JPH0784416B2 - Novel liquid crystal compound and liquid crystal composition - Google Patents
Novel liquid crystal compound and liquid crystal compositionInfo
- Publication number
- JPH0784416B2 JPH0784416B2 JP61185066A JP18506686A JPH0784416B2 JP H0784416 B2 JPH0784416 B2 JP H0784416B2 JP 61185066 A JP61185066 A JP 61185066A JP 18506686 A JP18506686 A JP 18506686A JP H0784416 B2 JPH0784416 B2 JP H0784416B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- biphenyl
- oxy
- benzene
- methyloctyl
- 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
- 150000001875 compounds Chemical class 0.000 title claims description 20
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 title description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 57
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- RUZLIIJDZBWWSA-INIZCTEOSA-N methyl 2-[[(1s)-1-(7-methyl-2-morpholin-4-yl-4-oxopyrido[1,2-a]pyrimidin-9-yl)ethyl]amino]benzoate Chemical group COC(=O)C1=CC=CC=C1N[C@@H](C)C1=CC(C)=CN2C(=O)C=C(N3CCOCC3)N=C12 RUZLIIJDZBWWSA-INIZCTEOSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- TWDAVWNDGHYAJZ-VIFPVBQESA-N (6s)-1-bromo-6-methyloctane Chemical compound CC[C@H](C)CCCCCBr TWDAVWNDGHYAJZ-VIFPVBQESA-N 0.000 description 4
- QXZJWSFANNPANS-HNNXBMFYSA-N C[C@H](CCCOC1=CC=C(C=C1)C1=CC=C(C=C1)C(=O)O)CC Chemical compound C[C@H](CCCOC1=CC=C(C=C1)C1=CC=C(C=C1)C(=O)O)CC QXZJWSFANNPANS-HNNXBMFYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PZVBWLCVBZSNMD-KRWDZBQOSA-N CC[C@H](C)CCCCCOC1=CC=C(C=C1)C2=CC=C(C=C2)C(=O)Cl Chemical compound CC[C@H](C)CCCCCOC1=CC=C(C=C1)C2=CC=C(C=C2)C(=O)Cl PZVBWLCVBZSNMD-KRWDZBQOSA-N 0.000 description 3
- ZPCNUQWEIDGGBE-KRWDZBQOSA-N C[C@H](CCCCCOC1=CC=C(C=C1)C1=CC=C(C=C1)C(=O)O)CC Chemical compound C[C@H](CCCCCOC1=CC=C(C=C1)C1=CC=C(C=C1)C(=O)O)CC ZPCNUQWEIDGGBE-KRWDZBQOSA-N 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- -1 methylhexyl Chemical group 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- SZWBRVPZWJYIHI-UHFFFAOYSA-N 4-n-Hexylphenol Chemical compound CCCCCCC1=CC=C(O)C=C1 SZWBRVPZWJYIHI-UHFFFAOYSA-N 0.000 description 2
- OGJLVQQJRHKHGO-HNNXBMFYSA-N CC[C@H](C)CCCOC1=CC=C(C=C1)C2=CC=C(C=C2)C(=O)Cl Chemical compound CC[C@H](C)CCCOC1=CC=C(C=C1)C2=CC=C(C=C2)C(=O)Cl OGJLVQQJRHKHGO-HNNXBMFYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XKVLZBNEPALHIO-YFKPBYRVSA-N (2s)-1-bromo-2-methylbutane Chemical compound CC[C@H](C)CBr XKVLZBNEPALHIO-YFKPBYRVSA-N 0.000 description 1
- QIXNVYCYRYRCAK-ZETCQYMHSA-N (4s)-1-bromo-4-methylhexane Chemical compound CC[C@H](C)CCCBr QIXNVYCYRYRCAK-ZETCQYMHSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- JPVUWCPKMYXOKW-UHFFFAOYSA-N 4-phenylbenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=CC=C1 JPVUWCPKMYXOKW-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- PHBQSOODLMGROT-UHFFFAOYSA-N methyl 4-(4-hydroxyphenyl)benzoate Chemical compound C1=CC(C(=O)OC)=CC=C1C1=CC=C(O)C=C1 PHBQSOODLMGROT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 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】 （技術分野） 本発明は、強誘電性液晶組成物の成分として有用で、か
つ、化学的安定性に優れた新規な液晶性化合物ならびに
この液晶性化合物の少くとも１種を含有する液晶組成物
に関する。TECHNICAL FIELD The present invention relates to a novel liquid crystal compound which is useful as a component of a ferroelectric liquid crystal composition and has excellent chemical stability, and at least 1 of the liquid crystal compound. A liquid crystal composition containing a seed.
