JPH0247457B2 - 44HAROGENOANSOKUKOSANN44 * TORANSUU4 *** TORANSUU4 *** ARUKIRUSHIKUROHEKISHIRU * SHIKUROHEKISHIRU * FUENIRUESUTERU - Google Patents
44HAROGENOANSOKUKOSANN44 * TORANSUU4 *** TORANSUU4 *** ARUKIRUSHIKUROHEKISHIRU * SHIKUROHEKISHIRU * FUENIRUESUTERUInfo
- Publication number
- JPH0247457B2 JPH0247457B2 JP8527182A JP8527182A JPH0247457B2 JP H0247457 B2 JPH0247457 B2 JP H0247457B2 JP 8527182 A JP8527182 A JP 8527182A JP 8527182 A JP8527182 A JP 8527182A JP H0247457 B2 JPH0247457 B2 JP H0247457B2
- Authority
- JP
- Japan
- Prior art keywords
- trans
- cyclohexyl
- liquid crystal
- phenyl ester
- point
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004973 liquid crystal related substance Substances 0.000 claims description 28
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 27
- -1 phenyl ester Chemical class 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- CZKLEJHVLCMVQR-UHFFFAOYSA-N 4-fluorobenzoyl chloride Chemical compound FC1=CC=C(C(Cl)=O)C=C1 CZKLEJHVLCMVQR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- AKCZQKBKWXBJOF-UHFFFAOYSA-N 4-(4-propylcyclohexyl)cyclohexan-1-one Chemical compound C1CC(CCC)CCC1C1CCC(=O)CC1 AKCZQKBKWXBJOF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VOEZZIYXTINFMJ-UTCHBHPLSA-N C1C[C@@H](CCC)CC[C@@H]1C1CCC(O)(C=2C=CC(OC)=CC=2)CC1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1C1CCC(O)(C=2C=CC(OC)=CC=2)CC1 VOEZZIYXTINFMJ-UTCHBHPLSA-N 0.000 description 1
- FFIXAFACUXWNCV-VVPTUSLJSA-N C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC(O)=CC=2)CC1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC(O)=CC=2)CC1 FFIXAFACUXWNCV-VVPTUSLJSA-N 0.000 description 1
- YZWGZGROOKJGIH-KBQPQWKXSA-N C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC(OC(=O)C=3C=CC(F)=CC=3)=CC=2)CC1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC(OC(=O)C=3C=CC(F)=CC=3)=CC=2)CC1 YZWGZGROOKJGIH-KBQPQWKXSA-N 0.000 description 1
- GZMMUVKMQPSLLS-YSXIEMCBSA-N C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC=CC=2)CC1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](C=2C=CC=CC=2)CC1 GZMMUVKMQPSLLS-YSXIEMCBSA-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
- XCNQSMOOHQLJID-UHFFFAOYSA-N C[O-].[Mg+]c1ccccc1 Chemical compound C[O-].[Mg+]c1ccccc1 XCNQSMOOHQLJID-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 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
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RBWRWAUAVRMBAC-UHFFFAOYSA-M magnesium;methoxybenzene;bromide Chemical compound [Mg+2].[Br-].COC1=CC=[C-]C=C1 RBWRWAUAVRMBAC-UHFFFAOYSA-M 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【発明の詳細な説明】
本発明は広い温度範囲で液晶相を示す、正の誘
電異方性を有する新規液晶物質及びそれを含有す
る液晶組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel liquid crystal material exhibiting a liquid crystal phase over a wide temperature range and having positive dielectric anisotropy, and a liquid crystal composition containing the same.
