JP2005047812A - Indan compound and nematic liquid crystal composition comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a 4,5,6-trisubstituted indan compound or a 5,6-disubstituted indan compound having a 1,4-butylene group and to provide a nematic liquid crystal composition having a high lower limit temperature (T<SB>→N</SB>) of a liquid crystal phase and a low upper limit temperature (T<SB>N-I</SB>) of the liquid crystal phase using the same and further having a wide temperature range of the liquid crystal phase and the compound. <P>SOLUTION: The indan compound is represented by the general formula and has the 1,4-butylene group. The liquid crystal composition comprises one or two or more kinds of the compound. Furthermore, a liquid crystal display element comprises the liquid crystal composition as a constituent material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（式中Ｒ^１は、水素原子、炭素数１〜１５のアルキル基、少なくとも一つのハロゲンにより置換された炭素数１〜１５のアルキル基、炭素数２〜１５のアルケニル基又は少なくとも一つのハロゲンにより置換された炭素数２〜１５のアルケニル基を表し、これらの基中に存在する１個又は２個以上のＣＨ_２基はそれぞれ独立してＯ原子が相互に直接結合しないものとして −Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−ＯＣＯ−Ｏ−により置き換えられても良く、
Ａ^１は、
（ａ） トランス−シクロへキサン−１，４−ジイル基（この基中に存在する１個のＣＨ_２基又は隣接していない２個以上のＣＨ_２基は−Ｏ−及び又は−Ｓ−に置き換えられてもよい）
（ｂ） １，４−フェニレン基（この基中に存在する１個の−ＣＨ＝基又は隣接していない２個以上の−ＣＨ＝基は −Ｎ＝ に置き換えられてもよい）
（ｃ） シクロヘキセレン−１，４−ジイル基、１，４−ビシクロ［２．２．２］オクチレン基、ピペリジン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基であり、上記の基（ａ）、基（ｂ）、基（ｃ）はＣＮ又はハロゲンで置換されていても良く、
ｎは、１又は２であり、
Ｙは、
【００１１】
【化７】

で表される。）で表される化合物。
【００１２】
また、本件発明は一般式（Ｉ）で表される化合物を１種又は２種以上を含有することを特徴とするネマチック液晶組成物を提供する。
【００１３】
更に、本件発明は一般式（Ｉ）で表される化合物及び一般式（ＩＩ）
【化８】

（式中、Ｒ^２及びＲ^３はそれぞれ独立的にＲ^１と同じ意味を表し、
Ｂ^１、Ｂ^２及びＢ^３はそれぞれ独立的に
（ａ） トランス−シクロへキサン−１，４−ジイル基（この基中に存在する１個のＣＨ_２基又は隣接していない２個以上のＣＨ_２基は−Ｏ−及び又は−Ｓ−に置き換えられてもよい）
（ｂ） １，４−フェニレン基（この基中に存在する１個の−ＣＨ＝基又は隣接していない２個以上の−ＣＨ＝基は −Ｎ＝ に置き換えられてもよい）
（ｃ） シクロヘキセレン−１，４−ジイル基、１，４−ビシクロ［２．２．２］オクチレン基、ピペリジン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基であり、上記の基（ａ）、基（ｂ）、基（ｃ）はＣＮ又はハロゲンで置換されていても良く、
ｏは０、１又は２であり、
Ｌ^１、Ｌ^２及びＬ^３はそれぞれ独立的に単結合、−ＣＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−又は−Ｃ≡Ｃ−を表し、Ｌ^２及びＢ^３が複数存在する場合はそれらは同一でも良く異なっていても良い。）から選ばれる化合物及び／又は一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群
【００１４】
【化９】

【００１５】
（式中Ｒ^４はＲ^１と同じ意味を表し、Ｃ^１、Ｃ^２及びＣ^３はそれぞれ独立して、
（ｄ） トランス−シクロへキサン−１，４−ジイル基（この基中に存在する１個のＣＨ_２基又は隣接していない２個以上のＣＨ_２基は−Ｏ−及び又は−Ｓ−に置き換えられてもよい）
（ｅ） １，４−フェニレン基（この基中に存在する１個の−ＣＨ＝基又は隣接していない２個以上の−ＣＨ＝基は −Ｎ＝ に置き換えられてもよい）
（ｆ） シクロヘキセレン−１，４−ジイル基、１，４−ビシクロ［２．２．２］オクチレン基、ピペリジン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基であり、上記の基（ｄ）、基（ｅ）、基（ｆ）はＣＮ又はハロゲンで置換されていても良いが、１，２，３，４−テトラヒドロナフタレン−２，６−ジイルを表す場合、無置換であるか、少なくとも２つ以上のハロゲンによって置換されており、
Ｋ^１、Ｋ^２及びＫ^３はそれぞれ独立的に単結合、−ＣＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−又は−Ｃ≡Ｃ−を表し、
Ｘ^１、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６はそれぞれ独立してＨ又はＦであり、
ｐ及びｑはそれぞれ独立して、０、１又は２であるが、ｐ及びｑの和は２以下であり、
Ｘ^２は、−Ｈ、−Ｆ、−Ｃｌ−、ＣＮ、−ＣＦ_３−、−ＣＦ_２−、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＣＨ_２ＣＦ_３又はＲ^１と同じ定義である。）から選ばれる１種又は２種以上の化合物を含有することを特徴とするネマチック液晶組成物を提供する。
【００１６】
【発明の実施の形態】
以下に本発明の一例について説明する。
一般式（Ｉ）において、Ｒ^１は、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基又は炭素数２〜１０のアルケニル基が好ましく、未置換の直鎖状炭素数１〜８のアルキル基又は炭素数２〜８のアルケニル基がより好ましく、アルケニル基では以下の式（ａ）〜（ｅ）の構造がさらに好ましい。
【００１７】
【化１０】

（構造式は右端で環に連結しているものとする。）
Ａ^１はトランス−１，４−シクロへキシレン基、１，４−フェニレン基、３−フルオロ−１，４−フェニレン基又は３，５−ジフルオロ−１，４−フェニレン基が好ましく、トランス−１，４−シクロへキシレン基がより好ましく、ｎは１が好ましい。
【００１８】
一般式（Ｉ）で表される化合物は具体的な構造として次の化合物が特に好ましい。
【化１１】

（式中、Ｒ^１は、炭素原子数１〜６のアルキル基又は炭素原子数２〜６のアルケニル基を表す。）
【００１９】
一般式（Ｉ）の化合物中の一般式（Ｉ−ａ）
【化１２】

【００２０】
は以下のようにして製造することができる。一般式（ＩＶ）
【化１３】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）で表されるヘキサン酸誘導体をリチウムジイソプロピルアミド、リチウムヘキサメチルジシラジドやブチルリチウムなどの強塩基を用いてエノール化した後、３，４，５−トリフルオロベンジルブロミドを反応させることにより一般式（Ｖ−ａ）
【００２１】
【化１４】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）で表されるエステルを得ることができる。このエステルを水酸化ナトリウムや水酸化カリウムを用いて加水分解し、得られたカルボン酸を塩化チオニル等を用いて酸塩化物に変換した後、塩化アルミニウムなどのルイス酸と反応させることによって、一般式（ＶＩ−ａ）
【００２２】
【化１５】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）で表されるインダノン誘導体を得ることができる。これを水素化ホウ素ナトリウムや水素化アルミニウムリチウム等を用いて還元し、得られたアルコールをｐ−トルエンスルホン酸等の酸触媒存在下、加熱することによって、一般式（ＶＩＩ−ａ）
【００２３】
【化１６】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）で表されるインデン誘導体を得ることができる。これをＰｄ−Ｃ、Ｒｈ−Ｃ、Ｐｔ−Ｃ、Ｐｄ（ＯＨ）_２等の金属触媒存在下、水素添加することによって、目的の一般式（Ｉ−ａ）で表される化合物を得ることができる。
【００２４】
また、一般式（Ｉ）の化合物中の一般式（Ｉ−ｂ）
【化１７】

は以下のようにして製造することができる。
【００２５】
（Ｉ−ａ）の製造において、３，４，５−トリフルオロベンジルブロミドの代わりに、３，５−ジフルオロベンジルブロミドを用いて、一般式（ＶＩＩＩ）
【化１８】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）で表される化合物を得ることができる。これに、ブチルリチウム、リチウムジイソプロピルアミド、リチウムヘキサメチルジシラジドなどの強塩基を用いてリチオ化した後、二酸化炭素を反応させ、一般式（ＩＸ）
【００２６】
【化１９】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）で表される化合物を得て、これを塩化チオニル等を用いて、酸塩化物とした後、アンモニアと反応させ、得られたアミドをオキシ塩化リン等で脱水し、目的の一般式（Ｉ−ｂ）で表される化合物を得ることができる。
【００２７】
また、（Ｉ−ｂ）は、（ＶＩＩＩ）をリチオ化した後、Ｎ，Ｎ−ジメチルホルムアミドと反応させて、ホルミル基を導入した後、ヒドロキシアミンを反応させ、さらに脱水する方法や、（ＶＩＩＩ）をリチオ化した後、ヨウ素を反応させ、さらにシアン化銅を反応させる方法などによっても製造することができる。
【００２８】
また、一般式（Ｉ）の化合物中の一般式（Ｉ−ｃ）
【００２９】
【化２０】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）は以下のようにして製造することができる。
【００３０】
（Ｉ−ａ）の製造において、３，４，５−トリフルオロベンジルブロミドの代わりに、３，４−ジクロロベンジルブロミドを用いて、一般式（Ｘ）
【化２１】

（式中、Ｒ及びｎは一般式（Ｉ）におけると同じ定義。）で表される化合物を得て、これに、シアン化銅を反応させる方法によって製造することができる。
【００３１】
本発明の液晶組成物において、第一成分として一般式（Ｉ）から選ばれる化合物を１種又は２種以上を含有するが、１種〜６種が好ましく、１種〜４種がより好ましく、１種〜３種が特に好ましい。
【００３２】
又、一般式（Ｉ）の含有率は５〜５０質量％の範囲であることが好ましく、１０〜４０質量％の範囲であることが特に好ましい。
【００３３】
一般式（Ｉ）から選ばれる化合物のうち少なくとも１種以上の組成物の誘電率異方性（Δε）が１．５以上の化合物を含有することが好ましく、２以上を示すことがより好ましい。
【００３４】
第二成分として一般式（ＩＩ）、一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群から選ばれる化合物を１種又は２種以上を含有するが、１種〜２０種が好ましく、１種〜１５種がより好ましく、１種〜１０種が特に好ましい。また、これらの含有率は１０質量％〜８０質量％が好ましい。
【００３５】
一般式（ＩＩ）においてＲ^２及びＲ^３は、未置換の直鎖状炭素数１〜１５のアルキル基、直鎖状炭素数１〜１５のアルコキシル基又は炭素数２〜１５のアルケニル基が好ましく、未置換の直鎖状炭素数１〜１０のアルキル基又は炭素数２〜１０のアルケニル基がより好ましく、未置換の直鎖状炭素数１〜８のアルキル基又は炭素数２〜６のアルケニル基が特に好ましく、アルケニル基では式（ａ）〜（ｅ）の構造がさらに好ましい。
また、Ｒ^２及びＲ^３は同一でも異なっていても良いが、同一分子中のＲ^２及びＲ^３は異なっていることがより好ましい。Ｌ^１及びＬ^２は、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−Ｃ≡Ｃ−又は単結合が好ましく、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−Ｃ≡Ｃ−又は単結合がより好ましく、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−Ｃ≡Ｃ−又は単結合が特に好ましく、Ｌ^１及びＬ^２が複数存在する場合少なくとも一つは単結合であることが好ましい。ｏは、０又は１が好ましい。
【００３６】
Ｃ^１、Ｃ^２及びＣ^３はそれぞれ独立してトランス−シクロへキサン−１，４−ジイル基、１，４−フェニレン基、３−フルオロ−１，４−フェニレン基又は３，５−ジフルオロ−１，４−フェニレン基が好ましく、トランス−シクロへキサン−１，４−ジイル基又は１，４−フェニレン基がより好ましく、Ｃ^１、Ｃ^２及びＣ^３の内少なくとも一つはトランス−１，４−シクロへキシレン基であることが好ましい。
【００３７】
一般式（ＩＩ）は以下の一般式（ＩＩａ）で表される構造が好ましい。
【化２２】

（式中、Ｒ^２及びＲ^３は炭素原子数１〜８のアルキル基又はアルコキシル基、炭素原子数２〜８のアルケニル基、炭素原子数３〜１６のアルケニルオキシ基を表し、Ｂ^３は１，４−フェニレン基又はトランス−シクロへキサン−１，４−ジイル基を表し、ｒは０又は１を表す。）
【００３８】
一般式（ＩＩａ）の化合物の含有率は１０〜８０質量％の範囲であることが好ましい。
又、一般式（ＩＩ）は具体的な構造として以下の一般式で表される構造も好ましい。
【化２３】

【００３９】
（式中、Ｒ^５及びＲ^６はそれぞれ独立して炭素原子数１〜８のアルキル基又はアルコキシル基、炭素原子数２〜８のアルケニル基、炭素原子数３〜１６のアルケニルオキシ基を表す。）で表される構造が好ましい。
又、一般式（ＩＩ）から選ばれる化合物を１種又は２種以上を含有するが、１種〜１５種が好ましく、１種〜１０種が特に好ましい。
【００４０】
一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）においてＲ^４は、未置換の直鎖状炭素数１〜１５のアルキル基又は炭素数２〜１５のアルケニル基が好ましく、未置換の直鎖状炭素数１〜１０のアルキル基又は炭素数２〜１０のアルケニル基がより好ましく、未置換の直鎖状炭素数１〜８のアルキル基又は炭素数２〜６のアルケニル基が特に好ましく、アルケニル基では式（ａ）〜（ｅ）の構造がさらに好ましい。Ｋ^１、Ｋ^２及びＫ^３は、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２ＣＨ_２−、−Ｃ≡Ｃ−、−（ＣＨ_２）_４−又は単結合が好ましく、−ＣＨ_２ＣＨ_２−、−Ｃ≡Ｃ−又は単結合がより好ましく、−ＣＨ_２ＣＨ_２−又は単結合が特に好ましく、Ｋ^１、Ｋ^２又はＫ^３が複数存在する場合少なくとも一つは単結合であることが好ましい。
ｐ及びｑは、０又は１が好ましい。Ｃ^１、Ｃ^２及びＣ^３はそれぞれ独立してトランス−シクロへキサン−１，４−ジイル基、１，４−フェニレン基、３−フルオロ−１，４−フェニレン基又は３，５−ジフルオロ−１，４−フェニレン基が好ましく、トランス−シクロへキサン−１，４−ジイル基又は１，４−フェニレン基がより好ましく、トランス−１，４−シクロへキシレン基が特に好ましい。
Ｘ^２は、−Ｈ、−Ｆ、−Ｃｌ−、ＣＮ、−ＣＦ_３−、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３、−ＣＨ_２ＣＦ_３又はＲ^１と同じ定義であるが、−Ｆ、−ＣＮ、−ＣＦ_３−、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、−ＯＣＦ_３が好ましく、−Ｆ、−ＣＮが特に好ましい。
【００４１】
一般式（ＩＩＩａ）は、以下の一般式（ＩＩＩａ−１）で表される構造
【化２４】

（式中、Ｒ^７は炭素原子数１〜８のアルキル基又はアルコキシル基、炭素原子数２〜８のアルケニル基を表し、Ｌ^５、Ｌ^６はそれぞれ独立して、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−（ＣＨ_２）_４−又は単結合を表し、環Ｉは１，４−フェニレン基又はトランス−シクロへキサン−１，４−ジイル基を表し、Ｘ^６はＨ又はＦを表し、ｎは０又は１を表し、Ｙ^４は−ＣＮ、−Ｆ、−Ｃｌ、−ＣＦ_３、−ＯＣＦ_３又は−ＯＣＨＦ_２を表す。）が好ましく、具体的な構造として以下の一般式
【００４２】
【化２５】

【００４３】
【化２６】

【００４４】
【化２７】

【００４５】
【化２８】

（式中、Ｒ^７は炭素原子数１〜８のアルキル基又はアルコキシル基、炭素原子数２〜８のアルケニル基を表し、Ｘ^３及びＸ^４はそれぞれ独立してＨ又はＦを表し、Ｙ^４はＣＮ、Ｆ、Ｃｌ、−ＣＦ_３、−ＯＣＦ_３又は−ＯＣＨＦ_２を表す。）で表される構造が特に好ましい。
一般式（ＩＩＩｂ）は具体的な構造として以下の一般式
【００４６】
【化２９】

【００４７】
【化３０】

【００４８】
（式中、Ｒ^７は炭素原子数１〜８のアルキル基又はアルコキシル基、炭素原子数２〜８のアルケニル基を表し、Ｙ^４は−ＣＮ、−Ｆ、−Ｃｌ、−ＣＦ_３、−ＯＣＦ_３又は−ＯＣＨＦ_２を表す。）で表される構造が好ましく、一般式（ＩＩＩｃ）は具体的な構造として以下の一般式
【００４９】
【化３１】