（従来技術） 現在、ネマテイツク液晶を利用したツイスト−ネマテイ
ツク型表示方式が広く普及している。この表示方式を利
用した液晶表示素子は、低電圧駆動、低消費電力等の特
長を有し、時計、電卓等の表示部に用いられている。し
かし、応答速度に関しては、他の発光型表示素子（発光
ダイオード等）に比較して遅く、高速応答性を必要とす
る光プリンターヘッド等への応用は制限されてきた。(Prior Art) At present, a twist-nematic display system using a nematic liquid crystal is widely used. A liquid crystal display element using this display system has features such as low voltage driving and low power consumption, and is used for a display unit of a timepiece, a calculator, or the like. However, the response speed is slower than that of other light emitting display devices (light emitting diodes, etc.), and its application to optical printer heads and the like that require high speed response has been limited.
1980年、クラークおよびラゲルバル（アプライド・フイ
ジクス・レターズ、36、899、1980）によつて発表され
た強誘電性液晶の光スイツチング現象を利用した表示方
式は、高速応答性を有しており光プリンターヘッド等の
オプトエレクトロニクスの分野への応用も可能となつ
た。In 1980, Clark and Lagerval (Applied Physics Letters, 36 , 899, 1980) announced a display method using the optical switching phenomenon of a ferroelectric liquid crystal, which has a high-speed response and an optical printer. It can be applied to the field of optoelectronics such as heads.
強誘電性液晶は、1975年、アール・ビー・メイアーらに
よつて初めて見出されたものであるが（ル・ジユルナー
ル・ドウ・フイジク36、Ｌ−69、（1975））、液晶物質
が強誘電性を示すには、次の条件を満足しなければなら
ない。Ferroelectric liquid crystals were first discovered by RB Meier et al. In 1975 (Le Jyurnal Dow Physik 36 , L-69, (1975)), but liquid crystal substances were strong. To exhibit dielectric properties, the following conditions must be satisfied.
分子構造中に不斉炭素原子を有し、かつ、光学活性
であること。It has an asymmetric carbon atom in its molecular structure and is optically active.
分子長軸方向に垂直な永久双極子モーメントを有す
ること。Must have a permanent dipole moment perpendicular to the long axis of the molecule.
カイラルスメクテイツクＣ相（SmC＊相）を有する
こと。Must have a chiral smectic C phase (SmC * phase).
従来の代表的な強誘電性液晶を構造式その他により次に
示す。A typical conventional ferroelectric liquid crystal is shown below by a structural formula and others.
（ａ）は、メイアーらにより見出された最初の強誘電性
液晶物質であり、（ｂ）は、自発分極の大きい化合物と
して知られている。いずれも、シツフ塩基であり、水分
に不安定である。（ｃ）は、水分には安定であるが、Sm
C＊相の温度範囲が狭い。 (A) is the first ferroelectric liquid crystal substance found by Meyer et al., And (b) is known as a compound having large spontaneous polarization. All are Schiff bases and are unstable to water. (C) is stable to water, but Sm
C * phase temperature range is narrow.
（発明の開示） 本発明者らは、化学的に安定で、強誘電性液晶組成物成
分として有用な新規化合物を提供することに成功した。DISCLOSURE OF THE INVENTION The present inventors have succeeded in providing a novel compound that is chemically stable and is useful as a component of a ferroelectric liquid crystal composition.
本発明に係る新規化合物は、化学的に安定な物質であつ
て、液晶組成物成分として使用した場合に、動作温度範
囲の広い表示素子を提供することができるものである。
すなわち、本発明に係る化合物は、液晶組成物において
SmC＊相の温度範囲を拡張する成分として有用なもので
ある。INDUSTRIAL APPLICABILITY The novel compound according to the present invention is a chemically stable substance, and when used as a component of a liquid crystal composition, can provide a display device having a wide operating temperature range.
