for 30 minutes. The mixture was cooled again to -10 ° C or lower, 5 cc of 30% hydrogen peroxide was added dropwise, and the mixture was gradually returned to room temperature and stirred for 1 hour. Then, the reaction mixture was cooled to −30 ° C., 10 cc of a saturated aqueous sodium hydrogen sulfite solution was added, and the mixture was stirred for 24 hours while gradually returning to room temperature.
[0095]
The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue was silica gel using hexane-benzene (2: 1 to 1: 1) as an eluent. Purification by column chromatography gave 2.42 g (93.8%) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-hydroxybiphenyl.
GC 96.6%, IR (neat): 3400 cm^-1(OH)
[0096]
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60% hydrogenation of a 20 ml solution of 1.07 g (2.74 mmol) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-hydroxybiphenyl obtained in (c) under ice-cooling in dimethylformamide. 0.25 g of sodium was added, and the mixture was stirred until foaming stopped. Further, 0.61 g (4.96 mmol) of n-propyl bromide was added, and the mixture was stirred at room temperature for 2 days.
[0097]
The reaction mixture was poured into a dilute hydrochloric acid aqueous solution, extracted with benzene, washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue was subjected to silica gel column chromatography using hexane-benzene (4: 1) as an eluent. And then recrystallized with a mixed solvent of acetone and methanol to give 0.95 g (79.8%) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-propyloxybiphenyl. Obtained.
[0098]
The purity of the product was 99.1% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 432 by Mass analysis and the relationship between the raw materials used.
[0099]
This product was observed for its phase change under a polarizing microscope using a Mettler hot stage FP-82, and the results are shown in Table 4.
[0100]
Example 12
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Reference Example 1-0.61 g of n-propyl bromide in (d). Was replaced with 0.96 g of n-octyl bromide.Reference Example 1Operating in the same manner as in (d), 0.83 g (60.1%) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-octyloxybiphenyl was obtained.
[0101]
The purity of this product was 97.0% by HPLC, and one spot by TLC.
In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement, the fact that a molecular ion peak was observed at 502 in Mass analysis, and the relationship between the raw materials used.
[0102]
This product was observed for its phase change under a polarizing microscope using a Mettler hot stage FP-82, and the results are shown in Table 4.
[0103]
Reference Example 2
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Under an argon atmosphere, 1.6 cc (7.3 mmol) of a 1.6 Mn-butyllithium / hexane solution was added at -70 ° C.Reference Example 1-It is added dropwise to a solution of 3 g (6.6 mmol) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-bromobiphenyl obtained in (b) in 20 cc of tetrahydrofuran and stirred at the same temperature for 2 hours. did. Further, 0.95 g (8.4 mmol) of N-formylpiperidine was added dropwise, and the mixture was gradually returned to room temperature and stirred for one day.
[0104]
The reaction mixture was poured into a dilute aqueous hydrochloric acid solution, extracted with benzene, washed with water, dried over sodium sulfate, and the solvent was distilled off. Crude 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4 ' 2.69 g of formylbiphenyl were obtained. GC 93.9%, IR (neat): 1700 cm^-1(CHO)
[0105]
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Under ice-cooling, 0.5 g (13.2 mmol) of sodium borohydride was obtained in (a) 2.6 g of crude 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-formylbiphenyl (6.5 mmol) was added to a solution composed of 10 cc of tetrahydrofuran and 10 cc of ethanol, and the mixture was stirred under reflux for 3 hours.
[0106]
The reaction mixture was poured into a dilute aqueous hydrochloric acid solution, extracted with benzene, washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue was eluted with hexane-benzene (1: 0 to 1: 1). Purification by silica gel column chromatography gave 2.28 g (87.4%) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-hydroxymethylbiphenyl. GC 99.4%, IR (neat): 3350 cm^-1(OH)
[0107]
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1.35 g of methyl iodide was added to a solution of 1.15 g (2.8 mmol) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-hydroxymethylbiphenyl obtained in (b) in 15 cc of tetrahydrofuran ( 9.5 mmol), 0.45 g (8.0 mmol) of potassium hydroxide and 60.1 g (0.38 mmol) of 18-crown-6 were sequentially added, and the mixture was stirred at room temperature for 2 days.
[0108]
The reaction mixture was poured into water, extracted with benzene, washed with water, dried over sodium sulfate, evaporated, and the residue was subjected to silica gel column chromatography using hexane-benzene (2: 1) as an eluent. And then recrystallized with a mixed solvent of acetone and methanol to obtain 0.91 g (76.5%) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-methoxymethylbiphenyl. Was.
