JPH02233656A - Alkenyl ether compound with liquid crystal nature - Google Patents
Alkenyl ether compound with liquid crystal natureInfo
- Publication number
- JPH02233656A JPH02233656A JP1053403A JP5340389A JPH02233656A JP H02233656 A JPH02233656 A JP H02233656A JP 1053403 A JP1053403 A JP 1053403A JP 5340389 A JP5340389 A JP 5340389A JP H02233656 A JPH02233656 A JP H02233656A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- compound
- formula
- cyanobenzene
- penzoyloxy
- 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 52
- -1 Alkenyl ether compound Chemical class 0.000 title claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 abstract description 4
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 abstract description 3
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 abstract description 3
- 210000002858 crystal cell Anatomy 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- REIVHYDACHXPNH-UHFFFAOYSA-N 2-fluoro-4-hydroxybenzonitrile Chemical compound OC1=CC=C(C#N)C(F)=C1 REIVHYDACHXPNH-UHFFFAOYSA-N 0.000 description 2
- LPNANKDXVBMDKE-UHFFFAOYSA-N 5-bromopent-1-ene Chemical compound BrCCCC=C LPNANKDXVBMDKE-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RQQKUZDJSZVTFZ-UHFFFAOYSA-N 4-pent-4-enoxybenzoic acid Chemical compound OC(=O)C1=CC=C(OCCCC=C)C=C1 RQQKUZDJSZVTFZ-UHFFFAOYSA-N 0.000 description 1
- ZFMZVPQITKHDHE-UHFFFAOYSA-N 4-pent-4-enoxybenzoyl chloride Chemical compound ClC(=O)C1=CC=C(OCCCC=C)C=C1 ZFMZVPQITKHDHE-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- GSJLXIQYSOVZQU-UHFFFAOYSA-N methyl 4-pent-4-enoxybenzoate Chemical compound COC(=O)C1=CC=C(OCCCC=C)C=C1 GSJLXIQYSOVZQU-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は液晶性アルケニルエーテル化合物およびそれを
含む液晶組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a liquid crystalline alkenyl ether compound and a liquid crystal composition containing the same.
液晶は最近主に表示素子の誘電体と．して極めて重要性
を増してきている。その理由は、かかる物質の誘電率お
よび屈折率の異方性に基づく電気光学効果Ｋ帰する。液
晶Ｋ基づく表示方式には、たとえば動的散乱方式、相転
移方式、ＤＡＰ方式、ゲスト・ホスト方式や９０″ツイ
ストセルを用いるＴＮ方式および１８０゜〜２７０°ツ
イストセルを用いるＳＴＮ′ｉたはＳＩＩＥ方式がある
。これらの表示方式に用いられる液晶材料Ｋは種々の特
性が要求される。たとえば液晶相温度範囲が広いこと、
水分、熱、空気、光、電気等の環境因子に対して安定で
あること、無色であることあるいは低電圧で液晶表示素
子を駆動させうろこと、適当な屈折率の異方性量（以下
Δｎと略す。）を有することなどである。Recently, liquid crystals have mainly been used as dielectric materials for display elements. It has become extremely important. The reason for this is the electro-optical effect K based on the anisotropy of the dielectric constant and refractive index of such materials. Display methods based on liquid crystal K include, for example, the dynamic scattering method, the phase change method, the DAP method, the guest-host method, the TN method using a 90" twist cell, and the STN'i or SIIE using a 180° to 270° twist cell. The liquid crystal material K used in these display methods is required to have various characteristics.For example, a wide liquid crystal phase temperature range,
It must be stable against environmental factors such as moisture, heat, air, light, and electricity, it must be colorless, it must be able to drive the liquid crystal display element with low voltage, and it must have an appropriate amount of refractive index anisotropy (hereinafter abbreviated as Δn). ).