That is, the compound according to the present invention is used in a liquid crystal composition.
It is useful as a component that extends the temperature range of the SmC * phase.
以下に本発明を詳細に説明する。The present invention will be described in detail below.
本発明に係る新規化合物は、一般式（Ｉ） （式中、Ｒは炭素原子数１〜18のアルキル基であり、ｎ
は３〜７の整数を表わす）で表わされる液晶性化合物で
ある。The novel compound according to the present invention has the general formula (I) (In the formula, R is an alkyl group having 1 to 18 carbon atoms, and n
Represents an integer of 3 to 7) and is a liquid crystal compound.
本発明に係る化合物は、次の図式により示される合成ル
ートにより製造することができる。The compound according to the present invention can be produced by the synthetic route shown by the following scheme.
図式中に示された（ｉ）〜（ix）の記号は、いずれも後
述の実施例中の対応する各化合物に符されている。The symbols (i) to (ix) shown in the scheme are all assigned to the corresponding compounds in the examples described later.
以下に、本発明に係る化合物およびその製造例ならびに
使用例を実施例によつて具体的に説明する。Hereinafter, the compounds according to the present invention, production examples thereof and use examples thereof will be specifically described with reference to Examples.
式中＊の符号は、光学活性原子を示すものであり、ルー
トの図式中には参照する実施例の番号が記入されてい
る。In the formula, the symbol * indicates an optically active atom, and the reference example number is entered in the route diagram.
実施例１ （Ｓ）−ｐ−ヘキシルフエニル４−〔（４″−メチルヘ
キシル）オキシ〕ビフエニル−４′−カルボキシレート
（iv）の合成 （ａ） （Ｓ）−メチル４−〔（４″−メチルヘキシ
ル）オキシ〕ビフエニル−４′−カルボキシレート
（ｉ）の合成 反応容器に、メチル４−ヒドロキシビフエニル−４′−
カルボキシレート67.5g、（Ｓ）−４−メチルヘキシル
ブロマイド（Mol.Cryst.Liq.Cryst.114、237−247 1984
の反応例に従い合成。b.p.71〜72℃/23.5mmHg）58.5g、
無水炭酸カリウム82gおよびシクロヘキサノン750ccを仕
込み、130〜140℃で５時間、撹拌した。 Example 1 Synthesis of (S) -p-hexylphenyl 4-[(4 "-methylhexyl) oxy] biphenyl-4'-carboxylate (iv) (a) (S) -methyl 4-[(4" -methyl Synthesis of Hexyl) oxy] biphenyl-4'-carboxylate (i) In a reaction vessel, methyl 4-hydroxybiphenyl-4'-
Carboxylate 67.5 g, (S) -4-methylhexyl bromide (Mol. Cryst. Liq. Cryst. 114 , 237-247 1984
Synthesized according to the reaction example of. bp71-72 ℃ / 23.5mmHg) 58.5g,
82 g of anhydrous potassium carbonate and 750 cc of cyclohexanone were charged, and the mixture was stirred at 130 to 140 ° C for 5 hours.
放冷後、反応液を水へあけ、遊離した有機層をベンゼン
で抽出した。ベンゼン層をよく水洗した後、芒硝で乾燥
させた。溶媒を留去し、残留分をアセトンより再結晶す
ることにより75gの（Ｓ）−メチル４−〔（４″−メチ
ルヘキシル）オキシ〕ビフエニル−４′−カルボキシレ
ート（ｉ）が得られた。このものの相変化を偏光顕微鏡
下で観察したところ以下のようであつた。After allowing to cool, the reaction solution was poured into water and the liberated organic layer was extracted with benzene. The benzene layer was washed well with water and then dried with mirabilite. The solvent was distilled off and the residue was recrystallized from acetone to obtain 75 g of (S) -methyl 4-[(4 "-methylhexyl) oxy] biphenyl-4'-carboxylate (i). When the phase change of this product was observed under a polarizing microscope, it was as follows.
（ｂ） （Ｓ）−４−〔（４″−メチルヘキシル）オキ
シ〕ビフエニル−４′−カルボン酸（ii）の合成 反応容器に、（Ｓ）−メチル４−〔（４″−メチルヘキ
シル）オキシ〕ビフエニル−４′−カルボキシレート
（ｉ）75g（テトラヒドロフラン200ccに溶解させたも
の）、メタノール200ccおよび95％苛性ソーダ30g（水15
0ccに溶解させたもの）を仕込み、還流下に４時間撹拌
した。 (B) Synthesis of (S) -4-[(4 ″ -methylhexyl) oxy] biphenyl-4′-carboxylic acid (ii) In a reaction vessel, (S) -methyl 4-[(4 ″ -methylhexyl) Oxy] biphenyl-4'-carboxylate (i) 75 g (dissolved in tetrahydrofuran 200 cc), methanol 200 cc and 95% caustic soda 30 g (water 15
(Dissolved in 0 cc) was charged and stirred under reflux for 4 hours.
次に、この反応液へ塩酸を投入して酸性とした後、析出
物を減圧過した。集した結晶を加熱乾燥することに
より67gの（Ｓ）−４−〔（４″−メチルヘキシル）オ
キシ〕ビフエニル−４′−カルボン酸（ii）が得られ
た。Next, hydrochloric acid was added to this reaction solution to make it acidic, and then the precipitate was subjected to reduced pressure. By heating and drying the collected crystals, 67 g of (S) -4-[(4 "-methylhexyl) oxy] biphenyl-4'-carboxylic acid (ii) was obtained.
（ｃ） （Ｓ）−４−〔（４″−メチルヘキシル）オキ
シ〕ビフエニル−４′−カルボニルクロライド（iii）
の合成 反応容器に、（Ｓ）−４−〔（４″−メチルヘキシル）
オキシ〕ビフエニル−４′−カルボン酸（ii）67g、ベ
ンゼン600ccおよび少量のピリジンを仕込み、還流下に
撹拌しながら塩化チオニル51gを滴下した。次いで同温
度で10時間反応させた後、溶媒と過剰の塩化チオニルを
留去すると、（Ｓ）−４−〔（４″−メチルヘキシル）
オキシ〕ビフエニル−４′−カルボニルクロライド（ii
i）70gが得られた。(C) (S) -4-[(4 ″ -methylhexyl) oxy] biphenyl-4′-carbonyl chloride (iii)
Synthesis of (S) -4-[(4 ″ -methylhexyl)
67 g of [oxy] biphenyl-4'-carboxylic acid (ii), 600 cc of benzene and a small amount of pyridine were charged, and 51 g of thionyl chloride was added dropwise with stirring under reflux. Then, after reacting at the same temperature for 10 hours, the solvent and excess thionyl chloride were distilled off to give (S) -4-[(4 ″ -methylhexyl).
Oxy] biphenyl-4'-carbonyl chloride (ii
i) 70 g was obtained.
（ｄ） （Ｓ）−ｐ−ヘキシルフエニル４−〔（４″−
メチルヘキシル）オキシ〕ビフエニル−４′−カルボキ
シレート（iv）の合成 反応容器に、ｐ−ヘキシルフエノール1.6g、ベンゼン10
cc、ピリジン0.8gを仕込み、撹拌しながら、室温下、
（Ｓ）−４−〔（４″−メチルヘキシル）オキシ〕ビフ
エニル−４′−カルボニルクロライド（iii）3g（ベン
ゼン20ccに溶解させたもの）を滴下した。室温下で２時
間、さらに還流下で３時間反応させた後、反応液を水に
注加した。遊離したベンゼン層をよく水洗し、芒硝で乾
燥させた。(D) (S) -p-hexylphenyl 4-[(4 ″-
Synthesis of (methylhexyl) oxy] biphenyl-4'-carboxylate (iv) In a reaction vessel, 1.6 g of p-hexylphenol and benzene 10
Charge cc and 0.8g of pyridine and stir at room temperature.
(S) -4-[(4 ″ -methylhexyl) oxy] biphenyl-4′-carbonyl chloride (iii) 3 g (dissolved in 20 benzene of benzene) was added dropwise at room temperature for 2 hours and further under reflux. After reacting for 3 hours, the reaction solution was poured into water, and the liberated benzene layer was washed well with water and dried with sodium sulfate.