[0109]
The purity of this product was 99.4% by HPLC and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 418 by Mass analysis, and the relationship between the raw materials used.
[0110]
This product was observed for its phase change under a polarizing microscope using a Mettler hot stage FP-82, and the results are shown in Table 4.
[0111]
Example 13
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Reference Example 2-In (c), 2.0 g of n-hexyl iodide was used instead of 1.35 g of methyl iodide.Reference Example 2The same operation as in (c) was performed to obtain 1.09 g (78.4%) of 4- (trans-4-pentylcyclohexyl) -2'-trifluoromethyl-4'-hexyloxymethylbiphenyl.
[0112]
The purity of this product was 97.2% by HPLC, and one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the results of IR measurement and the fact that a molecular ion peak was observed at 488 by Mass analysis, and the relationship between the raw materials used.
[0113]
This product was observed for its phase change under a polarizing microscope using a Mettler hot stage FP-82, and the results are shown in Table 4.
[0114]
Example 14
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In Example 1- (d), instead of 1.24 g of 4-octyloxybiphenyl-4'-boronic acid, 0.95 g of 4-octyloxyphenylboronic acid obtained in Example 9- (a) was used. Was operated in the same manner as in Example 1- (d) to obtain 1.37 g (83.0%) of 3-trifluoromethyl-4,4'-dioctyloxybiphenyl.
[0115]
The purity of this product was 99.3% by HPLC and one spot by TLC. In addition, it was confirmed that the substance obtained from the IR measurement and Mass analysis showed a molecular ion peak at 478, and the obtained substance was the title compound based on the relationship between the raw materials used.
[0116]
This product was observed for its phase change under a polarizing microscope using a Mettler hot stage FP-82, and the results are shown in Table 4.
[0117]
Example 15
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Under an argon atmosphere, 9.8 cc (15.6 mmol) of a 1.6 M n-butyllithium / hexane solution was applied at -70 ° C to 2-trifluoromethyl-4-bromooctyloxybenzene obtained in Example 1- (b). It was added dropwise to a solution of 4 g (11.3 mmol) of 25 cc of tetrahydrofuran. After stirring at the same temperature for 1 hour, a solution of 3.55 g (14.2 mmol) of n-pentylcyclohexylcyclohexanone in 10 cc of tetrahydrofuran was added dropwise, and the reaction mixture was gradually returned to room temperature.
[0118]
The reaction mixture was poured into a dilute hydrochloric acid aqueous solution, extracted with toluene, washed with water, dried over sodium sulfate, and then the solvent was distilled off. The mixture was stirred under reflux for 2 hours.
[0119]
The reaction mixture was poured into water, extracted with toluene, washed with water, dried over sodium sulfate, the solvent was distilled off, and the residue was distilled with GTO under reduced pressure to give 3-trifluoromethyl-4-octyloxy-. 3.86 g (67.4%) of [4- (trans-4-pentylcyclohexyl) -1-cyclohexen-1-yl] benzene was obtained. b. p. 235 ° C / 0.15 torr) HPLC 95.3%
[0120]
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3.86 g (7.6 mmol) of 3-trifluoromethyl-4-octyloxy- [4- (trans-4-pentylcyclohexyl) -1-cyclohexen-1-yl] benzene obtained in (a), 10% palladium A mixture of 0.1 g of carbon and 50 cc of ethyl acetate was hydrogenated for 12 hours.
[0121]
The reaction mixture was filtered to remove palladium carbon, and the solvent was distilled off. Under an argon atmosphere, the residue was dissolved in 20 cc of dimethyl sulfoxide, 1 g (8.9 mmol) of potassium tert-butoxide was added, and the mixture was stirred at 80 to 85 ° C for 30 hours.
[0122]
The reaction mixture was poured into a dilute aqueous hydrochloric acid solution, extracted with benzene, washed with water, dried over sodium sulfate, evaporated, and the residue was purified by silica gel column chromatography using hexane as an eluent. The crystals were recrystallized with an acetone-methanol mixed solvent to obtain 1.71 g (44.3%) of 2-trifluoromethyl-4-octyloxy-4- [trans-4- (trans-4-pentylcyclohexyl) cyclohexyl] benzene. Was.
[0123]
The purity of this product was 99.3% by HPLC, and it was one spot by TLC. In addition, it was confirmed that the obtained substance was the title compound from the result of IR measurement and the fact that a molecular ion peak was observed at 508 by Mass analysis, and the relationship between the raw materials used.
[0124]
This product was observed for its phase change under a polarizing microscope using a Mettler hot stage FP-82, and the results are shown in Table 4.
[0125]
Example 16
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A parent liquid crystal composition (B-1) comprising the above four kinds of phenylpyrimidine compounds was prepared.
[0126]
80 wt% of the base liquid crystal composition (B-1), 10 wt% of 3-trifluoromethyl-4,4 ″ -dioctyloxyterphenyl obtained in Example 1- (d), and the following known optically active compound (D -1)
Embedded image