【００５０】
【化３２】

【００５１】
【化３３】

【００５２】
（式中、Ｒ^７は炭素原子数１〜８のアルキル基又はアルコキシル基、炭素原子数２〜８のアルケニル基を表し、Ｙ^４は−ＣＮ、−Ｆ、−Ｃｌ、−ＣＦ_３、−ＯＣＦ_３又は−ＯＣＨＦ_２を表す。）
一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群から選ばれる化合物を１種又は２種以上を含有するが、１種〜１０種が好ましく、２種〜８種が特に好ましい。
【００５３】
本発明のネマチック液晶組成物は一般式（Ｉ）から選ばれる化合物を１種又は２種以上を含有し、さらに一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群から選ばれる化合物を１種又は２種以上含有することが好ましく、一般式（Ｉ）から選ばれる化合物を１種又は２種以上を含有し、さらに一般式（ＩＩ）から選ばれる化合物を１種又は２種以上含有することも好ましい。
【００５４】
一般式（Ｉ）の化合物を１種又は２種以上含有し、さらに一般式（ＩＩ）の化合物を１種又は２種以上含有し、さらに一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群から選ばれる化合物を少なくとも１種又は２種以上含有することが好ましく、少なくとも１種以上の一般式（ＩＩ）の化合物を含有し、さらに一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群から選ばれる化合物を少なくとも２種以上含有することが好ましい。
【００５５】
又、一般式（ＩＩＩａ）から選ばれる化合物を１種又は２種以上含有し、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群から選ばれる化合物を１種又は２種以上含有することが好ましく、一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群の含有率が１０〜５０質量％の範囲であることが好ましい。
【００５６】
一般式（Ｉ）で表される化合物を１種又は２種以上を含有し、その含有率が５〜５０質量％の範囲で、なおかつ一般式（ＩＩａ）の化合物を１種又は２種以上を含有し、その含有率が１０〜６０質量％の範囲で、なおかつ一般式（ＩＩＩａ）、一般式（ＩＩＩｂ）及び一般式（ＩＩＩｃ）からなる群から選ばれる化合物を１種又は２種以上を含有し、その含有率が５〜５０質量％の範囲であることが特に好ましい。
【００５７】
本発明のネマチック液晶組成物は広い液晶相温度範囲（液晶相下限温度と液晶相上限温度の差の絶対値）を有するが、液晶相温度範囲が８０℃以上であることが好ましく、９０℃以上であることがより好ましく、１００℃以上が特に好ましい。また、液晶相上限温度は７０℃以上が好ましく、８０℃以上がより好ましい。さらに、液晶相下限温度は−２０℃以下が好ましく、−３０℃以下がより好ましい。
【００５８】
上記ネマチック液晶組成物はＡＭ−ＬＣＤやＳＴＮ−ＬＣＤに有用であり、透過型あるいは反射型の液晶表示素子に用いることができる。本発明のネマチック液晶組成物は、上記の化合物以外に、通常のネマチック液晶、スメクチック液晶、コレステリック液晶などを含有していてもよい。
【００５９】
【実施例】
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「％」は『質量％』を意味する。
【００６０】
実施例中、測定した特性は以下の通りである。
Ｔ_Ｎ−Ｉ ：ネマチック相−等方性液体相転移温度（℃）を液晶相上限温度
とする
Ｔ_{→ Ｎ} ：固体相又はスメクチック相−ネマチック相転移温度（℃）を液
晶相下限温度とする
ΔＴ ：ネマチック液晶相温度範囲、｜Ｔ_Ｎ−Ｉ − Ｔ_{→ Ｎ} ｜
化合物記載に下記の略号を使用する。
【００６１】
末端のｎ（数字） Ｃ_ｎＨ_２ｎ＋１−
Ｅ −ＣＯＯ−
ｅ −ＯＣＯ−
Ａ −ＣＨ_２ＣＨ_２−
Ｂ −ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２−
ｔ −Ｃ≡Ｃ−
ＣＮ −Ｃ≡Ｎ
Ｏｎ −ＯＣ_ｎＨ_２ｎ＋１
Ｆ −Ｆ
ｆ 末端基のオルト位に結合したＦ原子
ｎｄｍ− Ｃ_ｎＨ_２ｎ＋１−Ｃ＝Ｃ−（ＣＨ_２）_ｍ−１−
【００６２】
【化３４】

【００６３】
（実施例１） ２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］−４，５，６−トリフルオロインダンの合成
【化３５】

【００６４】
ジイソプロピルアミン（５７ ｇ）のテトラヒドロフラン（２５０ ｍｌ）溶液に、−６０℃でブチルリチウム（１．６ Ｍヘキサン溶液、３６０ ｍｌ）を加え、３０分攪拌後、−２０℃まで昇温し、３０分攪拌した。反応液を−６０℃に冷却し、６−（トランス−４−プロピルシクロヘキシル）ヘキサン酸エチル（１２０ ｇ）のテトラヒドロフラン（１００ ｍｌ）溶液を滴下し、１時間攪拌後、３，４，５−トリフルオロベンジルブロミド（１０６ ｇ）を滴下した。攪拌しながら、０℃まで３時間かけて昇温後、反応液を２０％塩化アンモニウム水溶液にあけ、ヘキサンで抽出した。有機層を飽和炭酸水素ナトリウム水溶液および飽和食塩水で洗い、無水硫酸ナトリウムで乾燥後、濃縮し、６−（トランス−４−プロピルシクロヘキシル）−２−（３，４，５−トリフルオロベンジル）ヘキサン酸エチル粗生成物（１９５ ｇ）を得た。
【００６５】
６−（トランス−４−プロピルシクロヘキシル）−２−（３，４，５−トリフルオロベンジル）ヘキサン酸エチル粗生成物（１９５ ｇ）のエタノール（３００ ｍｌ）溶液に２０％水酸化ナトリウム水溶液（１６０ ｍｌ）を加え、４時間加熱還流した。反応液を室温まで放冷後、反応液が酸性になるまで３ Ｍ塩酸を加えた。有機層を分離し、さらに水層をジクロロメタンで抽出した。有機層を集め、飽和食塩水で洗い、濃縮し、６−（トランス−４−プロピルシクロヘキシル）−２−（３，４，５−トリフルオロベンジル）ヘキサン酸粗生成物（１９０ ｇ）を得た。
【００６６】
６−（トランス−４−プロピルシクロヘキシル）−２−（３，４，５−トリフルオロベンジル）ヘキサン酸粗生成物（１９０ ｇ）の１，２−ジクロロエタン（２００ ｍｌ）溶液に室温で塩化チオニル（１２５ ｇ）を滴下し、４時間加熱還流した。その後、溶媒と過剰の塩化チオニルを留去し、６−（トランス−４−プロピルシクロヘキシル）−２−（３，４，５−トリフルオロベンジル）ヘキサン酸塩化物の粗生成物（２０２ ｇ）を得た。
【００６７】
無水塩化アルミニウム（１００ ｇ）のジクロロメタン（１５０ ｍｌ）懸濁液に、内温を０〜５℃に保ちながら、６−（トランス−４−プロピルシクロヘキシル）−２−（３，４，５−トリフルオロベンジル）ヘキサン酸塩化物の粗生成物（２０２ ｇ）のジクロロメタン（１００ ｍｌ）溶液を滴下し、さらに２時間攪拌した。反応液を氷水にあけ、有機層を分離し、さらに水層をジクロロメタンで抽出した。有機層を集め、飽和食塩水で洗い、濃縮し、残渣をシリカゲルカラムクロマトグラフィー（ヘキサン／酢酸エチル＝２０：１）で精製し、２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］−５，６，７−トリフルオロインダン−１−オン（１３２ ｇ）を得た。
【００６８】
２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］−５，６，７−トリフルオロインダン−１−オン（１３２ ｇ）のメタノール（２５０ ｍｌ）溶液に激しく攪拌しながら、水素化ホウ素ナトリウム（６ ｇ）を加え、２時間攪拌した。反応液に飽和食塩水を加え、酢酸エチルで抽出、濃縮した。残渣にトルエン（３００ ｍｌ）、ｐ−トルエンスルホン酸一水和物（５ ｇ）を加え、４時間加熱還流した。反応液を室温まで放冷後、水を加え、トルエンで抽出後、飽和炭酸水素ナトリウム水溶液、水、飽和食塩水で洗い、濃縮した。残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］−５，６，７−トリフルオロインダン−１−エン（１０４ ｇ）を得た。
【００６９】
オートクレーブに２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］−５，６，７−トリフルオロインダン−１−エン（１０４ ｇ）、５％パラジウム−炭素（５０％含水、１０ ｇ）、酢酸エチル（３００ ｍｌ）を加え、水素（０．５ＭＰａ）圧下、室温で３時間攪拌した。反応液をセライトでろ過し、ろ液を濃縮、残渣をシリカゲルカラムクロマトグラフィー（ヘキサン）で精製し、２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］−４，５，６−トリフルオロインダン（９８ ｇ）を得た。
^１Ｈ ＮＭＲ （ＣＤＣｌ_３） δ ０．８−１．０５ （ｍ， ４ Ｈ）， ０．８９ （ｔ， Ｊ ＝ ７．２ Ｈｚ， ３ Ｈ）， １．１−１．４ （ｍ， １４ Ｈ）， １．７２−１．８８ （ｍ， ４ Ｈ）， ２．２−２．３ （ｍ， １ Ｈ）， ２．５−２．６５ （ｍ， ２ Ｈ）， ２．９４ （ｄｄ， Ｊ ＝ ８．３ ａｎｄ １６ Ｈｚ， １ Ｈ）， ３．０６ （ｄｄ， Ｊ ＝ ８．２ ａｎｄ １６ Ｈｚ， １ Ｈ）， ６．７４ （ｂｒｏａｄ ｔ， Ｊ ＝ ８ Ｈｚ， １ Ｈ）
ＭＳ ｍ／ｚ ３５２ （Ｍ^＋）
【００７０】
（実施例２） ５−シアノ−４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダンの合成
【化３６】

【００７１】
実施例１において、３，４，５−トリフルオロベンジルブロミドの代わりに、３，５−ジフルオロベンジルブロミドを用いて、４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン（７９ ｇ）を得た。
【００７２】
４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン（７９ ｇ）のテトラヒドロフラン（３００ ｍｌ）溶液に、−６０℃でブチルリチウム（１．６ Ｍヘキサン溶液、１７０ ｍｌ）を滴下し、１時間攪拌した。その後、二酸化炭素を吹き込み、１時間攪拌した後、室温まで昇温した。反応液を１ Ｍ塩酸にあけ、有機層を分離し、さらに水層を酢酸エチルで抽出した。有機層を集め、飽和食塩水で洗い、濃縮し、４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン−５−カルボン酸粗生成物（８３ ｇ）を得た。
【００７３】
４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン−５−カルボン酸粗生成物（８３ ｇ）の１，２−ジクロロエタン（１５０ ｍｌ）溶液に室温で塩化チオニル（４０ ｍｌ）を滴下し、４時間加熱還流した。その後、溶媒と過剰の塩化チオニルを留去した。残渣をジクロロメタン（２００ ｍｌ）に溶解し、０℃でアンモニアガスを吹き込み、さらに２時間攪拌した。反応液に１ Ｍ塩酸を加え、有機層を分離し、さらに水層を酢酸エチルで抽出した。有機層を集め、飽和食塩水で洗い、濃縮し、４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン−５−カルボン酸アミド粗生成物（８５ ｇ）を得た。
【００７４】
４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン−５−カルボン酸アミド粗生成物（８５ ｇ）のＮ，Ｎ−ジメチルホルムアミド（２００ ｍｌ）溶液に、オキシ塩化リン（３５ ｍｌ）を滴下した。さらに５０℃で１時間加熱し、室温まで放冷した。反応液を氷水にあけ、酢酸エチルで抽出、飽和炭酸水ナトリウム水溶液、飽和食塩水で洗った後、濃縮した。残渣をシリカゲルカラムクロマトグラフィー（トルエン）で精製し、５−シアノ−４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン（４９ ｇ）を得た。
^１Ｈ ＮＭＲ （ＣＤＣｌ_３） δ ０．８−１．０５ （ｍ， ４ Ｈ）， ０．８８ （ｔ， Ｊ ＝ ７．５ Ｈｚ， ３ Ｈ）， １．１−１．４ （ｍ， １４ Ｈ）， １．６５−１．８６ （ｍ， ４ Ｈ）， ２．３−２．４５ （ｍ， １ Ｈ）， ２．５７ （ｄｄ， Ｊ ＝ １６ ａｎｄ ９ Ｈｚ， １ Ｈ）， ２．７０ （ｄｄ， Ｊ ＝ １６ ａｎｄ ９ Ｈｚ， １ Ｈ）， ３．０−３．２ （ｍ， ２ Ｈ）， ６．８５ （ｄ， Ｊ
＝ ８ Ｈｚ， １ Ｈ）
ＭＳ ｍ／ｚ ３５９ （Ｍ^＋）
【００７５】
（実施例３） ５，６−ジシアノ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダンの合成
【化３７】

【００７６】
実施例１において、３，４，５−トリフルオロベンジルブロミドの代わりに、３，４−ジクロロベンジルブロミドを用いて、５，６−ジクロロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン（６８ ｇ）を得た。
５，６−ジクロロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン（６８ ｇ）のＮ，Ｎ−ジメチルホルムアミド（３００ ｍｌ）溶液に、シアン化銅（２５ ｇ）を加え、６時間加熱還流した。放冷後、反応液をセライトでろ過し、ろ液に水を加え、トルエンで抽出した。有機層を飽和食塩水、飽和炭酸水素ナトリウム水溶液、１ Ｍ塩酸、飽和食塩水で洗い、無水硫酸ナトリウムで乾燥後、濃縮した。残渣をシリカゲルカラムクロマトグラフィー（２回、トルエンおよびヘキサン／酢酸エチル＝４：１）で精製し、５，６−ジシアノ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダン（１７ ｇ）を得た。
^１Ｈ ＮＭＲ （ＣＤＣｌ_３） δ ０．８−１．０６ （ｍ， ４ Ｈ）， ０．８７ （ｔ， Ｊ ＝ ７．６ Ｈｚ， ３ Ｈ）， １．１−１．４ （ｍ， １４ Ｈ）， １．６４−１．８７ （ｍ， ４ Ｈ）， ２．３１−２．４７ （ｍ， １ Ｈ）， ２．６１ （ｄｄ， Ｊ ＝ １６ ａｎｄ ９ Ｈｚ， ２ Ｈ）， ３．１０ （ｄｄ， Ｊ ＝ １６ ａｎｄ ７ Ｈｚ， ２ Ｈ）， ７．６５ （ｓ， ２ Ｈ）ＭＳ ｍ／ｚ ３４８ （Ｍ^＋）
【００７７】
（実施例４及び比較例１） 液晶組成物の調整
実施例１で合成された２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］−４，５，６−トリフルオロインダンを含有するネマチック液晶組成物（Ｎｏ．１）及び類似の構成を有するネマチック液晶組成物（Ｎｏ．２）を調整しその物性値を測定し、その結果を表１に示す。
【００７８】
【表１】

【００７９】
表１に示すように、実施例４のネマチック液晶組成物は、液晶相の下限温度（Ｔ_{→ Ｎ}）が高く、液晶相上限温度（Ｔ_Ｎ−Ｉ）が低く、広い液晶温度範囲を有することが解る。このネマチック液晶組成物を用いて、表示品位の優れたＴＮおよびＳＴＮ液晶表示素子を作成することができた。
【００８０】
（実施例５及び比較例２） 液晶組成物の調整
実施例２で合成された５−シアノ−４，６−ジフルオロ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダンを含有するネマチック液晶組成物（Ｎｏ．３）及び類似の構成を有するネマチック液晶組成物（Ｎｏ．４）を調整しその物性値を測定し、その結果を表２に示す。
【００８１】
【表２】

【００８２】
表２に示すように、実施例５のネマチック液晶組成物は、液晶相の下限温度（Ｔ_{→ Ｎ}）が高く、液晶相上限温度（Ｔ_Ｎ−Ｉ）が低く、広い液晶温度範囲を有することが解る。このネマチック液晶組成物を用いて、表示品位の優れたＴＮおよびＳＴＮ液晶表示素子を作成することができた。
【００８３】
（実施例６及び比較例２） 液晶組成物の調整
実施例６で合成された５，６−ジシアノ−２−［４−（トランス−４−プロピルシクロヘキシル）ブチル］インダンを含有するネマチック液晶組成物（Ｎｏ．５）及び類似の構成を有するネマチック液晶組成物（Ｎｏ．４）を調整しその物性値を測定し、その結果を表３に示す。
【００８４】
【表３】

【００８５】
表３に示すように、実施例５のネマチック液晶組成物は、液晶相の下限温度（Ｔ_{→ Ｎ}）は比較例２と同等であるが、液晶相上限温度（Ｔ_Ｎ−Ｉ）が高く、広い液晶温度範囲を有することが解る。
【００８６】
このネマチック液晶組成物を用いて、表示品位の優れたＴＮおよびＳＴＮ液晶表示素子を作成することができた。
【００８７】
【発明の効果】
本発明のネマチック液晶組成物により、４，５，６−トリ置換インダン系化合物あるいは５，６−ジ置換インダン系化合物を用いた、液晶相の下限温度が高く、液晶相上限温度が低く、液晶相温度範囲の広いネマチック液晶組成物を提供することが可能となった。本願発明の液晶組成物を用いた液晶表示素子は広い温度範囲で優れた表示品位を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a nematic crystal composition useful as an electro-optical liquid crystal display material, a liquid crystal display element using the composition, and an indane compound useful as a constituent material of the nematic liquid crystal composition.
[0002]
[Prior art]
In liquid crystal display elements such as twisted nematic, super twisted nematic or active matrix, especially in small and medium portable liquid crystal display elements, the stability of display with respect to the operating environment temperature is an important point. Liquid crystal material with lower driving voltage that can reduce power consumption, driving voltage in the temperature range of -30 to 0 ° C. or 40 to 80 ° C., steepness, desired duty driving frequency dependency, etc. It has been demanded.
[0003]
In particular, the lower limit temperature of the liquid crystal phase (T_{→ N}) And liquid crystal phase upper limit temperature (T_NIThe liquid crystal phase temperature range (ΔT), which is the absolute value of the difference between (), is important because it has been used outdoors, taking advantage of the low power consumption characteristics of liquid crystal display elements. However, with the combination of conventional materials, although the liquid crystal phase temperature range can be expanded, the threshold voltage increases and the response speed increases accordingly, so that a sufficient liquid crystal phase temperature range is not obtained. (See Patent Document 1).
Therefore, development of a liquid crystal composition having a wide liquid crystal phase temperature range without deteriorating liquid crystal characteristics such as response speed and threshold voltage, or development of a liquid crystal material optimal for this application has been desired.
[0004]
On the other hand, liquid crystal compounds having indane in the skeleton are already known, and some compounds have been disclosed (see Patent Document 2). However, although there is disclosure of a compound having a fluorine atom at the 5-position and 6-position of the indane ring, it does not disclose what characteristics the compound has when used as a nematic liquid crystal composition. No compound having a 1,4-butylene group is disclosed.
[0005]
For some compounds, liquid crystal compositions using indane compounds have already been known, and specific examples of preferred compounds have been disclosed (see Patent Document 3). However, in the compounds disclosed herein, the substituent at the 2-position of the indane ring also has a special ring structure or a non-ring structure. Moreover, the liquid crystal composition disclosed herein is a liquid crystal composition used for a ferroelectric liquid crystal display device, and there is no disclosure regarding a nematic liquid crystal composition.
[0006]
From the above, a nematic liquid crystal composition using a compound having a substituent such as a fluorine atom at the 5-position and 6-position of the indane ring is not known, and an indane-based compound, particularly an indane-based compound having a 1,4-butylene group Development of a nematic liquid crystal composition having a wide range of liquid crystal phase temperature and having excellent characteristics using a compound has been desired.
[0007]
[Patent Document 1]
JP 2001-11450 A (page 6)
[Patent Document 2]
International Publication No. 94/18285 (26-31 pages)
[Patent Document 3]
WO99 / 19420 pamphlet (pages 30-35)
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a 4,5,6-trisubstituted indane compound or a 5,6-disubstituted indane compound having a 1,4-butylene group, and a minimum temperature (T_{→ N}) Is high and the liquid crystal phase upper limit temperature (T_NI) And a nematic liquid crystal composition having a wide liquid crystal phase temperature range, and the compound.
[0009]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have studied 4,5,6-trisubstituted indan compounds or 5,6-disubstituted indan compounds and nematic liquid crystal compositions containing the compounds. It came to be completed.
That is, the present invention provides the following liquid crystal compound.
[0010]
Formula (I)
[Chemical 6]

(Where R¹Is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 15 carbon atoms substituted by at least one halogen, an alkenyl group having 2 to 15 carbon atoms or a carbon number substituted by at least one halogen. Represents 2 to 15 alkenyl groups, one or more CH present in these groups₂Each group may independently be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —OCO—O—, wherein the O atoms are not directly bonded to each other;
A¹Is
(A) trans-cyclohexane-1,4-diyl group (one CH present in this group)₂2 or more CHs not adjacent or adjacent₂Group may be replaced by -O- and / or -S-)
(B) 1,4-phenylene group (one —CH═ group present in this group or two or more non-adjacent —CH═ groups may be replaced by —N =)
(C) Cyclohexene-1,4-diyl group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- 2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group
The group (a), the group (b), and the group (c) may be substituted with CN or halogen,
n is 1 or 2,
Y is
[0011]
[Chemical 7]

It is represented by ) A compound represented by
[0012]
The present invention also provides a nematic liquid crystal composition comprising one or more compounds represented by formula (I).
[0013]
Further, the present invention relates to a compound represented by general formula (I) and general formula (II).
[Chemical 8]

(Wherein R²And R³Are independently R¹Means the same as
B¹, B²And B³Each independently
(A) trans-cyclohexane-1,4-diyl group (one CH present in this group)₂2 or more CHs not adjacent or adjacent₂Group may be replaced by -O- and / or -S-)
(B) 1,4-phenylene group (one —CH═ group present in this group or two or more non-adjacent —CH═ groups may be replaced by —N =)
(C) Cyclohexene-1,4-diyl group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- 2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group
The group (a), the group (b), and the group (c) may be substituted with CN or halogen,
o is 0, 1 or 2;
L¹, L²And L³Are each independently a single bond, —CH₂CH₂-,-(CH₂)₄-, -OCH₂-, -CH₂Represents O- or -C≡C-, L²And B³When there are a plurality of these, they may be the same or different. And / or the group consisting of general formula (IIIa), general formula (IIIb) and general formula (IIIc)
[0014]
[Chemical 9]

[0015]
(Where R⁴Is R¹Means the same as C¹, C²And C³Are independent of each other
(D) trans-cyclohexane-1,4-diyl group (one CH present in this group)₂2 or more CHs not adjacent or adjacent₂Group may be replaced by -O- and / or -S-)
(E) 1,4-phenylene group (one —CH═ group present in this group or two or more non-adjacent —CH═ groups may be replaced by —N =)
(F) Cyclohexene-1,4-diyl group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- 2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group
The group (d), group (e) and group (f) may be substituted with CN or halogen, but 1,2,3,4-tetrahydronaphthalene- When it represents 2,6-diyl, it is unsubstituted or substituted by at least two or more halogens;
K¹, K²And K³Are each independently a single bond, —CH₂CH₂-,-(CH₂)₄-, -OCH₂-, -CH₂O— or —C≡C—
X¹, X³, X⁴, X⁵And X⁶Are each independently H or F;
p and q are each independently 0, 1 or 2, but the sum of p and q is 2 or less,
X²Are -H, -F, -Cl-, CN, -CF₃-, -CF₂-, -OCH₂F, -OCHF₂, -OCF₃, -CH₂CF₃Or R¹Is the same definition as And a nematic liquid crystal composition comprising one or more compounds selected from the group consisting of:
[0016]
DETAILED DESCRIPTION OF THE INVENTION
An example of the present invention will be described below.
In general formula (I), R¹Is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, an unsubstituted linear alkyl group having 1 to 8 carbon atoms or 2 to 2 carbon atoms. The alkenyl group of 8 is more preferable, and the structure of the following formulas (a) to (e) is more preferable in the alkenyl group.
[0017]
[Chemical Formula 10]

(The structural formula shall be connected to the ring at the right end.)
A¹Is preferably a trans-1,4-cyclohexylene group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene group, and trans-1,4 -A cyclohexylene group is more preferable, and n is preferably 1.
[0018]
The compound represented by the general formula (I) is particularly preferably the following compound as a specific structure.
Embedded image

(Wherein R¹Represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. )
[0019]
General formula (Ia) in compounds of general formula (I)
Embedded image

[0020]
Can be produced as follows. Formula (IV)
Embedded image

(Wherein R and n are the same definitions as in general formula (I).) The hexanoic acid derivative represented by general formula (I) was enolized using a strong base such as lithium diisopropylamide, lithium hexamethyldisilazide or butyllithium. Thereafter, by reacting 3,4,5-trifluorobenzyl bromide, general formula (Va)
[0021]
Embedded image

(Wherein, R and n are the same definitions as in general formula (I)). This ester is hydrolyzed with sodium hydroxide or potassium hydroxide, and the resulting carboxylic acid is converted into an acid chloride using thionyl chloride and the like, and then reacted with a Lewis acid such as aluminum chloride. Formula (VI-a)
[0022]
Embedded image

(Wherein R and n are the same definitions as in general formula (I).) Indanone derivatives represented by formula (I) can be obtained. This is reduced using sodium borohydride, lithium aluminum hydride or the like, and the resulting alcohol is heated in the presence of an acid catalyst such as p-toluenesulfonic acid, thereby giving a general formula (VII-a)
[0023]
Embedded image

(Wherein R and n are the same definitions as in general formula (I)). This is Pd-C, Rh-C, Pt-C, Pd (OH)₂The target compound represented by the general formula (Ia) can be obtained by hydrogenation in the presence of a metal catalyst such as.
[0024]
In addition, the general formula (Ib) in the compound of the general formula (I)
Embedded image

Can be produced as follows.
[0025]
In the production of (Ia), instead of 3,4,5-trifluorobenzyl bromide, 3,5-difluorobenzyl bromide was used, and general formula (VIII)
Embedded image

(Wherein R and n are the same definitions as in general formula (I)) can be obtained. This was lithiated using a strong base such as butyllithium, lithium diisopropylamide, or lithium hexamethyldisilazide, and then reacted with carbon dioxide to give a compound represented by the general formula (IX)
[0026]
Embedded image

(In the formula, R and n are the same definitions as in general formula (I).) A compound represented by formula (I) is obtained, and this is converted into an acid chloride using thionyl chloride and the like, and then reacted with ammonia to obtain The obtained amide can be dehydrated with phosphorus oxychloride or the like to obtain the target compound represented by the general formula (Ib).
[0027]
(Ib) is a method in which (VIII) is lithiated, then reacted with N, N-dimethylformamide to introduce a formyl group, then reacted with hydroxyamine, and further dehydrated (VIII) ) After lithiation, iodine can be reacted, and copper cyanide can be further reacted.
[0028]
In addition, the general formula (Ic) in the compound of the general formula (I)
[0029]
Embedded image

(Wherein R and n are the same definitions as in general formula (I)) can be produced as follows.
[0030]
In the production of (Ia), instead of 3,4,5-trifluorobenzyl bromide, 3,4-dichlorobenzyl bromide was used, and general formula (X)
Embedded image

(In the formula, R and n are the same definitions as in general formula (I).) A compound represented by the formula (I) is obtained, and it can be produced by a method in which copper cyanide is reacted.
[0031]
In the liquid crystal composition of the present invention, the compound selected from the general formula (I) as the first component contains one type or two or more types, preferably 1 type to 6 types, more preferably 1 type to 4 types, 1 type-3 types are especially preferable.
[0032]
Moreover, it is preferable that the content rate of general formula (I) is the range of 5-50 mass%, and it is especially preferable that it is the range of 10-40 mass%.
[0033]
Of the compounds selected from the general formula (I), at least one composition preferably contains a compound having a dielectric anisotropy (Δε) of 1.5 or more, more preferably 2 or more.
[0034]
The second component contains one or more compounds selected from the group consisting of general formula (II), general formula (IIIa), general formula (IIIb) and general formula (IIIc). Species are preferred, 1 to 15 species are more preferred, and 1 to 10 species are particularly preferred. Moreover, as for these content rates, 10 mass%-80 mass% are preferable.
[0035]
R in general formula (II)²And R³Is preferably an unsubstituted linear alkyl group having 1 to 15 carbon atoms, a linear alkoxyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and an unsubstituted linear alkyl group having 1 to 15 carbon atoms. 10 alkyl groups or alkenyl groups having 2 to 10 carbon atoms are more preferable, unsubstituted linear alkyl groups having 1 to 8 carbon atoms or alkenyl groups having 2 to 6 carbon atoms are particularly preferable. ) To (e) are more preferable.
R²And R³May be the same or different, but R in the same molecule²And R³Are more preferably different. L¹And L²Is -CH₂CH₂—, —COO—, —OCO—, —CH═CH—, —CH═N—N═CH—, —C≡C— or a single bond is preferred, and —CH₂CH₂—, —CH═CH—, —CH═N—N═CH—, —C≡C— or a single bond is more preferable, and —CH═N—N═CH—, —C≡C— or a single bond is particularly preferable. Preferably, L¹And L²When a plurality of are present, at least one is preferably a single bond. o is preferably 0 or 1.
[0036]
C¹, C²And C³Are preferably independently trans-cyclohexane-1,4-diyl group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene group. More preferably a trans-cyclohexane-1,4-diyl group or a 1,4-phenylene group;¹, C²And C³At least one of them is preferably a trans-1,4-cyclohexylene group.
[0037]
The general formula (II) preferably has a structure represented by the following general formula (IIa).
Embedded image

(Wherein R²And R³Represents an alkyl group or alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 3 to 16 carbon atoms, and B³Represents a 1,4-phenylene group or a trans-cyclohexane-1,4-diyl group, and r represents 0 or 1. )
[0038]
It is preferable that the content rate of the compound of general formula (IIa) is the range of 10-80 mass%.
The general formula (II) is also preferably a structure represented by the following general formula as a specific structure.
Embedded image

[0039]
(Wherein R⁵And R⁶Each independently represents an alkyl or alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 3 to 16 carbon atoms. ) Is preferable.
Moreover, although the compound chosen from general formula (II) contains 1 type, or 2 or more types, 1 type-15 types are preferable and 1 type-10 types are especially preferable.
[0040]
R in general formula (IIIa), general formula (IIIb) and general formula (IIIc)⁴Is preferably an unsubstituted linear alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and an unsubstituted linear alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. A group is more preferable, and an unsubstituted linear alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 6 carbon atoms is particularly preferable. In the alkenyl group, structures of formulas (a) to (e) are more preferable. K¹, K²And K³Is —COO—, —OCO—, —CH₂CH₂-, -C≡C-,-(CH₂)₄-Or a single bond is preferred, -CH₂CH₂-, -C≡C- or a single bond is more preferable, -CH₂CH₂-Or a single bond is particularly preferred, K¹, K²Or K³When a plurality of are present, at least one is preferably a single bond.
p and q are preferably 0 or 1. C¹, C²And C³Are each independently preferably trans-cyclohexane-1,4-diyl group, 1,4-phenylene group, 3-fluoro-1,4-phenylene group or 3,5-difluoro-1,4-phenylene group. Trans-cyclohexane-1,4-diyl group or 1,4-phenylene group is more preferable, and trans-1,4-cyclohexylene group is particularly preferable.
X²Are -H, -F, -Cl-, CN, -CF₃-, -OCH₂F, -OCHF₂, -OCF₃, -CH₂CF₃Or R¹Is the same definition as -F, -CN, -CF₃-, -OCH₂F, -OCHF₂, -OCF₃Are preferred, and -F and -CN are particularly preferred.
[0041]
General formula (IIIa) is a structure represented by the following general formula (IIIa-1)
Embedded image

(Wherein R⁷Represents an alkyl group having 1 to 8 carbon atoms or an alkoxyl group, an alkenyl group having 2 to 8 carbon atoms, and L⁵, L⁶Are each independently -CH₂CH₂-, -CH = CH-, -C≡C-,-(CH₂)₄-Or a single bond, ring I represents a 1,4-phenylene group or a trans-cyclohexane-1,4-diyl group, X⁶Represents H or F, n represents 0 or 1, Y⁴Are -CN, -F, -Cl, -CF₃, -OCF₃Or -OCHF₂Represents. ) Is preferred, and the specific structure
[0042]
Embedded image

[0043]
Embedded image

[0044]
Embedded image

[0045]
Embedded image

(Wherein R⁷Represents an alkyl group having 1 to 8 carbon atoms or an alkoxyl group, an alkenyl group having 2 to 8 carbon atoms, and X³And X⁴Each independently represents H or F, Y⁴Is CN, F, Cl, -CF₃, -OCF₃Or -OCHF₂Represents. ) Is particularly preferable.
General formula (IIIb) has the following general formula as a specific structure:
[0046]
Embedded image

[0047]
Embedded image

[0048]
(Wherein R⁷Represents an alkyl group having 1 to 8 carbon atoms or an alkoxyl group, an alkenyl group having 2 to 8 carbon atoms, and Y⁴Are -CN, -F, -Cl, -CF₃, -OCF₃Or -OCHF₂Represents. ) Is preferred, and the general formula (IIIc) is represented by the following general formula as a specific structure:
[0049]
Embedded image

[0050]
Embedded image

[0051]
Embedded image

[0052]
(Wherein R⁷Represents an alkyl group having 1 to 8 carbon atoms or an alkoxyl group, an alkenyl group having 2 to 8 carbon atoms, and Y⁴Are -CN, -F, -Cl, -CF₃, -OCF₃Or -OCHF₂Represents. )
1 type or 2 types or more are included for the compound chosen from the group which consists of general formula (IIIa), general formula (IIIb), and general formula (IIIc), 1 type-10 types are preferable, 2 types-8 types are Particularly preferred.
[0053]
The nematic liquid crystal composition of the present invention contains one or more compounds selected from general formula (I), and is further selected from the group consisting of general formula (IIIa), general formula (IIIb) and general formula (IIIc). It is preferable to contain one or more selected compounds, one or more compounds selected from general formula (I) are contained, and one compound selected from general formula (II) or It is also preferable to contain 2 or more types.
[0054]
1 type, 2 or more types of compounds of general formula (I) are contained, and also 1 type or 2 types or more of compounds of general formula (II) are contained, and further general formula (IIIa), general formula (IIIb), and general formula It is preferable to contain at least one or more compounds selected from the group consisting of (IIIc), containing at least one compound of general formula (II), and further comprising general formula (IIIa) and general formula ( It is preferable to contain at least two compounds selected from the group consisting of IIIb) and general formula (IIIc).
[0055]
Further, it may contain one or more compounds selected from general formula (IIIa), and may contain one or more compounds selected from the group consisting of general formula (IIIb) and general formula (IIIc). Preferably, the content of the group consisting of general formula (IIIa), general formula (IIIb) and general formula (IIIc) is in the range of 10 to 50% by mass.
[0056]
1 type or 2 types or more of the compound represented by general formula (I) is contained, the content rate is the range of 5-50 mass%, and also 1 type or 2 types or more of compounds of general formula (IIa) are included. In the range of 10 to 60% by mass and containing one or more compounds selected from the group consisting of general formula (IIIa), general formula (IIIb) and general formula (IIIc) And it is especially preferable that the content rate is the range of 5-50 mass%.
[0057]
The nematic liquid crystal composition of the present invention has a wide liquid crystal phase temperature range (absolute value of the difference between the liquid crystal phase lower limit temperature and the liquid crystal phase upper limit temperature), but the liquid crystal phase temperature range is preferably 80 ° C. or higher, preferably 90 ° C. or higher. Is more preferable, and 100 ° C. or higher is particularly preferable. Further, the upper limit temperature of the liquid crystal phase is preferably 70 ° C. or higher, more preferably 80 ° C. or higher. Furthermore, the liquid crystal phase lower limit temperature is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.
[0058]
The nematic liquid crystal composition is useful for AM-LCDs and STN-LCDs, and can be used for transmissive or reflective liquid crystal display elements. The nematic liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal and the like in addition to the above compounds.
[0059]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
[0060]
In the examples, the measured characteristics are as follows.
T_NI  : Nematic phase-isotropic liquid phase transition temperature (° C) is the upper limit temperature of liquid crystal phase
Be
T_{→ N}  : Liquid phase or solid phase-nematic phase transition temperature (° C)
The lower limit of crystal phase temperature
ΔT: Nematic liquid crystal phase temperature range, | T_NI  -T_{→ N}  ｜
The following abbreviations are used in compound descriptions.
[0061]
Terminal n (number) C_nH_{2n + 1}−
E-COO-
e -OCO-
A -CH₂CH₂−
B-CH₂CH₂CH₂CH₂−
t -C≡C-
CN -C≡N
On-OC_nH_{2n + 1}
FF
f F atom bonded to the ortho position of the terminal group
ndm- C_nH_{2n + 1}-C = C- (CH₂)_m-1−
[0062]
Embedded image

[0063]
Example 1 Synthesis of 2- [4- (trans-4-propylcyclohexyl) butyl] -4,5,6-trifluoroindane
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[0064]
To a solution of diisopropylamine (57 g) in tetrahydrofuran (250 ml) was added butyllithium (1.6 M hexane solution, 360 ml) at −60 ° C., stirred for 30 minutes, then warmed to −20 ° C. Stir. The reaction solution was cooled to −60 ° C., a solution of ethyl 6- (trans-4-propylcyclohexyl) hexanoate (120 g) in tetrahydrofuran (100 ml) was added dropwise, stirred for 1 hour, Fluorobenzyl bromide (106 g) was added dropwise. While stirring, the temperature was raised to 0 ° C. over 3 hours, and then the reaction solution was poured into a 20% aqueous ammonium chloride solution and extracted with hexane. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, concentrated, and 6- (trans-4-propylcyclohexyl) -2- (3,4,5-trifluorobenzyl) hexane. A crude ethyl acid product (195 g) was obtained.
[0065]
To a solution of ethyl 6- (trans-4-propylcyclohexyl) -2- (3,4,5-trifluorobenzyl) hexanoate crude product (195 g) in ethanol (300 ml) was added a 20% aqueous sodium hydroxide solution (160 ml) was added and heated to reflux for 4 hours. The reaction solution was allowed to cool to room temperature, and 3 M hydrochloric acid was added until the reaction solution became acidic. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The organic layer was collected, washed with saturated brine, and concentrated to obtain 6- (trans-4-propylcyclohexyl) -2- (3,4,5-trifluorobenzyl) hexanoic acid crude product (190 g). .
[0066]
To a solution of crude 6- (trans-4-propylcyclohexyl) -2- (3,4,5-trifluorobenzyl) hexanoic acid (190 g) in 1,2-dichloroethane (200 ml) at room temperature was thionyl chloride (200 ml). 125 g) was added dropwise and heated to reflux for 4 hours. Thereafter, the solvent and excess thionyl chloride were distilled off to obtain a crude product (202 g) of 6- (trans-4-propylcyclohexyl) -2- (3,4,5-trifluorobenzyl) hexanoic acid chloride. Obtained.
[0067]
To a suspension of anhydrous aluminum chloride (100 g) in dichloromethane (150 ml), while maintaining the internal temperature at 0 to 5 ° C., 6- (trans-4-propylcyclohexyl) -2- (3,4,5-tri A solution of a crude product of fluorobenzyl) hexanoic acid chloride (202 g) in dichloromethane (100 ml) was added dropwise, and the mixture was further stirred for 2 hours. The reaction solution was poured into ice water, the organic layer was separated, and the aqueous layer was further extracted with dichloromethane. The organic layer was collected, washed with saturated brine, concentrated, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 20: 1) to give 2- [4- (trans-4-propylcyclohexyl) butyl]- 5,6,7-trifluoroindan-1-one (132 g) was obtained.
[0068]
Sodium borohydride was stirred vigorously into a solution of 2- [4- (trans-4-propylcyclohexyl) butyl] -5,6,7-trifluoroindan-1-one (132 g) in methanol (250 ml). (6 g) was added and stirred for 2 hours. Saturated brine was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. Toluene (300 ml) and p-toluenesulfonic acid monohydrate (5 g) were added to the residue, and the mixture was heated to reflux for 4 hours. The reaction mixture was allowed to cool to room temperature, water was added, and the mixture was extracted with toluene, washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and concentrated. The residue was purified by silica gel column chromatography (hexane) to obtain 2- [4- (trans-4-propylcyclohexyl) butyl] -5,6,7-trifluoroindan-1-ene (104 g).
[0069]
In an autoclave, 2- [4- (trans-4-propylcyclohexyl) butyl] -5,6,7-trifluoroindan-1-ene (104 g), 5% palladium-carbon (50% water content, 10 g), Ethyl acetate (300 ml) was added, and the mixture was stirred at room temperature for 3 hours under hydrogen (0.5 MPa) pressure. The reaction mixture was filtered through celite, the filtrate was concentrated, the residue was purified by silica gel column chromatography (hexane), and 2- [4- (trans-4-propylcyclohexyl) butyl] -4,5,6-trifluoro. Indan (98 g) was obtained.
¹H NMR (CDCl₃) 0.8-1.05 (m, 4 H), 0.89 (t, J = 7.2 Hz, 3 H), 1.1-1.4 (m, 14 H), 1.72 -1.88 (m, 4 H), 2.2-2.3 (m, 1 H), 2.5-2.65 (m, 2 H), 2.94 (dd, J = 8.3 and 16 Hz, 1 H), 3.06 (dd, J = 8.2 and 16 Hz, 1 H), 6.74 (broad t, J = 8 Hz, 1 H)
MS m / z 352 (M⁺)
[0070]
Example 2 Synthesis of 5-cyano-4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane
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[0071]
In Example 1, 3,6-difluorobenzyl bromide was used instead of 3,4,5-trifluorobenzyl bromide, and 4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl was used. Indane (79 g) was obtained.
[0072]
To a solution of 4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane (79 g) in tetrahydrofuran (300 ml) at −60 ° C., butyl lithium (1.6 M hexane solution, 170 ml) was added dropwise and stirred for 1 hour. Thereafter, carbon dioxide was blown in, and after stirring for 1 hour, the temperature was raised to room temperature. The reaction solution was poured into 1 M hydrochloric acid, the organic layer was separated, and the aqueous layer was further extracted with ethyl acetate. The organic layer was collected, washed with saturated brine, and concentrated to obtain 4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane-5-carboxylic acid crude product (83 g). It was.
[0073]
Thionyl chloride was added to a solution of 4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane-5-carboxylic acid crude product (83 g) in 1,2-dichloroethane (150 ml) at room temperature. (40 ml) was added dropwise and heated to reflux for 4 hours. Thereafter, the solvent and excess thionyl chloride were distilled off. The residue was dissolved in dichloromethane (200 ml), and ammonia gas was blown at 0 ° C., followed by further stirring for 2 hours. 1 M hydrochloric acid was added to the reaction solution, the organic layer was separated, and the aqueous layer was further extracted with ethyl acetate. The organic layer was collected, washed with saturated brine, concentrated, and 4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane-5-carboxylic acid amide crude product (85 g) was obtained. Obtained.
[0074]
To a solution of crude 4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane-5-carboxylic acid amide (85 g) in N, N-dimethylformamide (200 ml) was added oxy Phosphorus chloride (35 ml) was added dropwise. Furthermore, it heated at 50 degreeC for 1 hour, and stood to cool to room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with a saturated aqueous sodium carbonate solution and saturated brine, and concentrated. The residue was purified by silica gel column chromatography (toluene) to obtain 5-cyano-4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane (49 g).
¹H NMR (CDCl₃) 0.8-1.05 (m, 4 H), 0.88 (t, J = 7.5 Hz, 3 H), 1.1-1.4 (m, 14 H), 1.65 −1.86 (m, 4 H), 2.3-2.45 (m, 1 H), 2.57 (dd, J = 16 and 9 Hz, 1 H), 2.70 (dd, J = 16 and 9 Hz, 1 H), 3.0-3.2 (m, 2 H), 6.85 (d, J
= 8 Hz, 1 H)
MS m / z 359 (M⁺)
[0075]
Example 3 Synthesis of 5,6-dicyano-2- [4- (trans-4-propylcyclohexyl) butyl] indane
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[0076]
In Example 1, instead of 3,4,5-trifluorobenzyl bromide, 3,4-dichlorobenzyl bromide was used, and 5,6-dichloro-2- [4- (trans-4-propylcyclohexyl) butyl was used. Indane (68 g) was obtained.
To a solution of 5,6-dichloro-2- [4- (trans-4-propylcyclohexyl) butyl] indane (68 g) in N, N-dimethylformamide (300 ml) was added copper cyanide (25 g), Heated to reflux for 6 hours. After allowing to cool, the reaction mixture was filtered through celite, water was added to the filtrate, and the mixture was extracted with toluene. The organic layer was washed with saturated brine, saturated aqueous sodium hydrogen carbonate solution, 1 M hydrochloric acid and saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (twice with toluene and hexane / ethyl acetate = 4: 1) to give 5,6-dicyano-2- [4- (trans-4-propylcyclohexyl) butyl] indane (17 g )
¹H NMR (CDCl₃) 0.8-1.06 (m, 4 H), 0.87 (t, J = 7.6 Hz, 3 H), 1.1-1.4 (m, 14 H), 1.64 -1.87 (m, 4 H), 2.31-2.47 (m, 1 H), 2.61 (dd, J = 16 and 9 Hz, 2 H), 3.10 (dd, J = 16 and 7 Hz, 2 H), 7.65 (s, 2 H) MS m / z 348 (M⁺)
[0077]
(Example 4 and Comparative Example 1) Preparation of liquid crystal composition
Nematic liquid crystal composition (No. 1) containing 2- [4- (trans-4-propylcyclohexyl) butyl] -4,5,6-trifluoroindane synthesized in Example 1 and a similar structure A nematic liquid crystal composition (No. 2) was prepared and its physical properties were measured, and the results are shown in Table 1.
[0078]
[Table 1]

[0079]
As shown in Table 1, the nematic liquid crystal composition of Example 4 has a lower limit temperature (T_{→ N}) Is high and the liquid crystal phase upper limit temperature (T_NI) Is low and has a wide liquid crystal temperature range. Using this nematic liquid crystal composition, TN and STN liquid crystal display elements having excellent display quality could be produced.
[0080]
(Example 5 and Comparative Example 2) Preparation of liquid crystal composition
A nematic liquid crystal composition (No. 3) containing 5-cyano-4,6-difluoro-2- [4- (trans-4-propylcyclohexyl) butyl] indane synthesized in Example 2 and a similar structure were prepared. The nematic liquid crystal composition (No. 4) was prepared and its physical properties were measured. The results are shown in Table 2.
[0081]
[Table 2]

[0082]
As shown in Table 2, the nematic liquid crystal composition of Example 5 has a lower limit temperature (T_{→ N}) Is high and the liquid crystal phase upper limit temperature (T_NI) Is low and has a wide liquid crystal temperature range. Using this nematic liquid crystal composition, TN and STN liquid crystal display elements having excellent display quality could be produced.
[0083]
(Example 6 and Comparative Example 2) Preparation of liquid crystal composition
A nematic liquid crystal composition (No. 5) containing 5,6-dicyano-2- [4- (trans-4-propylcyclohexyl) butyl] indane synthesized in Example 6 and a nematic liquid crystal composition having a similar structure The physical properties (No. 4) were adjusted and the physical properties thereof were measured. The results are shown in Table 3.
[0084]
[Table 3]

[0085]
As shown in Table 3, the nematic liquid crystal composition of Example 5 has a lower limit temperature (T_{→ N}) Is equivalent to Comparative Example 2, but the liquid crystal phase upper limit temperature (T_NI) Is high and has a wide liquid crystal temperature range.
[0086]
Using this nematic liquid crystal composition, TN and STN liquid crystal display elements having excellent display quality could be produced.
[0087]
【The invention's effect】
According to the nematic liquid crystal composition of the present invention, a 4,5,6-trisubstituted indane compound or a 5,6-disubstituted indane compound has a high liquid crystal phase minimum temperature, a liquid crystal phase maximum temperature low, It became possible to provide a nematic liquid crystal composition having a wide phase temperature range. A liquid crystal display device using the liquid crystal composition of the present invention has excellent display quality over a wide temperature range.

Claims (15)

Formula (I)

Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 15 carbon atoms substituted with at least one halogen, an alkenyl group having 2 to 15 carbon atoms or at least one halogen. Represents a substituted alkenyl group having 2 to 15 carbon atoms, and one or two or more CH ₂ groups present in these groups are each independently —O—, wherein O atoms are not directly bonded to each other, May be replaced by -S-, -CO-, -COO-, -OCO- or -OCO-O-;
A ¹ is,
(A) trans-cyclohexane-1,4-diyl group (one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups are represented by —O— and / or —S—) May be replaced)
(B) 1,4-phenylene group (one —CH═ group present in this group or two or more non-adjacent —CH═ groups may be replaced by —N =)
(C) Cyclohexene-1,4-diyl group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- A group selected from the group consisting of a 2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the groups (a), (b) and (c) May be substituted with CN or halogen,
n is 1 or 2,
Y is the following formula

Is a group selected from An indane compound represented by: A nematic liquid crystal composition comprising one or more compounds represented by formula (I) according to claim 1. Formula (II)

(Wherein R ² and R ³ each independently represent the same meaning as R ¹ ,
B ¹ , B ² and B ³ are each independently (a) a trans-cyclohexane-1,4-diyl group (one CH ₂ group present in this group or two or more non-adjacent groups). CH ₂ group may be replaced by -O- and / or -S-)
(B) 1,4-phenylene group (one —CH═ group present in this group or two or more non-adjacent —CH═ groups may be replaced by —N =)
(C) Cyclohexene-1,4-diyl group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- A group selected from the group consisting of a 2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the groups (a), (b) and (c) May be substituted with CN or halogen,
o is 0, 1 or 2;
L ¹ , L ² and L ³ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CH═N—N═CH— or —C≡C—, and when there are a plurality of L ² and B ^3, they may be the same or different. good. And / or the group consisting of general formula (IIIa), general formula (IIIb) and general formula (IIIc)

(Wherein R ⁴ represents the same meaning as R ^1, and C ¹ , C ² and C ³ are each independently
(D) trans-cyclohexane-1,4-diyl group (one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups are represented by —O— and / or —S—) May be replaced)
(E) 1,4-phenylene group (one —CH═ group present in this group or two or more non-adjacent —CH═ groups may be replaced by —N =)
(F) cyclohexylene-1,4-diyl group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- A group selected from the group consisting of a 2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the group (d), the group (e) and the group (f) May be substituted with CN or halogen, but when it represents 1,2,3,4-tetrahydronaphthalene-2,6-diyl, it is unsubstituted or substituted with at least two or more halogens ,
K ¹ , K ² and K ³ each independently represent a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O— or —C≡C—,
X ¹ , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently H or F;
p and q are each independently 0, 1 or 2, but the sum of p and q is 2 or less,
X ² is the same definition as —H, —F, —Cl—, —CN, —CF ₃ , —CF ₂ H, —OCH ₂ F, —OCHF ₂ , —OCF ₃ , —CH ₂ CF ₃ or R ^1. It is. The nematic liquid crystal composition according to claim 2, which contains one or more compounds selected from the group consisting of: The nematic liquid crystal composition according to claim 2 or 3, wherein the content of the compound of the general formula (I) is in the range of 5 to 50% by mass. The nematic liquid crystal composition according to claim 3, comprising at least two compounds selected from the group consisting of general formula (IIIa), general formula (IIIb) and general formula (IIIc). A compound containing at least one compound of the general formula (II) and further containing at least two compounds selected from the group consisting of the general formula (IIIa), the general formula (IIIb) and the general formula (IIIc). 3. The nematic liquid crystal composition according to 3. As a compound of general formula (II), general formula (IIa)

(Wherein R ² and R ³ represent an alkyl group or alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having ³ to 16 carbon atoms, and B ³ represents 1 , 4-phenylene group or trans-cyclohexane-1,4-diyl group, and r represents 0 or 1.) The nematic liquid crystal composition according to claim 3 or 6. The nematic liquid crystal composition according to claim 7, wherein the content of the compound of the general formula (IIa) is in the range of 10 to 80% by mass. 3. One or more compounds selected from general formula (IIIa) are contained, and one or more compounds selected from the group consisting of general formula (IIIb) and general formula (IIIc) are contained. The nematic liquid crystal composition according to 5 or 6. The nematic liquid crystal composition according to claim 9, wherein the content of the group consisting of general formula (IIIa), general formula (IIIb), and general formula (IIIc) is in the range of 10 to 50 mass%. 1 type or 2 types or more of the compound represented by general formula (I) is contained, the content rate is the range of 5-50 mass%, and also 1 type or 2 types or more of compounds of general formula (IIa) are included. In the range of 10 to 60% by mass and containing one or more compounds selected from the group consisting of general formula (IIIa), general formula (IIIb) and general formula (IIIc) The nematic liquid crystal composition according to claim 10, wherein the content is in the range of 5 to 50 mass%. The liquid crystal display element using the nematic liquid crystal composition in any one of Claims 2-11. An active matrix liquid crystal display device using the nematic liquid crystal composition according to claim 2. A super twisted nematic (STN) liquid crystal display element using the nematic liquid crystal composition according to claim 2 and having a twist angle of 180 ° to 270 °. A twisted nematic (TN) liquid crystal display element using the nematic liquid crystal composition according to claim 2 and having a twist angle of 80 ° to 130 °.