ベンゼンを留去し、残留分をアセトンより２回再結晶す
ることにより（Ｓ）−ｐ−ヘキシルフエニル４−
〔（４″−メチルヘキシル）オキシ〕ビフエニル−４′
−カルボキシレート（iv）1.5gが得られた。Benzene was distilled off and the residue was recrystallized twice from acetone to give (S) -p-hexylphenyl 4-
[(4 "-methylhexyl) oxy] biphenyl-4 '
-1.5 g of carboxylate (iv) were obtained.
このものの含量は液体クロマトグラフイーにて99％以
上、薄層クロマトグラフイーにて１スポツトであつた。The content of this product was 99% or more by liquid chromatography and 1 spot by thin layer chromatography.
また、赤外線吸収スペクトル測定によれば、特性値は、
2800〜3000cm-1、1730cm-1、1270cm-1であつた。According to infrared absorption spectrum measurement, the characteristic value is
It was 2800 to 3000 cm -1 , 1730 cm -1 , and 1270 cm -1 .
また、マススペクトル分析では、472に分子イオンピー
ク、295に基準ピークが認められ、このものの化学構造
が支持された。Moreover, in the mass spectrum analysis, a molecular ion peak was observed at 472 and a reference peak at 295, supporting the chemical structure of this.
このものを、メトラーホツトステージFP−82にはさみ、
偏光顕微鏡下で相変化を観察したところ以下のようであ
つた。Scissor this with METTLER Hotstage FP-82,
Observation of the phase change under a polarization microscope revealed the following.
＃：偏光顕微鏡観察では、相変化が不明瞭であつたの
で、示差熱量計測定により求めた。 #: Since the phase change was unclear by observation with a polarizing microscope, it was determined by measurement with a differential calorimeter.
実施例２〜５ 実施例１に準拠して、同様にして、各種の誘導体を合成
した。実施例１〜５で得られた化合物のそれぞれについ
て相転移温度を測定した結果を表１に示す。〔表中、Ｒ
は、前記一般式（Ｉ）におけるＲであり、それにより各
化合物を示す。〕 実施例６ （Ｓ）−ｐ−ヘキシルフエニル４−〔（６″−メチルオ
クチル）オキシ〕ビフエニル−４′−カルボキシレート
（ix）の合成 （ａ） （Ｓ）−６−メチルオクチルブロマイド（ｖ）
の合成 反応容器に、粉末マグネシウム13.8gおよびテトラヒド
ロフラン（水素化リチウムアルミニウムで処理した後に
蒸留して精製したもの）160ccを仕込み、これに（Ｓ）
−２−メチルブチルブロマイド（Mol.Cryst.Liq.Cryst.
48、37〜52、1978の反応例に従つて合成:b.p.123〜124
℃）78gを滴下してグリニヤール試薬を調製した。Examples 2 to 5 Various derivatives were synthesized in the same manner as in Example 1. The results of measuring the phase transition temperature of each of the compounds obtained in Examples 1 to 5 are shown in Table 1. [In the table, R
Is R in the above general formula (I), and thereby represents each compound. ] Example 6 Synthesis of (S) -p-hexylphenyl 4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carboxylate (ix) (a) (S) -6-methyloctyl bromide (v)
Into a reaction vessel, 13.8 g of powdered magnesium and 160 cc of tetrahydrofuran (purified by treatment with lithium aluminum hydride and then distilled) were charged, and (S)
-2-Methylbutyl bromide (Mol.Cryst.Liq.Cryst.
48 , 37-52, 1978 Synthesized according to the reaction example: bp123-124
(° C) 78 g was added dropwise to prepare a Grignard reagent.
別に、反応容器に、1,4−ジブロモブタン123g、テトラ
ヒドロフラン（THF）350cc、および0.1mol/のジリチ
ウムテトラクロロキユープレート−THF溶液（Li2CuCl4/
THF）18ccを仕込み、０℃以下で、上記のグリニヤール
試薬を滴下した。Separately, 123 g of 1,4-dibromobutane, 350 cc of tetrahydrofuran (THF), and 0.1 mol / dilithium tetrachloroquine plate-THF solution (Li 2 CuCl 4 /
(THF) 18 cc was charged, and the above Grignard reagent was added dropwise at 0 ° C. or lower.
０℃以下で１時間、10℃で１時間、さらに室温下で１時
間撹拌した後、反応液を希塩酸中に注加した。遊離した
有機層をベンゼンで抽出し、ベンゼン層を充分に水洗し
た。ベンゼン層を芒硝で乾燥させた後、溶媒を留去し、
残留分を減圧蒸留すると、（Ｓ）−６−メチルオクチル
ブロマイド（ｖ）60gが得られた。b.p.102〜114℃/27mm
Hg （ｂ） （Ｓ）−メチル４−〔（６″−メチルオクチ
ル）オキシ〕ビフエニル−４′−カルボキシレート（v
i）の合成 反応容器に、メチル４−ヒドロキシビフエニル−４′−
カルボキシレート38g、（Ｓ）−６−メチルオクチルブ
ロマイド（ｖ）38g、無水炭酸カリウム53gおよびシクロ
ヘキサノン500ccを仕込み、130〜140℃で５時間撹拌し
た。放冷後、反応液を水へあけ、遊離した有機層をベン
ゼンで抽出した。ベンゼン層をよく水洗した後、芒硝で
乾燥させた。溶媒を留去し、残留分をアセトンより再結
晶すると50gの（Ｓ）−メチル４−〔（６″−メチルオ
クチル）オキシ〕ビフエニル−４′−カルボキシレート
（vi）が得られた。After stirring at 0 ° C or lower for 1 hour, at 10 ° C for 1 hour, and further at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid. The liberated organic layer was extracted with benzene, and the benzene layer was thoroughly washed with water. After drying the benzene layer with sodium sulfate, the solvent was distilled off,
The residue was distilled under reduced pressure to obtain 60 g of (S) -6-methyloctyl bromide (v). bp102-114 ℃ / 27mm
Hg (b) (S) -methyl 4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carboxylate (v
Synthesis of i) In a reaction vessel, methyl 4-hydroxybiphenyl-4'-
38 g of carboxylate, 38 g of (S) -6-methyloctyl bromide (v), 53 g of anhydrous potassium carbonate and 500 cc of cyclohexanone were charged, and the mixture was stirred at 130 to 140 ° C for 5 hours. After allowing to cool, the reaction solution was poured into water and the liberated organic layer was extracted with benzene. The benzene layer was washed well with water and then dried with mirabilite. The solvent was distilled off, and the residue was recrystallized from acetone to obtain 50 g of (S) -methyl 4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carboxylate (vi).
（ｃ） （Ｓ）−４−〔（６″−メチルオクチル）オキ
シ〕ビフエニル−４′−カルボン酸（vii）の合成 反応容器に、（Ｓ）−メチル４−〔（６″−メチルオク
チル）オキシ〕ビフエニル−４′−カルボキシレート
（vi）50g（テトラヒドロフラン200ccに溶解させたも
の）、メタノール200ccおよび95％苛性ソーダ15g（水15
00ccに溶解させたもの）を仕込み、還流下に４時間撹拌
した。 (C) Synthesis of (S) -4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carboxylic acid (vii) In a reaction vessel, (S) -methyl 4-[(6 ″ -methyloctyl) Oxy] biphenyl-4'-carboxylate (vi) 50 g (dissolved in tetrahydrofuran 200 cc), methanol 200 cc and 95% caustic soda 15 g (water 15
(Dissolved in 00cc) was charged and stirred under reflux for 4 hours.
次に、反応液へ塩酸を投入して酸性とした後、析出物も
減圧過した。集した結晶を加熱乾燥すると45gの
（Ｓ）−４−〔（６″−メチルオクチル）オキシ〕ビフ
エニル−４′−カルボン酸（vii）が得られた。Next, hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was also depressurized. The collected crystals were dried by heating to obtain 45 g of (S) -4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carboxylic acid (vii).