一般に、液晶表示素子を低電圧で駆動させるためには、
誘電率の異方性量（以下Δ会と略す。）の大きい液晶材
料が良いとされている。このような化合物として、４−
ｎ−アルキルベンゾイルオキシ−３′−フロロー４′−
シアノベンゼン（特開昭５８−８３６６５号）あるいは
４−ｎ−アルコキシベンゾイルオキシ−３′−フロロー
４′−シアノベンゼン（ Ｒｅｌｙ． Ｃｈｉｓ．Ａｃ
ｔａ ， ６？ ｔｂ）ｚ ＋ ５ｑ２ａｍλ）などが
知られているが、これらの多くは液晶相を持ち難くモノ
トロビック液晶であることが多い。Generally, in order to drive a liquid crystal display element at low voltage,
It is said that a liquid crystal material with a large dielectric constant anisotropy (hereinafter abbreviated as Δ) is good. Such compounds include 4-
n-alkylbenzoyloxy-3'-fluoro4'-
Cyanobenzene (JP-A-58-83665) or 4-n-alkoxybenzoyloxy-3'-fluoro-4'-cyanobenzene (Rely. Chis. Ac
Ta, 6? tb)z + 5q2amλ) and the like are known, but many of these are difficult to have a liquid crystal phase and are often monotropic liquid crystals.
また、液晶表示セルの干渉縞を防止するために、Δｎと
セル厚ｄ（μ１ｒＬ）の積は一定の値に設定されている
。そのため、Δｎの大きな液晶材料を使用すればｄの値
を小さくでき、応答時間（τ）は、′周知のτｏｅ ｄ
”の式よ夛短かくなる。Furthermore, in order to prevent interference fringes in the liquid crystal display cell, the product of Δn and cell thickness d (μ1rL) is set to a constant value. Therefore, if a liquid crystal material with a large Δn is used, the value of d can be reduced, and the response time (τ) can be reduced by the well-known τoe d
” The expression is much shorter.
現在、単一の化合物で表示素子を十分に駆動させ得る化
合物はなく、実際には数種の液晶性化合物を混合した液
晶混合物が使用されている。そのため、液晶性化合物が
他の液晶混合物に対して相溶性が良いことも要求される
。Currently, there is no single compound that can sufficiently drive a display element, and in fact, a liquid crystal mixture of several types of liquid crystal compounds is used. Therefore, it is also required that the liquid crystal compound has good compatibility with other liquid crystal mixtures.
本発明において、液晶性化合物とは、液晶化合物あるい
は液晶表示素子を駆動させるための何らかの面に関与す
る化合物のことをいう。In the present invention, the liquid crystal compound refers to a liquid crystal compound or a compound that is involved in some aspect for driving a liquid crystal display element.
本発明は、液晶表示素子に使用される液晶材料に求めら
れる諸特性の中で、液晶相を持ち、Δｅが大きく、Δｎ
が比較的大きく、他の液晶性化合物との相溶性の良い液
晶性化合物を提供することであル、低電圧で液晶表示素
子を駆動させることを可能にする本発明の組成物を提供
することである。Among the various properties required for a liquid crystal material used in a liquid crystal display element, the present invention is characterized by having a liquid crystal phase, having a large Δe, and having a large Δn.
To provide a composition of the present invention, which has a relatively large liquid crystal compound and has good compatibility with other liquid crystal compounds, and which makes it possible to drive a liquid crystal display element with a low voltage. It is.
本発明の液晶性化合物は、一般式
（式中、Ｒは炭素数２〜７のアルケニル基を表鳴）で示
されるアルケニルエーテルであることを特徴とする。The liquid crystal compound of the present invention is characterized by being an alkenyl ether represented by the general formula (wherein R represents an alkenyl group having 2 to 7 carbon atoms).
本発明の液晶性化合物の合成法は、っぎの式で示される
。The method for synthesizing the liquid crystalline compound of the present invention is shown by the following formula.
上記の合成法をさらＫ説明すると
第１段階はＰ−ヒドロオキシ安息香酸メチル（ｎ）にメ
タノールあるいはエタノールなどの溶媒中で、水酸化ナ
トリウムあるいは水酸化カリウムなどの触媒を用い、ア
ルケニルブロマイドＣＩＩ［）ト−Ｃ−ｆル化させるこ
とによシＰ−アルキルオキシ安息香酸メチル〔■〕を得
る。ただし、アルヶニルブロマイド（ＩＩＩ）はその対
応するクロライド、アイオダイド、トシレートあるいは
メシレートなどでも良い。To further explain the above synthesis method, the first step is to convert methyl P-hydroxybenzoate (n) into alkenyl bromide CII[) using a catalyst such as sodium hydroxide or potassium hydroxide in a solvent such as methanol or ethanol. Methyl cycloP-alkyloxybenzoate [■] is obtained by to-C-fluorination. However, alganyl bromide (III) may also be its corresponding chloride, iodide, tosylate or mesylate.
第２段階は第１段階で得られ九Ｐ−アルキルオキシ安息
香酸メチル（ＩＶ）を加水分解することによシ、Ｐ−ア
ルキルオキシ安息香酸（Ｖ）を得る。用いられる触媒と
しては、一般Ｋ使用される酸触媒（硫酸、塩酸など）あ
るいは塩基触媒（水酸化ナトリウム、水酸化カリウムな
ど）で良い。In the second step, P-alkyloxybenzoic acid (V) is obtained by hydrolyzing the 9-P-alkyloxybenzoic acid methyl (IV) obtained in the first step. The catalyst used may be a commonly used acid catalyst (sulfuric acid, hydrochloric acid, etc.) or a basic catalyst (sodium hydroxide, potassium hydroxide, etc.).
第３段階は第２段階で得られたＰ−アルキルオキシ安息
香酸（Ｖ）を塩化チオニルなどを用いて、トルエンなど
の不活性溶媒中あるいは無溶媒でＰ一アルキルオキシ安
息香酸クロライド〔■〕を得る。The third step is to convert the P-alkyloxybenzoic acid (V) obtained in the second step to P-alkyloxybenzoic acid chloride [■] using thionyl chloride or the like in an inert solvent such as toluene or without a solvent. obtain.
第４段階は第３段階で得られたＰ−アルキルオキシ安息
香酸クロライド（Ｖｌ）と３−フロロ−４−シアノフェ
ノール１〕を、無溶媒あるいはトルエンなどの不活性溶
媒中、塩基触媒（ピリジン、トリエチルアミンなど）を
用いて本発明の化合物である４−（４−アルキルオキシ
）ペンゾイルオキシー３′−フロロー４′−シアノベン
ゼンＣＩ）を得る。In the fourth step, the P-alkyloxybenzoic acid chloride (Vl) obtained in the third step and 3-fluoro-4-cyanophenol 1] are mixed without a solvent or in an inert solvent such as toluene with a base catalyst (pyridine, triethylamine, etc.) to obtain the compound of the present invention, 4-(4-alkyloxy)penzoyloxy-3'-fluoro-4'-cyanobenzene CI).