液晶を使用した表示素子は時計、電卓などに広
く使用される様になつて来た。この液晶表示素子
は液晶物質の光学異方性及び誘電異方性という性
質を利用したものであるが、液晶相にはネマチツ
ク液晶相、スメクチツク液晶相、コレステリツク
液晶相があり、そのうちネマチツク液晶を利用し
たものが最も広く実用化されている。即ちそれら
にはTN(ねじれネマチツク)型、DS型(動的散
乱型)、ゲスト・ホスト型、DAP型などがあり、
それぞれに使用される液晶物質に要求される性質
は異る。しかし、いずれにしても、これら表示素
子に使用される液晶物質は自然界のなるべく広い
範囲で液晶相を示すものが望ましいが、現在のと
ころ単一物質でその様な条件をみたす様な物質は
なく、数種の液晶物質又は非液晶物質を混合して
一応実用に耐える様な物を得ているのが現状であ
る。又、これらの物質は水分、光、熱、空気等に
対しても安定でなければならないのは勿論であ
り、更に表示素子を駆動させる必要なしきい電
圧、飽和電圧がなるべく低いこと、又応答速度を
早くするためには粘度が出来るだけ低いことが望
ましい。ところで液晶温度範囲を高温の方に広く
するためには高融点の液晶物質を成分として使用
する必要があるが、一般に高融点の液晶物質は粘
度が高く、従つてそれを含む液晶組成物も粘度が
高くなるので、高温、例えば80℃位まで使用出来
る様な液晶表示素子の応答速度、特に低温でのそ
れは著るしくおそくなる傾向にあつた。しかるに
本発明者らは高い液晶温度範囲をもちながら低粘
度の液晶物質を見つけ本発明に到つた。 Display elements using liquid crystals have come to be widely used in watches, calculators, etc. This liquid crystal display element utilizes the properties of optical anisotropy and dielectric anisotropy of liquid crystal materials, and there are three liquid crystal phases: nematic liquid crystal phase, smectic liquid crystal phase, and cholesteric liquid crystal phase, among which nematic liquid crystal is used. The one that has been put into practical use is the most widely used. That is, they include TN (twisted nematic) type, DS (dynamic scattering type), guest-host type, DAP type, etc.
The properties required of the liquid crystal materials used for each type are different. However, in any case, it is desirable that the liquid crystal substances used in these display elements exhibit a liquid crystal phase over as wide a range as possible in nature, but there is currently no single substance that satisfies such conditions. Currently, materials that can be put to practical use are obtained by mixing several types of liquid crystal substances or non-liquid crystal substances. In addition, these materials must of course be stable against moisture, light, heat, air, etc., and the threshold voltage and saturation voltage necessary to drive the display element must be as low as possible, and the response speed must be as low as possible. In order to speed up the process, it is desirable that the viscosity be as low as possible. By the way, in order to widen the liquid crystal temperature range toward higher temperatures, it is necessary to use a liquid crystal substance with a high melting point as a component, but liquid crystal substances with a high melting point generally have a high viscosity, and therefore the liquid crystal composition containing it also has a high viscosity. As a result, the response speed of liquid crystal display elements that can be used at high temperatures, for example, up to about 80° C., particularly at low temperatures, has tended to become significantly slower. However, the present inventors found a liquid crystal material with a high liquid crystal temperature range and low viscosity, and arrived at the present invention.
即ち本発明は一般式
(上式中Rは炭素数1〜10のアルキル基を示し、
XはF又はClのいずれかを示す)
で表わされる4−ハロゲノ安息香酸−4−〔トラ
ンス−4′−(トランス−4″−アルキルシクロヘキ
シル)シクロヘキシル〕フエニルエステル及びそ
れを含有する液晶組成物である。 That is, the present invention is based on the general formula (In the above formula, R represents an alkyl group having 1 to 10 carbon atoms,
4-halogenobenzoic acid-4-[trans-4'-(trans-4''-alkylcyclohexyl)cyclohexyl] phenyl ester represented by (X represents either F or Cl) and a liquid crystal composition containing the same It is.
本発明の化合物は高い透明点を有し、例えば本
発明の化合物の一つである4−フルオロ安息香酸
−4−〔トランス−4′−(トランス−4″−プロピル
シクロヘキシル)シクロヘキシル〕フエニルエス
テルのC−S点は107℃、S−N点は195.8℃、N
−I点は300℃以上の広い温度範囲で液晶相を示
し、これを組成物の成分として加える事によりそ
の液晶組成物の粘度を高くせず、透明点を上げる
ことが出来る。又本発明の化合物の誘電異方性値
は+2程度であるが、組成物のしきい値電圧、飽
和電圧をそれ程変化させない。又水分、熱、光等
に対する安定性も良好である。 The compounds of the present invention have a high clearing point, such as 4-fluorobenzoic acid-4-[trans-4'-(trans-4''-propylcyclohexyl)cyclohexyl] phenyl ester, which is one of the compounds of the present invention. The C-S point is 107℃, the S-N point is 195.8℃, N
Point -I shows a liquid crystal phase in a wide temperature range of 300° C. or higher, and by adding it as a component of the composition, the clearing point can be raised without increasing the viscosity of the liquid crystal composition. Further, although the dielectric anisotropy value of the compound of the present invention is about +2, it does not change the threshold voltage and saturation voltage of the composition so much. It also has good stability against moisture, heat, light, etc.
つぎに本発明の化合物の製造法を示すと、まず
4−ブロモアニソールと金属マグネシウムを反応
させて、4−メトキシフエニルマグネシウムブロ
ミドとし、これを4−(トランス−4′−アルキル
シクロヘキシル)シクロヘキサノン(対応するシ
クロヘキサノールを無水クロム酸で酸化すること
により得られる)と反応させて4−メトキシ−
〔1′−ヒドロキシ−4′−(トランス−4″−アルキル
シクロヘキシル)シクロヘキシル〕ベンゼンとす
る。次いでこれを硫酸水素カリウム触媒にて脱水
して4−メトキシ−〔4′−(トランス−4″−アルキ
ルシクロヘキシル)シクロヘキサン−1′−イル〕
ベンゼンとする。ついでこれをエタノール溶媒中
ラネーニツケル触媒を用いて、常圧、30℃にて還
元すると4−メトキシ−〔4′−(トランス−4″−ア
ルキルシクロヘキシル)シクロヘキシル〕ベンゼ
ンである。これはトランス体とシス体の混合物で
あるので、エタノールで再結晶して4−メトキシ
−〔トランス−4′−(トランス−4″−アルキルシク
ロヘキシル)シクロヘキシル〕ベンゼンが得られ
る。ついで臭化水素酸で脱メチル化して4−〔ト
ランス−4′−(トランス−4″−アルキルシクロヘ
キシル)シクロヘキシル〕フエノールが得られ
る。これにピリジン存在下4−ハロゲノ安息香酸
クロリドと反応させて目的の4−ハロゲノ安息香
酸−4−〔トランス−4′−(トランス−4″−アルキ
ルシクロヘキシル)シクロヘキシル〕フエニルエ
ステルを製造した。 Next, the method for producing the compound of the present invention will be described. First, 4-bromoanisole and metallic magnesium are reacted to form 4-methoxyphenylmagnesium bromide, and this is converted into 4-(trans-4'-alkylcyclohexyl)cyclohexanone ( 4-methoxy-
[1'-hydroxy-4'-(trans-4"-alkylcyclohexyl)cyclohexyl]benzene. This is then dehydrated with a potassium hydrogen sulfate catalyst to form 4-methoxy-[4'-(trans-4"- alkylcyclohexyl)cyclohexane-1′-yl]
Let it be benzene. This is then reduced using a Raney Nickel catalyst in an ethanol solvent at normal pressure and 30°C to yield 4-methoxy-[4'-(trans-4''-alkylcyclohexyl)cyclohexyl]benzene. 4-Methoxy-[trans-4'-(trans-4''-alkylcyclohexyl)cyclohexyl]benzene is obtained by recrystallizing from ethanol. Then, demethylation with hydrobromic acid yields 4-[trans-4'-(trans-4''-alkylcyclohexyl)cyclohexyl]phenol. This is reacted with 4-halogenobenzoic acid chloride in the presence of pyridine to obtain the desired product. 4-halogenobenzoic acid-4-[trans-4'-(trans-4''-alkylcyclohexyl)cyclohexyl]phenyl ester was prepared.
以上を化学式で示すと
以下、実施例により本発明の化合物の製造法及
び使用例について更に詳細に説明する。 If the above is expressed as a chemical formula, Hereinafter, the production method and usage examples of the compound of the present invention will be explained in more detail with reference to Examples.
実施例 1
〔4−フルオロ安息香酸−4−〔トランス−
4′−(トランス−4″−プロピルシクロヘキシル)
シクロヘキシル〕フエニルエステルの製造〕
削り状マグネシウム1.2g(0.049モル)を3つ
口フラスコに入れ、4−ブロモアニソール9.2g
(0.049モル)をテトラヒドロフランに溶かした溶
液30mlを、窒素気流中で反応温度を30〜35℃に保
ち、撹拌しながらゆつくり滴下して行くと反応し
て3時間でマグネシウムは溶けて均一になり4−
メトキシフエニルマグネシウムプロミドを生ず
る。これに4−(トランス−4′−プロピルシクロ
ヘキシル)シクロヘキサノンの10.9g(0.049モ
ル)をテトラヒドロフランに溶かして50mlとした
ものを反応温度を5〜10℃に保ちつつなるべく速
かに滴下する。滴下後、35℃まで昇温し30分撹拌
し、ついで3N塩酸50mlを加える。反応液を分液
漏斗にとり200mlのトルエンで3回抽出後、合わ
せたトルエン層を水で洗液が中性になるまで洗浄
してからトルエンを減圧留去する。残留した油状
物は4−メトキシ−〔1′ヒドロキ−4′−(トランス
−4″−プロピルシクロヘキシル)シクロヘキシ
ル〕ベンゼンであり、これに硫酸水素カリウム6
gを加え窒素気流中160℃で2時間脱水する。冷
却後200mlのトルエンを加えてから硫酸水素カリ
ウムを別し、トルエン層を洗液から中性になる
まで水洗する。次いでトルエンを減圧留去し、残
る油状物をエタノールで再結晶して得られるのが
4−メトキシ−〔4′−(トランス−4″−プロピルシ
クロヘキシル)シクロヘキセン−1′−イル)ベン
ゼンである。ここで得られた全量7.0gをラネー
ニツケル触媒1.0gと共にエタノール120mlに溶か
し常圧50℃で接触還元を行ない、水素500mlを吸
収させた。触媒を別し、そのまま再結晶させ
る。得られたものはシス体とトランス体の混合物
なので、さらにエタノールで再結晶をくり返し、
トランス体を単離する。これが、4−メトキシ−
〔トランス−4′−(トランス−4″−プロピルシクロ
ヘキシル)シクロヘキシル〕ベンゼンで収量28
g、収率18%で得られた。Example 1 [4-fluorobenzoic acid-4-[trans-
4′-(trans-4″-propylcyclohexyl)
Production of cyclohexyl phenyl ester Put 1.2 g (0.049 mol) of magnesium turnings into a three-necked flask and add 9.2 g of 4-bromoanisole.
(0.049 mol) dissolved in tetrahydrofuran was slowly added dropwise while stirring in a nitrogen stream while keeping the reaction temperature at 30 to 35°C. The reaction occurred and the magnesium was dissolved and became homogeneous in 3 hours. 4-
This produces methoxyphenylmagnesium bromide. To this, 10.9 g (0.049 mol) of 4-(trans-4'-propylcyclohexyl)cyclohexanone dissolved in tetrahydrofuran to make 50 ml was added dropwise as quickly as possible while maintaining the reaction temperature at 5 to 10°C. After dropping, the temperature was raised to 35°C, stirred for 30 minutes, and then 50 ml of 3N hydrochloric acid was added. The reaction solution is placed in a separatory funnel and extracted three times with 200 ml of toluene. The combined toluene layers are washed with water until the washings become neutral, and the toluene is distilled off under reduced pressure. The remaining oil is 4-methoxy-[1'hydroxy-4'-(trans-4''-propylcyclohexyl)cyclohexyl]benzene, which is treated with 6 potassium hydrogen sulfate.
g and dehydrated in a nitrogen stream at 160°C for 2 hours. After cooling, add 200 ml of toluene, separate the potassium hydrogen sulfate, and wash the toluene layer with water until the washing liquid becomes neutral. The toluene was then distilled off under reduced pressure, and the remaining oil was recrystallized from ethanol to obtain 4-methoxy-[4'-(trans-4''-propylcyclohexyl)cyclohexen-1'-yl)benzene. The total amount of 7.0 g obtained here was dissolved in 120 ml of ethanol together with 1.0 g of Raney nickel catalyst and catalytic reduction was performed at normal pressure of 50°C to absorb 500 ml of hydrogen.The catalyst was separated and recrystallized as it was. Since it is a mixture of cis and trans forms, it is further recrystallized with ethanol.
Isolate the trans isomer. This is 4-methoxy-
Yield 28 with [trans-4′-(trans-4″-propylcyclohexyl)cyclohexyl]benzene
g, with a yield of 18%.