（ｄ） （Ｓ）−４−〔（６″−メチルオクチル）オキ
シ〕ビフエニル−４′−カルボニルクロライド（viii）
の合成 反応容器に、（Ｓ）−４−〔（６″−メチルオクチル）
オキシ〕ビフエニル−４′−カルボン酸（vii）45g、ベ
ンゼン500ccおよび少量のピリジンを仕込み、還流下に
撹拌しながら塩化チオニル32gを滴下した。次いで同温
度で10時間反応させた後、溶媒と過剰の塩化チオニルを
留去すると47gの（Ｓ）−４−〔（６″−メチルオクチ
ル）オキシ〕ビフエニル−４′−カルボニルクロライド
（viii）が得られた。(D) (S) -4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carbonyl chloride (viii)
Synthesis of (S) -4-[(6 ″ -methyloctyl)
Oxy] biphenyl-4'-carboxylic acid (vii) (45 g), benzene (500 cc) and a small amount of pyridine were charged, and thionyl chloride (32 g) was added dropwise with stirring under reflux. Then, after reacting at the same temperature for 10 hours, the solvent and excess thionyl chloride were distilled off to obtain 47 g of (S) -4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carbonyl chloride (viii). Was obtained.
（ｅ） （Ｓ）−ｐ−ヘキシルフエニル４−〔（６″−
メチルオクチル）オキシ〕ビフエニル−４′−カルボキ
シレート（ix）の合成 反応容器に、ｐ−ヘキシルフエノール1.5g、ベンゼン10
ccおよびピリジン0.7gを仕込み、撹拌しながら、室温下
（Ｓ）−４−〔（６″−メチルオクチル）オキシ〕ビフ
エニル−４′−カルボニルクロライド（viii）3g（ベン
ゼン20ccに溶解させた）を滴下した。室温下で２時間、
さらに還流下で３時間反応させた後、反応液を水に注加
した。遊離したベンゼン層をよく水洗し、芒硝で乾燥さ
せた。ベンゼンを留去し、残留分をアセトンより２回再
結晶すると（Ｓ）−ｐ−ヘキシルフエニル４−〔（６″
−メチルオクチル）オキシ〕ビフエニル−４′−カルボ
キシレート（ix）1.9gが得られた。(E) (S) -p-hexylphenyl 4-[(6 ″-
Synthesis of methyloctyl) oxy] biphenyl-4'-carboxylate (ix) In a reaction vessel, p-hexylphenol (1.5 g) and benzene (10) were added.
cc and 0.7 g of pyridine were charged, and 3 g of (S) -4-[(6 ″ -methyloctyl) oxy] biphenyl-4′-carbonyl chloride (viii) (dissolved in 20 benzene of benzene) was stirred at room temperature. 2 hours at room temperature
After reacting for 3 hours under reflux, the reaction solution was poured into water. The liberated benzene layer was washed well with water and dried with mirabilite. When benzene was distilled off and the residue was recrystallized twice from acetone, (S) -p-hexylphenyl 4-[(6 "
1.9 g of -methyloctyl) oxy] biphenyl-4'-carboxylate (ix) were obtained.
このものの含量は、液体クロマトグラフイーにて99％以
上、薄層クロマトグラフイーにて１スポツトであつた。The content of this product was 99% or more by liquid chromatography and 1 spot by thin layer chromatography.
また、赤外線吸収スペクトル測定によれば特性値は、28
00〜3000cm-1、1730cm-1、1270cm-1であつた。また、マ
ススペクトル分析では、501に分子イオンピーク、323に
基準ピークが認められ、このものの化学構造が支持され
た。Moreover, according to the infrared absorption spectrum measurement, the characteristic value is 28
It was 00-3000 cm -1 , 1730 cm -1 , 1270 cm -1 . Further, in the mass spectrum analysis, a molecular ion peak was observed at 501 and a reference peak at 323, supporting the chemical structure of this.
このものをメトラーホツトステージFP−82にはさみ、偏
光顕微鏡下で相変化を観察したところ、以下のようであ
つた。This product was sandwiched between METTLER Hotstage FP-82 and the phase change was observed under a polarizing microscope. The results were as follows.