このようにして得られた本発明の化合物の１つである４
−（４−ペンテニルオキシ）ペンゾイルオキシー３′−
フロロー４′−シアノベンゼンの４１ｄｌ点は、結晶−
ネマチツク相転移点（以下ＣＮ点と略す。）は３８℃で
ｓｂ、ネマチック相一等方性液体相転移点（以下ＮＩ点
と略す。）は４１℃であった。これは対応する鎖長を持
った４−ｎ−ヘキシルベンゾイルオキシ−３′−フロロ
ー４′−シアノベンゼン（結晶一等方性液体相転移点（
以下ＣＩ点と略す。）３５℃、ＮＩ点８℃）および４
−ｎ−ペンテニルオキシベンゾイルオキシ−３′−フロ
ロー４′−シアノベンゼン（ＣＩ点６６℃、ＮＩ点４１
℃）がモノトロビック液晶であるのに対し、本発明の化
合物である４−（４−ペンテニルオキシ）ペンゾイルオ
キシー３′−フロロー４′−シアノベンゼンはエナンチ
オト口ピック液晶であった。One of the compounds of the present invention thus obtained, 4
-(4-pentenyloxy)penzoyloxy-3'-
The 41dl point of Fluoro 4'-cyanobenzene is the crystal-
The nematic phase transition point (hereinafter abbreviated as CN point) was sb at 38°C, and the nematic phase monoisotropic liquid phase transition point (hereinafter abbreviated as NI point) was 41°C. This is 4-n-hexylbenzoyloxy-3'-fluoro-4'-cyanobenzene (crystalline isotropic liquid phase transition point (
Hereinafter, it will be abbreviated as CI point. ) 35°C, NI point 8°C) and 4
-n-pentenyloxybenzoyloxy-3'-fluoro-4'-cyanobenzene (CI point 66°C, NI point 41
C) was a monotropic liquid crystal, whereas the compound of the present invention, 4-(4-pentenyloxy)penzoyloxy-3'-fluoro-4'-cyanobenzene, was an enantiotopic liquid crystal.
以上の比較からもわかるとおシ、本発明の液晶性アルケ
ニルエーテル化合物は、公知の類似化合物と比べてよシ
液晶相を有しやすいのが特徴である。As can be seen from the above comparison, the liquid crystalline alkenyl ether compound of the present invention is characterized in that it tends to have a liquid crystal phase more easily than known similar compounds.
本発明の液晶性アルケニル化合物は、Δｅが大き〈、液
晶セルに入れた時のしきい値電圧を低くできることよ）
、液晶表示素子をより低電圧で駆動させることを可能に
する。The liquid crystalline alkenyl compound of the present invention has a large Δe (this makes it possible to lower the threshold voltage when placed in a liquid crystal cell).
, it is possible to drive a liquid crystal display element at a lower voltage.
また、比較的大きいΔｎを有するので、よ）応答速度の
速い液晶表示素子を作製できる。Furthermore, since it has a relatively large Δn, a liquid crystal display element with a high response speed can be manufactured.
さらに、他の液晶性化合物、例えばエステル系、シツフ
系、エタン系、アセチレン系、アゾキシ系、ビフエニル
系、シクロヘキサン系、シクロヘキセン系、ピリジン系
、ピリミジン系、ジオキサン系等の既存の液晶性化合物
との相溶性が優れているので、それらの化合物または混
合物と混合することによｂｍ々の用途に適した液晶材料
とすることができる。Furthermore, with other liquid crystal compounds such as ester, Schiff, ethane, acetylene, azoxy, biphenyl, cyclohexane, cyclohexene, pyridine, pyrimidine, dioxane, etc. Since they have excellent compatibility, by mixing them with compounds or mixtures thereof, liquid crystal materials suitable for various BBM applications can be obtained.
本発明の液晶組成物は少くとも２つの液晶または液晶性
化合物を含み、その少くとも一方は前記〔Ｉ〕式にて表
わされる液晶性化合物であることを特徴とする。The liquid crystal composition of the present invention is characterized in that it contains at least two liquid crystals or liquid crystal compounds, at least one of which is a liquid crystal compound represented by the above formula [I].
本発明の液晶組成物の成分としてＣＩ）式と混合して用
いられる化合物としてつぎの（１）〜（ｘｘｘｌｉｉ）
式で表わされる既知の化合物群をあげることができる。The following compounds (1) to (xxxlii) are used as a component of the liquid crystal composition of the present invention in combination with formula CI).
A group of known compounds represented by the formula can be mentioned.
一〇Ｎ ，ハロゲン原子、Ｒ１または−ＯＲ”を示しＲ
およびＲ１はアルキル基またはアルケニル基を示す。1〇N, halogen atom, R1 or -OR”
and R1 represents an alkyl group or an alkenyl group.
以下実施例によシ本発明をさらに具体的に説明するが、
本発明はこれらの例に限定されるものではない。The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these examples.
また各例中にて記号はつぎの通）とする。In addition, the symbols in each example are as follows.
ＣＮ点：結晶一ネマチツク相転移点
ＮＩ点：ネマチツク相一等方性液体相転移点ＣＩ点：結
晶一等方性液体相転移点
実施例１
４−（４−ペンテニルオキシ）ペンゾイルオキシー３′
−フロロー４′−シアノベンゼンの合成第１段階
２００ａ三ツ口フラスコに、ｐ−ヒドロキシ安息香酸メ
チル１７．０Ｎ（０．１１モル）、５−ブロモー１−ペ
ンテン２５．０．９（０．１７モル）、水酸化カリウム
７．６ｇ（０。１３モル）およびメタノール９０ゴを加
え、８時間還流した。放冷後、２Ｎ水酸化ナトリウム水
溶液１００ゴおよびトルエンｌＱＱｄを加え抽出した。CN point: Crystalline mononematic phase transition point NI point: Nematic phase monoisotropic liquid phase transition point CI point: Crystalline monoisotropic liquid phase transition point Example 1 4-(4-pentenyloxy)penzoyloxy-3'
- Synthesis of fluoro-4'-cyanobenzene First step 200a In a three-necked flask, 17.0N (0.11 mol) of methyl p-hydroxybenzoate and 25.0.9 (0.17 mol) of 5-bromo-1-pentene were added. , 7.6 g (0.13 mol) of potassium hydroxide and 90 g of methanol were added, and the mixture was refluxed for 8 hours. After cooling, 100g of a 2N aqueous sodium hydroxide solution and 1QQd of toluene were added for extraction.
中性Ｋなるまで有機層を水洗し、無水硫酸マグネシウム
上で乾燥後、乾燥剤を除去して減圧濃縮した。これをジ
クロロメタン溶媒にてシリカゲルカラムを通し、溶媒を
留去して２ ３． ２ Ｆのｐ−（４−ペンテニルオキ
シ）安息香酸メチルを得た。The organic layer was washed with water until neutral K, dried over anhydrous magnesium sulfate, the desiccant was removed, and the mixture was concentrated under reduced pressure. This was passed through a silica gel column using dichloromethane solvent, and the solvent was distilled off.23. 2F methyl p-(4-pentenyloxy)benzoate was obtained.
第２段階
３ＱＱｍ／三ツ口フラスコに第１段階で得られたｐ−（
４−ペンテニルオキシ）安息香酸メチル２３．：ｌ（０
．１１モル）、水酸化カリウム８．９ＩＩ（０．１６モ
ル）、水５０ｒｎｌ及びメタノール５０ｒ１ｌｌを加え
、１時間還流した。放冷後、これを氷冷した希塩酸にそ
そぎ、析出した結晶を戸過し、充分水を除去した後、ヘ
プタンとトルエンの混合溶媒から再結晶し、乾燥後、１
７．Ｏｉのｐ一（４−ペンテニルオキシ）安息香酸を得
た。Second stage 3QQm/3-necked flask containing p-(
Methyl 4-pentenyloxy)benzoate23. :l(0
．． 11 mol), 8.9 II (0.16 mol) of potassium hydroxide, 50 rnl of water and 50 rnl of methanol were added, and the mixture was refluxed for 1 hour. After cooling, it was poured into ice-cooled dilute hydrochloric acid, the precipitated crystals were filtered out, water was sufficiently removed, recrystallized from a mixed solvent of heptane and toluene, and after drying,
7. Oi p-(4-pentenyloxy)benzoic acid was obtained.
第３段階
２００ｄナスフラスコに、第２段階で得られたｐ−（４
−ペンテニルオキシ）安息香酸１２．９ｇ（０．０６モ
ル）、塩化チオニル１ １．２ ，Ｆ（０．０ ９モル
）及びトルエン３９ｄを加え、３時間加熱した。Third stage: In a 200d eggplant flask, the p-(4
12.9 g (0.06 mol) of -pentenyloxy)benzoic acid, 1 1.2 ,F thionyl chloride (0.09 mol) and 39 d of toluene were added and heated for 3 hours.