このもの15gを臭化水素酸(47%)200mlと酢
酸200mlと共に20時間還流する。反応終了後500ml
の水を加え、析出した結晶を過する。よく水で
洗つた後、アセトン−エタノール混合溶媒で再結
晶した。これが4−〔トランス−4′−(トランス−
4″−プロピルシクロヘキシル)シクロヘキシル〕
フエノールである。収量11g、収率77%。このも
のも液晶相を示し、そのC−Sm点は195℃、Sm
−N点は202.5℃、N−I点は207.8℃であつた。
この様にして製造した4−〔トランス−4′−(トラ
ンス−4″−プロピルシクロヘキシル)シクロヘキ
シル〕フエノールの1gをピリジン30mlに溶かし
た溶液に、4−フルオロ安息香酸クロリド1gを
加え、一晩放置する。トルエン200mlを加え、分
液漏斗でそのトルエン層を、まず6N塩酸で、つ
いで2N苛性ソーダ溶液で、最後に水で中性にな
るまで洗浄する。それを無水硫酸ナトリウムで乾
燥後、トルエン層を減圧で留去する。析出した結
晶をエタノールで、ついでアルコールで再結晶す
ると目的の4−フルオロ安息香酸−4−〔トラン
ス−4′−(トランス−4″−プロピルシクロヘキシ
ル)シクロヘキシル〕フエニルエステルを得た。
収量0.9g、収率64%。又そのC−Sm点は107℃、
Sm−N点は195.8、N−I点は300℃以上であつ
た。 15 g of this material is refluxed for 20 hours with 200 ml of hydrobromic acid (47%) and 200 ml of acetic acid. 500ml after reaction
of water and filter the precipitated crystals. After thoroughly washing with water, it was recrystallized from an acetone-ethanol mixed solvent. This is 4-[trans-4′-(trans-
4″-propylcyclohexyl)cyclohexyl]
It is phenol. Yield 11g, yield 77%. This material also shows a liquid crystal phase, and its C-Sm point is 195℃, Sm
-N point was 202.5°C, and N-I point was 207.8°C.
To a solution of 1 g of 4-[trans-4'-(trans-4''-propylcyclohexyl)cyclohexyl]phenol prepared in this manner dissolved in 30 ml of pyridine, 1 g of 4-fluorobenzoic acid chloride was added and left overnight. Add 200 ml of toluene and wash the toluene layer in a separatory funnel first with 6N hydrochloric acid, then with 2N caustic soda solution, and finally with water until neutral.After drying it over anhydrous sodium sulfate, remove the toluene layer. is distilled off under reduced pressure. The precipitated crystals are recrystallized from ethanol and then from alcohol to obtain the desired 4-fluorobenzoic acid-4-[trans-4'-(trans-4''-propylcyclohexyl)cyclohexyl]phenyl ester. I got it.
Yield 0.9g, yield 64%. Also, its C-Sm point is 107℃,
The Sm-N point was 195.8, and the N-I point was 300°C or higher.
以下同様な方法で4−〔トランス−4′−(トラン
ス−4″−プロピルシクロヘキシル)シクロヘキサ
ノンの代りに他のアルキル基を有する4−〔トラ
ンス−4′−(トランス−4″−アルキルシクロヘキ
シル)シクロヘキサノンを使用し、又XがClの場
合は4−フルオロ安息香酸クロリドの代りに4−
クロロ安息香酸クロリドを使つて全く同様にして
つぎのものを製造した。 Then, in the same manner, 4-[trans-4'-(trans-4''-alkylcyclohexyl)cyclohexanone having another alkyl group instead of 4-[trans-4'-(trans-4''-propylcyclohexyl)cyclohexanone] and when X is Cl, 4-fluorobenzoic acid chloride is used instead of 4-fluorobenzoic acid chloride.
The following was prepared in exactly the same manner using chlorobenzoic acid chloride.
4−フルオロ安息香酸−4−〔トランス−4′−
(トランス−4″−メチルシクロヘキシル)シクロ
ヘキシル〕フエニルエステル、4フルオロ安息香
酸−4−〔トランス−4′−(トランス−4″−エチル
シクロヘキシル)シクロヘキシル〕フエニルエス
テル、4−フルオロ安息香酸−4−〔トランス−
4′−(トランス−4″−ブチルシクロヘキシル)シ
クロヘキシル〕フエニルエステル、C−Sm点115
℃、Sm−N点204.3℃、N−I点275.8。4−フ
ルオロ安息香酸−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〕フエニルエステル、4−フルオロ安息香酸−
4−〔トランス−4′−(トランス−4″−ヘキシルシ
クロヘキシル)シクロヘキシル〕フエニルエステ
ル、4−フルオロ安息香酸−4−〔トランス−
4′−(トランス−4″−ヘプチルシクロヘキシル)
シクロヘキシル〕フエニルエステル、4−フルオ
ロ安息香酸−4−〔トランス−4′−(トランス−
4″−オクチルシクロヘキシル)シクロヘキシル〕
フエニルエステル、4−フルオロ安息香酸−4−
〔トランス−4′−(トランス−4″−ノニルシクロヘ
キシル)シクロヘキシル〕フエニルエステル、4
−フルオロ安息香酸−4−〔トランス−4′−(トラ
ンス−4″−デシルシクロヘキシル)シクロヘキシ
ル〕フエニルエステル、4−クロロ安息香酸−4
−〔トランス−4′−(トランス−4″−メチルシクロ
ヘキシル)シクロヘキシル〕フエニルエステル、
4−クロロ安息香酸−4−〔トランス−4′−(トラ
ンス−4″−エチルシクロヘキシル)シクロヘキシ
ル〕フエニルエステル、4−クロロ安息香酸−4
−〔トランス−4′−(トランス−4″−プロピルシク
ロヘキシル)シクロヘキシル)シクロヘキシル〕
フエニルエステル、C−Sm点141.0℃、Sm−N
点201.6℃、N−I点300℃以上。4−クロロ安息
香酸−4−〔トランス−4′−(トランス−4″−ブチ
ルシクロヘキシル)シクロヘキシル〕フエニルエ
ステル、C−Sm点140.0℃、Sm−N点179.7℃、
N−I点300℃、4−クロロ安息香酸−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〕フエニルエステル、4−
クロロ安息香酸−4−〔トランス−4′−(トランス
−4″−ヘキシルシクロヘキシル)シクロヘキシ
ル〕フエニルエステル、4−クロロ安息香酸−4
−〔トランス−4′−(トランス−4−ヘプチルシク
ロヘキシル)シクロヘキシル〕フエニルエステ
ル、4−クロロ安息香酸−4−〔トランス−4′−
(トランス−4″−オクチルシクロヘキシル)シク
ロヘキシル〕フエニルエステル、4−クロロ安息
香酸−4−〔トランス−4′−(トランス−4″−ノニ
ルシクロヘキシル)シクロヘキシル〕フエニルエ
ステル、4−クロロ安息香酸−4−〔トランス−
4′−(トランス−4″−デシルシクロヘキシル)シ
クロヘキシル〕フエニルエステル。 4-Fluorobenzoic acid-4-[trans-4'-
(trans-4″-methylcyclohexyl)cyclohexyl] phenyl ester, 4-fluorobenzoic acid-4-[trans-4′-(trans-4″-ethylcyclohexyl)cyclohexyl] phenyl ester, 4-fluorobenzoic acid-4 - [Trans-
4′-(trans-4″-butylcyclohexyl)cyclohexyl]phenyl ester, C-Sm point 115
°C, Sm-N point 204.3 °C, N-I point 275.8. 4-fluorobenzoic acid-4-[trans-4'-(trans-4''-pentylcyclohexyl)cyclohexyl] phenyl ester, 4-fluorobenzoic acid-
4-[trans-4′-(trans-4″-hexylcyclohexyl)cyclohexyl]phenyl ester, 4-fluorobenzoic acid-4-[trans-
4′-(trans-4″-heptylcyclohexyl)
cyclohexyl] phenyl ester, 4-fluorobenzoic acid-4-[trans-4'-(trans-
4″-octylcyclohexyl)cyclohexyl]
Phenyl ester, 4-fluorobenzoic acid-4-
[trans-4′-(trans-4″-nonylcyclohexyl)cyclohexyl] phenyl ester, 4
-Fluorobenzoic acid-4-[trans-4'-(trans-4''-decylcyclohexyl)cyclohexyl] phenyl ester, 4-chlorobenzoic acid-4
- [trans-4′-(trans-4″-methylcyclohexyl)cyclohexyl] phenyl ester,
4-chlorobenzoic acid-4-[trans-4′-(trans-4″-ethylcyclohexyl)cyclohexyl] phenyl ester, 4-chlorobenzoic acid-4
−[trans-4′-(trans-4″-propylcyclohexyl)cyclohexyl)cyclohexyl]
Phenyl ester, C-Sm point 141.0℃, Sm-N
Point 201.6℃, N-I point 300℃ or higher. 4-chlorobenzoic acid-4-[trans-4′-(trans-4″-butylcyclohexyl)cyclohexyl] phenyl ester, C-Sm point 140.0°C, Sm-N point 179.7°C,
N-I point 300℃, 4-chlorobenzoic acid-4-[trans-4'-(trans-4''-pentylcyclohexyl)cyclohexyl] phenyl ester, 4-
Chlorobenzoic acid-4-[trans-4'-(trans-4''-hexylcyclohexyl)cyclohexyl] phenyl ester, 4-chlorobenzoic acid-4
-[trans-4'-(trans-4-heptylcyclohexyl)cyclohexyl]phenyl ester, 4-chlorobenzoic acid-4-[trans-4'-
(trans-4″-octylcyclohexyl)cyclohexyl] phenyl ester, 4-chlorobenzoic acid-4-[trans-4′-(trans-4″-nonylcyclohexyl)cyclohexyl] phenyl ester, 4-chlorobenzoic acid- 4-[trans-
4′-(trans-4″-decylcyclohexyl)cyclohexyl] phenyl ester.
実施例 2(使用例)
トランス−4−プロピル−(4′−ジアノフエニル)
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 42%
トランス−4−ヘプチル−(4′−シアノフエニル)
シクロヘキサン 30%
なる組成の液晶組成物のN−I点は52℃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。Example 2 (Usage example) Trans-4-propyl-(4'-dianophenyl)
Cyclohexane 28% trans-4-pentyl-(4'-cyanophenyl)
Cyclohexane 42% trans-4-heptyl-(4'-cyanophenyl)
The NI point of a liquid crystal composition having a composition of 30% cyclohexane is 52°C.
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.
この液晶組成物97部に実施例1で製造した4−
フルオロ安息香酸−4−〔トランス−4′−(トラン
ス−4″−プロピルシクロヘキシル)シクロヘキシ
ル〕フエニルエステル3部を加えた液晶組成物の
N−I点は61℃に上り、これを前記と同様のTN
セルにしたときのしきい値電圧は1.55V、飽和電
圧は2.14Vであつた。又粘度は20℃で28cpであつ
た。 To 97 parts of this liquid crystal composition, 4-
The N-I point of the liquid crystal composition to which 3 parts of fluorobenzoic acid-4-[trans-4'-(trans-4''-propylcyclohexyl)cyclohexyl] phenyl ester was added rose to 61°C, and this was determined as above. TN
When used as a cell, the threshold voltage was 1.55V and the saturation voltage was 2.14V. The viscosity was 28 cp at 20°C.
Claims (1)
XはF又はClのいずれかを示す) で表わされる4−ハロゲノ安息香酸−4−〔トラ
ンス−4′−(トランス−4″−アルキルシクロヘキ
シル)シクロヘキシル〕フエニルエステル。 2 一般式 (上式中Rは炭素数1〜10のアルキル基を示し、
XはF又はClのいずれかを示す) で表わされる4−ハロゲノ安息香酸−4−〔トラ
ンス−4′−(トランス−4″−アルキルシクロヘキ
シル)シクロヘキシル〕フエニルエステルを少く
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 above formula, R represents an alkyl group having 1 to 10 carbon atoms,
4-halogenobenzoic acid-4-[trans-4'-(trans-4''-alkylcyclohexyl)cyclohexyl] phenyl ester represented by (X represents either F or Cl). 2 General formula (In the above formula, R represents an alkyl group having 1 to 10 carbon atoms,
(X represents either F or Cl) Characteristic liquid crystal composition.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8527182A JPH0247457B2 (en) | 1982-05-20 | 1982-05-20 | 44HAROGENOANSOKUKOSANN44 * TORANSUU4 *** TORANSUU4 *** ARUKIRUSHIKUROHEKISHIRU * SHIKUROHEKISHIRU * FUENIRUESUTERU |
US06/477,973 US4502974A (en) | 1982-03-31 | 1983-03-23 | High temperature liquid-crystalline ester compounds |
EP19830301866 EP0090671B1 (en) | 1982-03-31 | 1983-03-31 | Carbocylic esters having liquid-crystal properties at high temperatures |
DE8383301866T DE3360300D1 (en) | 1982-03-31 | 1983-03-31 | Carbocylic esters having liquid-crystal properties at high temperatures |