Was added to obtain a chiral Sc composition (M-1).
[0127]
At the same time, a chiral Sc composition (M-) comprising 90 wt% of the parent liquid crystal composition (B-1) and 10 wt% of the known optically active compound (D-1), excluding the compound of Example 1- (d). 2) was created.
The phase transition temperatures of these compositions are shown below.
[0128]

Each of the composition (M-1) and the composition (M-2) was injected into a commercially available liquid crystal cell (manufactured by EHC, polyimide alignment film, 2 μm gap) to prepare a liquid crystal element.
[0129]
Each liquid crystal element was sandwiched between two polarizing plates, and a response time was obtained from a change in transmitted light intensity by applying a ± 5 V / μm, 200 Hz rectangular wave. The spontaneous polarization was measured by the Sawyer tower method, and the tilt angle was measured from the moving angle of the extinction position when the polarity of the applied voltage was inverted.
Table 1 shows the results. The measurement temperature is 25 ° C.
[0130]
[Table 1]

[0131]
As described above, the compound of the present invention is effective in shortening the response time, increasing the tilt angle, and raising the chiral Sc upper limit temperature by adding the compound of the present invention, as compared with the case of not adding the compound. It is a useful compound that can be used to improve the desired properties when preparing a crystalline liquid crystal composition.
[0132]
Example 17
SaidExample 1687 wt% of the base liquid crystal composition (B-1) prepared in the above, 10 wt% of 3-trifluoromethyl-4-octyl-4 ″ -heptyl terphenyl obtained in Example 11- (b), and the following known optical activities: A compound (D-2, JP-A-5-213930) was added at 3 wt% to prepare a chiral Sc composition (M-3).
[0133]
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[0134]
At the same time, a chiral Sc composition (M-) comprising 97 wt% of the parent liquid crystal composition (B-1) and 3 wt% of the known optically active compound (D-2), excluding the compound of Example 11- (b). 4) was prepared.
The phase transition temperatures of these compositions are shown below.
[0135]

Each of the composition (M-3) and the composition (M-4) was injected into a commercially available liquid crystal cell (manufactured by EHC, polyimide alignment film, 2 μm gap) to form a liquid crystal element.Example 16The response time, spontaneous polarization and tilt angle were measured in the same manner as in the above. Table 2 shows the results.
[0136]
[Table 2]

[0137]
As described above, the compound of the present invention is effective in shortening the response time and lowering the chiral Sc minimum temperature as compared with the case where no compound is added. It is a useful compound that can be used to improve the desired properties when making it.
[0138]
Example 18
Example 17In which, instead of the compound of Example 11- (b),Example 15Using the compound of-(b),Example 17A chiral Sc composition (M-5) was prepared in the same manner as described above, and compared with the composition (M-4) containing no compound of Example 11- (b). The phase transition temperature is shown below, and the measurement results of the response time, spontaneous polarization and tilt angle are shown in Table 3.
[0139]

[0140]
[Table 3]

[0141]
As described above, by adding the compound of the present invention, the chiral Sc lower limit temperature can be reduced without reducing the chiral Sc phase temperature width as compared with the case where no compound is added, and the compound is effective for shortening the response time. Yes, it is a useful compound that can be used to impart desired properties when preparing a ferroelectric liquid crystal composition.
[0142]
Example 19
The compound obtained in Example 11- (b) and the compound obtained in Example 4- (b) are compounds having the following phase transition temperatures (° C.).

The respective compounds of Example 11- (b) and Example 4- (b) were mixed at a ratio of 30 wt% and 70 wt% to prepare a Sc composition (B-2), and its phase transition temperature ( ° C). The results are shown below.
[0143]

As described above, the Sc phase temperature width of the compound of Example 4- (b) is 12.3 ° C., but the compound of Example 11- (b) having no Sc phase is added to the compound to obtain Sc. The phase temperature width became 20 degrees and was expanded by 7.7 degrees. Furthermore, by mixing, each of them is not a single product, but a practically ideal phase series, that is, I → Ne → S_A→ A composition exhibiting a phase sequence of Sc was obtained. Such a compound having no Sc phase is also useful for preparing a composition.
[0144]
Example 20
ZLI-1132 which is a commercially available nematic liquid crystal composition has no liquid crystal phaseReference Example 2-(C) 10 wt% of a compound (mp 58.7 ° C) was added (nematic composition M-6), and the transition temperature (T) from the nematic phase to the isotropic liquid was calculated._NI), Refractive index anisotropy (Δn), and threshold voltage (V_th) Was measured. In addition, ZLI-1132 itself was also measured. The results are shown below.
[0145]

[0146]
As shown above,Reference Example 2- (c)The compound is T_NIΔn and V_thIs greatly reduced, and is useful as a material for adjusting the intended properties when a nematic liquid crystal composition is prepared.
[0147]
[Table 4]

Claims (2)

General formula (I)

( Wherein , R ¹ represents an alkyl group, an alkoxy group or an alkoxyalkyl group having 1 to 14 carbon atoms, R ² represents an alkyl group, an alkoxy group or an alkoxyalkyl group having 5 to 14 carbon atoms,

And m and n each independently represent 0 or 1.
However, m and n are not 0 at the same time, and when m and n are 1 at the same time, neither A nor B

A trifluoromethylbenzene derivative represented by General formula (I)

( Wherein , R ¹ represents an alkyl group, an alkoxy group or an alkoxyalkyl group having 1 to 14 carbon atoms, R ² represents an alkyl group, an alkoxy group or an alkoxyalkyl group having 5 to 14 carbon atoms,

And m and n each independently represent 0 or 1.
However, m and n are not 0 at the same time, and when m and n are 1 at the same time, neither A nor B

A liquid crystal composition comprising at least one trifluoromethylbenzene derivative represented by the following formula: