JPH0158168B2 - - Google Patents
Info
- Publication number
- JPH0158168B2 JPH0158168B2 JP7792882A JP7792882A JPH0158168B2 JP H0158168 B2 JPH0158168 B2 JP H0158168B2 JP 7792882 A JP7792882 A JP 7792882A JP 7792882 A JP7792882 A JP 7792882A JP H0158168 B2 JPH0158168 B2 JP H0158168B2
- Authority
- JP
- Japan
- Prior art keywords
- trans
- cyclohexyl
- biphenyl
- liquid crystal
- pentylcyclohexyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 42
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 26
- 235000010290 biphenyl Nutrition 0.000 claims description 21
- 239000004305 biphenyl Substances 0.000 claims description 21
- 239000004973 liquid crystal related substance Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- -1 Substituted-4'-bromobiphenyl Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 6
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- AUXIEQKHXAYAHG-UHFFFAOYSA-N 1-phenylcyclohexane-1-carbonitrile Chemical compound C=1C=CC=CC=1C1(C#N)CCCCC1 AUXIEQKHXAYAHG-UHFFFAOYSA-N 0.000 description 1
- OZLFNAZSDVXEFU-UHFFFAOYSA-N 4-(4-pentylcyclohexyl)cyclohexan-1-one Chemical compound C1CC(CCCCC)CCC1C1CCC(=O)CC1 OZLFNAZSDVXEFU-UHFFFAOYSA-N 0.000 description 1
- XXUSEPRYHRDKFV-CTYIDZIISA-N C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(C#N)C=C1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(C#N)C=C1 XXUSEPRYHRDKFV-CTYIDZIISA-N 0.000 description 1
- FURZYCFZFBYJBT-JCNLHEQBSA-N C1C[C@@H](CCCCC)CC[C@@H]1C1=CC=C(C#N)C=C1 Chemical compound C1C[C@@H](CCCCC)CC[C@@H]1C1=CC=C(C#N)C=C1 FURZYCFZFBYJBT-JCNLHEQBSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JWQLJPBJNSPKSG-UHFFFAOYSA-M magnesium;phenylbenzene;bromide Chemical compound [Mg+2].[Br-].C1=CC=CC=C1C1=CC=[C-]C=C1 JWQLJPBJNSPKSG-UHFFFAOYSA-M 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は広い温度範囲で液晶相を示し、かつ低
粘性の新規な液晶物質及びそれらを含有する組成
物に関する。
液晶表示素子は液晶物質が有する光学異方性及
び誘電異方性を利用したものであるが、その表示
方式にはTN型、DS型、ゲスト・ホスト型、
DAP型、ホワイト・テイラー型など各種の方式
があり、それぞれの方式により使用される液晶物
質に要求される性質も異る。例えば表示素子の種
類によつて、液晶物質として誘電異方性△εが正
のものを必要としたり、負のものを必要とした
り、或はその中間的な値のものが適したりする。
しかしいずれにしても使用される液晶物質はでき
るだけ広い温度範囲で液晶相を示し、又水分、
熱、空気、光などに対して安定である必要があ
る。現在のところ単一化合物でこの様な条件をす
べてみたすものはなく、数種の液晶化合物や非液
晶化合物を混合して一応実用に耐えるものを得て
いるのが現状である。最近広い温度範囲、すなわ
ち低温（−20℃位）から高温（80℃近く）まで動
作する液晶表示素子が要求されている。この要求
をみたすためにはより広い温度範囲で液晶相を示
し、かつ低粘性な液晶が必要とされている。本発
明はこのような要求をみたす液晶の構成成分とし
て有用な新規な化合物を提供するものである。
即ち本発明は一般式
（式中、Ｒは炭素数が１〜10を有するアルキル
基、R′は炭素数１〜10を有するアルキル基又は
アルコキシ基を示す）
で表わされる４―置換―4′―〔トランス―4″―
（トランス―４―置換シクロヘキシル）シクロ
ヘキシル〕ビフエニルである。
本発明の４―ペンチル―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〕ビフエニルは結晶―スメクチツク
点（Ｃ―Sm点）30℃以下、スメクチツク―透明
点（Sm―点）は300℃以上と広い温度範囲で液
晶相を示し、少量の添加で温度範囲の広い低粘性
なネマチツク液晶組成物をつくるのに好適な物質
である。
つぎに本発明の化合物の製造法を示すと、４―
置換―4′―ブロモビフエニルにマグネシウムを作
用させ４―置換―4′―ビフエニルマグネシウムブ
ロミドとし、それに４―（トランス―4′―置換シ
クロヘキシル）シクロヘキサノンと反応させ、４
―置換―4′―〔4″―（トランス―４―置換シク
ロヘキシル）シクロヘキサン―1″―オール〕ビフ
エニル（）とする。ついでこれを硫酸水素カリ
ウムを触媒として脱水して４―置換―4′―〔4″―
（トランス―４―置換シクロヘキシル）シクロ
ヘキセン―1″―イル〕ビフエニル（）を得る。
これをｎ―ヘプタン溶媒中ラネーニツケル触媒を
用いて、常圧50℃にて還元し、それを再結晶する
ことによつてシス体を除き、目的物である４―置
換―4′―〔トランス―4″―（トランス―４―置
換シクロヘキシル）シクロヘキシル〕ビフエニル
（）を得る。
以上を化学式で示すと、
又、本発明の化合物は次の方法でも得られる。
４―ブロモビフエニルに金属マグネシウムを反応
させ４―ビフエニルマグネシウムブロミドとし、
これに４―（トランス―4′―置換シクロヘキシ
ル）シクロヘキサノンを反応させ４―〔4″―トラ
ンス―４―置換シクロヘキシル）シクロヘキサ
ン―1″―オール〕ビフエニル（）とし、ついで
硫酸水素カリウムで脱水し４―〔4″―（トランス
―４―置換シクロヘキシル）シクロヘキセン―
1″―イル〕ビフエニル（）とした後、ラネーニ
ツケル触媒で還元して４―〔トランス―4″―（ト
ランス―４―置換シクロヘキシル）シクロヘキ
シル〕ビフエニル（）を得る。つぎにこれを塩
化アルミニウムとアルカノイルクロライドとでフ
リーデル・クラフツ反応させて４―アルカノイル
―〔トランス―4″―（トランス―４―置換シク
ロヘキシル）シクロヘキシル〕ビフエニル（）
を得、これをウルフ・キツシユナー還元して、目
的物である４―置換―4′―〔トランス―4″―（ト
ランス―４―置換シクロヘキシル）シクロヘキ
シル〕ビフエニル（）を得る。以上を式で示す
とつぎのようになる。
（上式中R″は水素もしくは炭素数１〜９を有
するアルキル基を示す。）
以下、実施例で本発明の化合物の製造法及び使
用法についてさらに詳細に説明する。
実施例 １
４―ペンチル―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〕ビフエニルの製造
４―ペンチル―4′―ブロモビフエニル2.8g
（0.0092モル）を50mlのテトラヒドロフランに溶
かした液を窒素気流中マグネシウム0.22g（0.0092
モル）と反応させ４―ペンチル―4′―ビフエニル
マグネシウムブロミドとする。この反応液を０℃
に冷やし、４―（トランス―4′―ペンチルシクロ
ヘキシル）シクロヘキサノン2.3g（0.0092モル）
のテトラヒドロフラン溶液50mlを加える。50℃で
還流を２時間行なつた後3N―塩酸50mlを加え、
生成物をトルエン200mlで抽出する。水洗し、溶
媒を留去した後、硫酸水素カリウムを4g加え、
窒素雰囲気下200℃で２時間脱水する。冷却後ト
ルエン200mlを加えてから硫酸水素カリウムを
別し、次いで洗液が中性になるまで水洗する。無
水硫酸ナトリウムで脱水後溶媒を留去し、トルエ
ンで再結晶して得られた結晶が４―ペンチル―
4′―〔4″―（トランス―４―ペンチルシクロヘ
キシル）シクロヘキセン―1″―イン〕ビフエニル
である。このもの1.4g（0.0031モル）をｎ―ヘプ
タン200mlに溶かしラネーニツケル0.7gを加え常
圧下60℃で接触還元を行なつた。反応をガスクロ
マトグラフイーで追跡し、原料が消失した時点、
即ち12時間後に還元を終えた。このものはシス体
とトランス体の混合物であるので、トルエンで再
結晶させトランス体を取り出した。これが目的物
である４―ペンチル―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〕ビフエニルである。収量0.5g（0.001モ
ル）。このものはＣ―Sm点室温以下、Sm―Ｉ点
300℃以上と非常に広い液晶温度範囲を有してい
た。
実施例 ２
４―エチル―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〕ビフエニルの製造（別法）
金属マグネシウム3.6g（0.148モル）に４―ブロ
モビフエニル34.5g（0.148モル）をテトラヒドロ
フラン100mlに溶かした液を滴下し、窒素気流中
反応温度を35℃に保つと、２時間後マグネシウム
は溶けて均一溶液となる。これに、４―（トラン
ス―4′―ペンチルシクロヘキシル）シクロヘキサ
ノン29.6g（0.118モル）を溶かしたテトラヒドロ
フラン100mlを冷却しながら30℃以下で滴下する。
更に２時間還流させた後3N―塩酸200mlを加え、
トルエン１で抽出する。水洗を施し、溶媒を減
圧留去して得られる残留物が４―〔4″―（トラン
ス―４―ペンチルシクロヘキシル）シクロヘキ
サン―1″―オール〕ビフエニルである。このもの
に硫酸水素カリウム7gを加え、窒素気流中200℃
で脱水する。冷却後トルエン１で溶かし、硫酸
水素カリウムを別し、トルエン層を水洗した
後、溶媒を減圧留去し、トルエンで再結晶する。
得られた結晶物が４―〔4″―（トランス―４―
ペンチルシクロヘキシル）シクロヘキセン―1″―
イル〕ビフエニルである。このもの14.0g（0.0362
モル）をエタノール300mlとラネーニツケル4.0g
を加え、オートクレーブ中５Kg／cm280℃で３時間
還元する。触媒を別し、トルエンで洗つた後、
再結晶させ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〕
ビフエニルを得る。このもの2.0g（0.0052モル）
を二硫化炭素100mlに溶かし、更に無水塩化アル
ミニウム1.0g（0.0077モル）を懸濁させ、そこへ
０〜10℃に保ちながらアセチルクロライド0.42g
（0.0054モル）を滴下する。１時間半後、徐々に
昇温させ２時間還流する。冷却後6N―塩酸500ml
に内容物を注ぎ生ずる固形物を過し、その過
物をエタノールで再結晶する。これが４―アセチ
ル―〔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〕ビフエニル
である。このものの1.7g（0.0039モル）をエチレ
ングリコール200mlに溶かし、水酸化カリウム
0.49gと水化ヒドラジン0.52gを加え４時間還流す
る。エチレングリコールを留去し、トルエン200
mlを抽出し6N―塩酸で洗い、更に洗液が中性に
なるまで水洗した。トルエンを減圧留去し、新し
いトルエンで再結晶して目的物である４―エチル
―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〕ビフエニ
ル0.2gを得た。そのＣ―Ｓ点は68.0℃、Ｓ―Ｎ点
は290℃、Ｎ―Ｉ点は300℃以上であつた。
実施例 ３〜６
実施例１と同様にして（）式の置換基の異な
つたものについて合成した。それを実施例１及び
２の結果と共に第１表に示す。
The present invention relates to novel liquid crystal substances that exhibit a liquid crystal phase over a wide temperature range and have low viscosity, and compositions containing them. Liquid crystal display elements utilize the optical anisotropy and dielectric anisotropy of liquid crystal materials, and their display methods include TN type, DS type, guest-host type,
There are various types such as DAP type and White-Taylor type, and each type requires different properties of the liquid crystal material used. For example, depending on the type of display element, a liquid crystal material with a positive dielectric anisotropy Δε may be required, a material with a negative dielectric anisotropy may be required, or a material with an intermediate value may be suitable.
However, in any case, the liquid crystal materials used exhibit a liquid crystal phase over a wide temperature range, and also contain moisture and
It must be stable against heat, air, light, etc. At present, there is no single compound that satisfies all of these conditions, and the current situation is to obtain compounds that can be put to practical use by mixing several types of liquid crystal compounds and non-liquid crystal compounds. Recently, there has been a demand for liquid crystal display elements that can operate over a wide temperature range, from low temperatures (approximately -20°C) to high temperatures (nearly 80°C). In order to meet this demand, a liquid crystal that exhibits a liquid crystal phase over a wider temperature range and has low viscosity is required. The present invention provides a novel compound useful as a constituent of liquid crystals that satisfies these requirements. That is, the present invention is based on the general formula (In the formula, R is an alkyl group having 1 to 10 carbon atoms, and R' is an alkyl group or alkoxy group having 1 to 10 carbon atoms.) ―
(trans-4-substituted cyclohexyl)cyclohexyl]biphenyl. 4-pentyl-4′-[trans-4″-
(Trans-4-pentylcyclohexyl)cyclohexyl]biphenyl exhibits a liquid crystal phase over a wide temperature range, with a crystal-smectic point (C-Sm point) of 30°C or lower and a smectic-clearing point (Sm-point) of 300°C or higher. It is a suitable substance for making a low-viscosity nematic liquid crystal composition with a wide temperature range by adding . Next, the method for producing the compound of the present invention is shown below.
Substituted-4'-bromobiphenyl is reacted with magnesium to form 4-substituted-4'-biphenylmagnesium bromide, which is then reacted with 4-(trans-4'-substituted cyclohexyl)cyclohexanone,
-Substituted-4'-[4''-(trans-4-substituted cyclohexyl)cyclohexane-1''-ol]biphenyl (). Next, this was dehydrated using potassium hydrogen sulfate as a catalyst to obtain 4-substituted-4′-[4″-
(trans-4-substituted cyclohexyl)cyclohexen-1″-yl]biphenyl () is obtained.
This is reduced using a Raney-nickel catalyst in n-heptane solvent at normal pressure of 50°C, and is recrystallized to remove the cis isomer. 4″-(trans-4-substituted cyclohexyl)cyclohexyl]biphenyl () is obtained. Showing the above as a chemical formula, The compound of the present invention can also be obtained by the following method.
4-bromobiphenyl is reacted with metallic magnesium to produce 4-biphenylmagnesium bromide,
This was reacted with 4-(trans-4'-substituted cyclohexyl)cyclohexanone to form 4-[4''-trans-4-substituted cyclohexyl)cyclohexane-1''-ol]biphenyl (), and then dehydrated with potassium hydrogen sulfate to give 4 -[4″-(trans-4-substituted cyclohexyl)cyclohexene-
1″-yl]biphenyl () is then reduced with a Raney Nickel catalyst to obtain 4-[trans-4″-(trans-4-substituted cyclohexyl)cyclohexyl]biphenyl (). Next, this is subjected to a Friedel-Crafts reaction with aluminum chloride and alkanoyl chloride to cause 4-alkanoyl-[trans-4″-(trans-4-substituted cyclohexyl)cyclohexyl]biphenyl ()
This is subjected to Wolf-Kitsschuner reduction to obtain the target product 4-substituted-4′-[trans-4″-(trans-4-substituted cyclohexyl)cyclohexyl]biphenyl (). The above is shown by the formula It becomes as follows. (In the above formula, R″ represents hydrogen or an alkyl group having 1 to 9 carbon atoms.) Hereinafter, the method for producing and using the compound of the present invention will be explained in more detail in Examples. Example 1 4-pentyl -4'- [Trans-4''-(trans-4-pentylcyclohexyl)cyclohexyl] Production of biphenyl 4-pentyl-4'-bromobiphenyl 2.8g
(0.0092 mol) dissolved in 50 ml of tetrahydrofuran, 0.22 g (0.0092 mol) of magnesium was dissolved in 50 ml of tetrahydrofuran.
mol) to form 4-pentyl-4'-biphenylmagnesium bromide. This reaction solution was heated to 0°C.
Cool to 2.3 g (0.0092 mol) of 4-(trans-4'-pentylcyclohexyl)cyclohexanone.
Add 50 ml of tetrahydrofuran solution. After refluxing at 50°C for 2 hours, 50ml of 3N hydrochloric acid was added.
Extract the product with 200 ml of toluene. After washing with water and distilling off the solvent, 4g of potassium hydrogen sulfate was added.
Dehydrate at 200°C for 2 hours under nitrogen atmosphere. After cooling, add 200 ml of toluene, separate the potassium hydrogen sulfate, and then wash with water until the washing liquid becomes neutral. After dehydration over anhydrous sodium sulfate, the solvent was distilled off and the crystals obtained by recrystallizing from toluene were 4-pentyl-
4′-[4″-(trans-4-pentylcyclohexyl)cyclohexene-1″-yne]biphenyl. 1.4 g (0.0031 mol) of this product was dissolved in 200 ml of n-heptane, 0.7 g of Raney nickel was added, and catalytic reduction was carried out at 60° C. under normal pressure. The reaction was followed by gas chromatography, and when the raw materials disappeared,
That is, the reduction was completed after 12 hours. Since this product was a mixture of cis and trans forms, it was recrystallized with toluene to remove the trans form. This is the target product, 4-pentyl-4'-[trans-4''-(trans-4-pentylcyclohexyl)cyclohexyl]biphenyl. Yield: 0.5 g (0.001 mol). This product has a C-Sm point below room temperature, Sm-I point
It had an extremely wide liquid crystal temperature range of over 300℃. Example 2 Production of 4-ethyl-4′-[trans-4″-(trans-4-pentylcyclohexyl)cyclohexyl]biphenyl (alternative method) 34.5 g (0.148 mol) of 4-bromobiphenyl in 3.6 g (0.148 mol) of metallic magnesium ) dissolved in 100 ml of tetrahydrofuran is added dropwise and the reaction temperature is maintained at 35°C in a nitrogen stream.After 2 hours, magnesium dissolves to form a homogeneous solution.To this, 4-(trans-4'-pentylcyclohexyl) is added dropwise. 100 ml of tetrahydrofuran in which 29.6 g (0.118 mol) of cyclohexanone is dissolved is added dropwise at a temperature below 30°C while cooling.
After further refluxing for 2 hours, 200ml of 3N hydrochloric acid was added.
Extract with toluene 1. The residue obtained by washing with water and distilling off the solvent under reduced pressure is 4-[4''-(trans-4-pentylcyclohexyl)cyclohexane-1''-ol]biphenyl. Add 7g of potassium hydrogen sulfate to this mixture and heat at 200°C in a nitrogen stream.
Dehydrate. After cooling, the mixture is dissolved in 1 part of toluene, the potassium hydrogen sulfate is separated, the toluene layer is washed with water, the solvent is distilled off under reduced pressure, and the mixture is recrystallized with toluene.
The obtained crystalline substance is 4-[4″-(trans-4-
pentylcyclohexyl) cyclohexene-1″-
[il] biphenyl. This stuff 14.0g (0.0362
300ml of ethanol and 4.0g of Raney nickel
was added and reduced in an autoclave at 5 kg/cm 2 at 80°C for 3 hours. After separating the catalyst and washing it with toluene,
Recrystallize 4-[Trans-4″-(Trans-4
-pentylcyclohexyl) cyclohexyl]
Get biphenyl. 2.0g (0.0052mol) of this stuff
is dissolved in 100 ml of carbon disulfide, further suspended with 1.0 g (0.0077 mol) of anhydrous aluminum chloride, and 0.42 g of acetyl chloride is added thereto while maintaining the temperature at 0 to 10°C.
(0.0054 mol) was added dropwise. After 1 and a half hours, the temperature was gradually increased and the mixture was refluxed for 2 hours. After cooling 6N-hydrochloric acid 500ml
Pour the contents into a filtrate, filter the resulting solid, and recrystallize the filtrate from ethanol. This is 4-acetyl-[trans-4″-(trans-4-pentylcyclohexyl)cyclohexyl]biphenyl. Dissolve 1.7g (0.0039 mol) of this in 200ml of ethylene glycol, and dissolve potassium hydroxide.
Add 0.49 g and 0.52 g of hydrazine hydrate and reflux for 4 hours. Distill ethylene glycol and add toluene 200
ml was extracted, washed with 6N-hydrochloric acid, and further washed with water until the washing solution became neutral. Toluene was distilled off under reduced pressure and recrystallized with fresh toluene to obtain 0.2 g of the target product, 4-ethyl-4'-[trans-4''-(trans-4-pentylcyclohexyl)cyclohexyl]biphenyl. -S point was 68.0°C, S-N point was 290°C, and N-I point was 300°C or higher.Examples 3 to 6 Similar to Example 1, regarding different substituents of formula () The results are shown in Table 1 along with the results of Examples 1 and 2.
【表】
実施例 ７（使用例）
トランス―４―プロピル―（4′―シアノフエニ
ル）シクロヘキサン 28％
トランス―４―ペンチル―（4′―シアノフエニ
ル）シクロヘキサン 43％
トランス―４―ヘプチル―（4′―シアノフエニ
ル）シクロヘキサン 29％
なる組成の液晶組成物のネマチツク液晶温度範囲
は−３〜52℃、誘電異方性値△εは＋10.5であ
る。この液晶組成物をセル厚10μmのTNセル
（ねじれネマチツクセル）に封入したものの動作
しきい電圧は1.53V、飽和電圧は2.12Vであつた。
又粘度は20℃で23cpであつた。この組成物98部
に本発明の化合物である、４―ペンチル―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〕ビフエニル２部
を加えた液晶組成物のネマチツク液晶温度範囲は
−３〜56.2℃に広がり、△εは＋11.0、上記セル
に入れたものの動作しきい電圧は1.55V、飽和電
圧は2.15Vであつた。又粘度は20℃で24.9cpであ
つた。この様に本発明の化合物は少量の添加で低
粘性で広いネマチツク温度範囲をもつ組成物をつ
くるのに有効であることがわかる。[Table] Example 7 (Usage example) Trans-4-propyl-(4'-cyanophenyl)cyclohexane 28% Trans-4-pentyl-(4'-cyanophenyl)cyclohexane 43% Trans-4-heptyl-(4'- A liquid crystal composition having a composition of 29% cyanophenylcyclohexane has a nematic liquid crystal temperature range of -3 to 52 DEG C. and a dielectric anisotropy value Δε of +10.5. When this liquid crystal composition was sealed in a TN cell (twisted nematic cell) with a cell thickness of 10 μm, the operating threshold voltage was 1.53V and the saturation voltage was 2.12V.
The viscosity was 23 cp at 20°C. The compound of the present invention, 4-pentyl-4'-, was added to 98 parts of this composition.
The nematic liquid crystal temperature range of the liquid crystal composition to which 2 parts of [trans-4″-(trans-4-pentylcyclohexyl)cyclohexyl]biphenyl was added was widened from −3 to 56.2°C, and Δε was +11.0 when placed in the above cell. The operating threshold voltage was 1.55 V and the saturation voltage was 2.15 V.The viscosity was 24.9 cp at 20°C.Thus, the compound of the present invention has a low viscosity and a wide nematic temperature range even when added in a small amount. It can be seen that it is effective for creating compositions with
Claims (1)
基、R′は炭素数１〜10を有するアルキル基又は
アルコキシ基を示す） で表わされる４―置換―4′―〔トランス―4″―
（トランス―４―置換シクロヘキシル）シクロ
ヘキシル〕ビフエニル。 ２ 一般式 （式中、Ｒは炭素数が１〜10を有するアルキル
基、R′は炭素数１〜10を有するアルキル基又は
アルコキシ基を示す） で表わされる４―置換―4′―〔トランス―4″―
（トランス―４―置換シクロヘキシル）シクロ
ヘキシル〕ビフエニルを少なくとも一種含有する
ことを特徴とする液晶組成物。[Claims] 1. General formula (In the formula, R is an alkyl group having 1 to 10 carbon atoms, and R' is an alkyl group or alkoxy group having 1 to 10 carbon atoms.) ―
(trans-4-substituted cyclohexyl)cyclohexyl]biphenyl. 2 General formula (In the formula, R is an alkyl group having 1 to 10 carbon atoms, and R' is an alkyl group or alkoxy group having 1 to 10 carbon atoms.) ―
A liquid crystal composition containing at least one type of (trans-4-substituted cyclohexyl)cyclohexyl]biphenyl.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7792882A JPS58194822A (en) | 1982-05-10 | 1982-05-10 | 4-substituted-4'-(trans-4"-(trans-4'''-substituted cyclohexyl) cyclohexyl)biphenyl |
| US06/460,071 US4477369A (en) | 1982-01-22 | 1983-01-21 | New high temperature liquid-crystalline substances consisting of 4 or 5 six-member-rings and liquid-crystalline compositions containing same |
| DE8383300354T DE3362745D1 (en) | 1982-01-22 | 1983-01-24 | Carbocyclic compounds with liquid-crystal properties |
| EP19830300354 EP0084974B1 (en) | 1982-01-22 | 1983-01-24 | Carbocyclic compounds with liquid-crystal properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7792882A JPS58194822A (en) | 1982-05-10 | 1982-05-10 | 4-substituted-4'-(trans-4"-(trans-4'''-substituted cyclohexyl) cyclohexyl)biphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58194822A JPS58194822A (en) | 1983-11-12 |
| JPH0158168B2 true JPH0158168B2 (en) | 1989-12-11 |
Family
ID=13647742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7792882A Granted JPS58194822A (en) | 1982-01-22 | 1982-05-10 | 4-substituted-4'-(trans-4"-(trans-4'''-substituted cyclohexyl) cyclohexyl)biphenyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58194822A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04110975U (en) * | 1991-03-14 | 1992-09-25 | 矢崎総業株式会社 | Rotation-pulse conversion device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI814958B (en) | 2019-04-24 | 2023-09-11 | 日商捷恩智股份有限公司 | Liquid crystal compositions and their uses, and liquid crystal display elements |
-
1982
- 1982-05-10 JP JP7792882A patent/JPS58194822A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04110975U (en) * | 1991-03-14 | 1992-09-25 | 矢崎総業株式会社 | Rotation-pulse conversion device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58194822A (en) | 1983-11-12 |
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