実施例７〜10 実施例６に準拠して、同様にして、各種の誘導体を合成
した。実施例６〜10で得られた化合物のそれぞれの相転
移温度を測定した結果を表２に示す。〔表中、Ｒは前記
一般式（Ｉ）におけるＲであり、それにより各化合物を
示す。〕 実施例11 表面にポリイミド系高分子膜を塗布し、ラビング処理し
た２枚の透明電極を有するガラス基板に、マイラーフイ
ルムをはさんで、液晶セルを組立てた。なお、２枚の基
板は、そのラビング方向は平行になるようにされ、セル
間隔は９μｍである。この液晶セルに各実施例で得られ
た化合物を封入し、等方性液体からSmC＊相まで徐冷し
た。この液晶セルを２枚の偏光板にはさみ、電圧を印加
し、極性を反転させると表示状態が変化した。このよう
に、各実施例で得られた各化合物のSmC＊相は、強誘電
性を示し、電気光学素子として使用し得るものである。 Examples 7 to 10 Various derivatives were synthesized in the same manner as in Example 6. The results of measuring the phase transition temperatures of the compounds obtained in Examples 6 to 10 are shown in Table 2. [In the table, R is R in the above general formula (I), and thereby represents each compound. ] Example 11 A liquid crystal cell was assembled by sandwiching a Mylar film on a glass substrate having two transparent electrodes that were coated with a polyimide-based polymer film and rubbed. The two substrates were so arranged that their rubbing directions were parallel to each other, and the cell spacing was 9 μm. The liquid crystal cell was filled with the compound obtained in each example and gradually cooled from the isotropic liquid to the SmC * phase. The liquid crystal cell was sandwiched between two polarizing plates, a voltage was applied, and the polarities were inverted to change the display state. As described above, the SmC * phase of each compound obtained in each example exhibits ferroelectricity and can be used as an electro-optical element.
本発明に係る化合物は、化学的に安定であつて強誘電性
液晶組成物の温度範囲を拡張する成分として有用なもの
である。The compound according to the present invention is chemically stable and is useful as a component for extending the temperature range of a ferroelectric liquid crystal composition.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤井 恒宣 埼玉県草加市稲荷１−７−１ 関東化学株 式会社中央研究所内 (56)参考文献 特開 昭53−23883（ＪＰ，Ａ) 特開 昭53−125983（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tsunenobu Fujii 1-7-1 Inari, Soka-shi, Saitama Kanto Chemical Co., Ltd. Central Research Laboratory (56) Reference JP-A-53-23883 (JP, A) JP Sho 53-125983 (JP, A)
Claims (2)
ｎは３〜７の整数を表わす）で表わされる化合物。1. A general formula (I) (In the formula, R is an alkyl group having 1 to 18 carbon atoms,
n represents an integer of 3 to 7).
ｎは３〜７の整数を表わす）で表わされる液晶性化合物
の少くとも１種を含有することを特徴とする液晶組成
物。2. General formula (I) (In the formula, R is an alkyl group having 1 to 18 carbon atoms,
and n represents an integer of 3 to 7), at least one liquid crystal compound represented by formula (1) is contained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61185066A JPH0784416B2 (en) | 1986-08-08 | 1986-08-08 | Novel liquid crystal compound and liquid crystal composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61185066A JPH0784416B2 (en) | 1986-08-08 | 1986-08-08 | Novel liquid crystal compound and liquid crystal composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6341446A JPS6341446A (en) | 1988-02-22 |
| JPH0784416B2 true JPH0784416B2 (en) | 1995-09-13 |
Family
ID=16164209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61185066A Expired - Lifetime JPH0784416B2 (en) | 1986-08-08 | 1986-08-08 | Novel liquid crystal compound and liquid crystal composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0784416B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2598670B2 (en) * | 1988-04-01 | 1997-04-09 | 旭電化工業株式会社 | Optically active aryl ester compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1596012A (en) * | 1976-08-16 | 1981-08-19 | Secr Defence | Optically active liquid crystal materials and liquid crystal devices containing them |
| GB1603076A (en) * | 1977-04-05 | 1981-11-18 | Secr Defence | Esters of (+)-4-(2'-methylbutyl)phenol and their use as liquid crystal materials |
-
1986
- 1986-08-08 JP JP61185066A patent/JPH0784416B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6341446A (en) | 1988-02-22 |
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