US06/683,631 US4701547A (en) | 1982-03-31 | 1984-12-19 | High temperature liquid-crystalline ester compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8527182A JPH0247457B2 (en) | 1982-05-20 | 1982-05-20 | 44HAROGENOANSOKUKOSANN44 * TORANSUU4 *** TORANSUU4 *** ARUKIRUSHIKUROHEKISHIRU * SHIKUROHEKISHIRU * FUENIRUESUTERU |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58203945A JPS58203945A (en) | 1983-11-28 |
JPH0247457B2 true JPH0247457B2 (en) | 1990-10-19 |
Family
ID=13853899
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8527182A Expired - Lifetime JPH0247457B2 (en) | 1982-03-31 | 1982-05-20 | 44HAROGENOANSOKUKOSANN44 * TORANSUU4 *** TORANSUU4 *** ARUKIRUSHIKUROHEKISHIRU * SHIKUROHEKISHIRU * FUENIRUESUTERU |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0247457B2 (en) |
-
1982
- 1982-05-20 JP JP8527182A patent/JPH0247457B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS58203945A (en) | 1983-11-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4477369A (en) | New high temperature liquid-crystalline substances consisting of 4 or 5 six-member-rings and liquid-crystalline compositions containing same | |
JPS6239136B2 (en) | ||
JPS6144863B2 (en) | ||
JPS644497B2 (en) | ||
JPS6313411B2 (en) | ||
JPH0244290B2 (en) | ||
JPH0247457B2 (en) | 44HAROGENOANSOKUKOSANN44 * TORANSUU4 *** TORANSUU4 *** ARUKIRUSHIKUROHEKISHIRU * SHIKUROHEKISHIRU * FUENIRUESUTERU | |
JPH033650B2 (en) | ||
JPH0247984B2 (en) | TORANSUU44ARUKIRUUTORANSUU4 **** 44HAROGENOBENZOIRUOKISHI ** OKUTADEKAHIDOROOTORANSUUPPTERUFUENIRU | |
JPS59141527A (en) | Partially reduced naphthalene derivative | |
JPH0320378B2 (en) | ||
JPH0229055B2 (en) | JISHIKUROHEKISHIRUBENZENJUDOTAI | |
JPS597149A (en) | 4-(trans-4'-(trans-4"-alkylcyclohexyl)cyclohexyl)phenyl 4-cyanobenzoate | |
JPS6092228A (en) | 4-halogenobiphenyl derivative consisting of four rings | |
JPS5942344A (en) | Bicyclohexylphenyl ester derivative of 2,4-dichlorobenzoic acid | |
JPH0158168B2 (en) | ||
JPS6361292B2 (en) | ||
JPS5916853A (en) | Ester derivative of 4-(trans-4'-(trans-4"-alkylcyclohexyl) cyclohexyl)phenol | |
JPS5859930A (en) | Iodobenzene derivative having 4-(trans-4'-(trans-4"- alkylcyclohexyl)cyclohexyl) group | |
JPS597137A (en) | 4-(trans-4'-(trans-4"-alkylcyclohexyl)cyclohexyl)phenyl 3-alpha,alpha,alpha-trifluoromethylbenzoate | |
JPH0239499B2 (en) | 44 * TORANSUU4 *** TORANSUU4 *** ARUKIRUSHIKUROHEKISHIRU * SHIKUROHEKISHIRU * ANSOKUKOSAN44HAROGENNOFUENIRUESUTERU | |
JPH0247982B2 (en) | TORIFURUOROMECHIRUKIOJUSURUTAKANESUTERUKAGOBUTSU | |
JPS597138A (en) | 4-(trans-4'-(trans-4"-alkylcyclohexyl)cyclohexyl)phenyl 3-halogenobenzoate | |
JPS5910552A (en) | 4-(trans-4'-(trans-4"-alkylcyclohexyl)cyclohexyl)phenyl 4-alpha,alpha,alpha-trifluoromethylbenzoate | |
JPH0220615B2 (en) |