放冷後、減圧濃縮して蒸留し、１１．７１／のｐ−（４
−ペンテニルオキシ）安息香酸クロライドを得た。After cooling, it was concentrated under reduced pressure and distilled to give 11.71/p-(4
-pentenyloxy)benzoic acid chloride was obtained.
沸点は３ ｒｒｘＨ１ｇで１４９℃であった。The boiling point was 149°C at 3rrxH1g.
第４段階
２００ゴ三ツ口フラスコに３−フロロ−４−シアノフェ
ノール６．４ＪＦ（０．０５モル）、ピリジン６．２．
９（０．０８モル）及びトルエン２０ｌＩｌｌを加え、
室温で撹拌しながら、第４段階で得られたｐ−（４ーペ
ンテニルオキシ）安息香酸クロライド１１．７．９（０
．０５モル）の５０ｍｌ｝ルエン溶液を滴下して６時間
撹拌した。その後、水５ＱｍＪを加え水層を除去し、炭
酸水素ナトリウム水溶液で洗浄後、中性になるまで水洗
した。無水硫酸マグネシウムにテ乾燥し、ヘプタンとベ
ンゼンの混合溶媒で再結晶して乾燥後，５．８．９の４
−（４−ペンテニルオキシ）ペンゾイルオキシ−３′−
フロロー４′−シアノベンゼンを得た。この化合物のＮ
ＭＲスペクトルは構造を支持した。Fourth stage: In a 200 g three-necked flask, 6.4 JF (0.05 mol) of 3-fluoro-4-cyanophenol and 6.2 JF of pyridine.
9 (0.08 mol) and 20 lIll of toluene were added,
While stirring at room temperature, add p-(4-pentenyloxy)benzoic acid chloride 11.7.9 (0
．． A solution of 0.05 mol) in 50 ml of toluene was added dropwise and stirred for 6 hours. Thereafter, 5 QmJ of water was added, and the aqueous layer was removed, washed with an aqueous sodium bicarbonate solution, and then washed with water until neutral. After drying over anhydrous magnesium sulfate, recrystallizing with a mixed solvent of heptane and benzene, and drying,
-(4-pentenyloxy)penzoyloxy-3'-
Fluoro 4'-cyanobenzene was obtained. N of this compound
MR spectra supported the structure.
ＣＮ点＝３８℃、ＮＩ点：４１℃であった。The CN point was 38°C, and the NI point was 41°C.
実施例２
実施例１の５−ブロモー１−ペンテン（ ０． １ ７
モル）ヲ他のアルキルブロマイド（ ０． １ ７モル
）に代え、他は同様に行ない、下記の化合物を合成した
。Example 2 5-bromo-1-pentene (0.1 7
The following compound was synthesized in the same manner except that mol) was replaced with another alkyl bromide (0.17 mol).
４−アリルオキシベンゾイルオキシ−３′−フロロ−４
′ーシアノベンゼン、
４−（（Ｅ）−２−ブテニルオキシ）ペンゾイルオキシ
ー３′−フロロー４′−シアノベンゼン、
４−（３−ブテニルオキシ）ペンゾイルオキシー３′−
フロロ−４′−シアノベンゼン（ＣＩ点：４１℃、ＮＩ
点＝１１℃）、
４−（（Ｅ）−２−ペンテニルオキシ）ペンゾイルオキ
シー３′−フロロー４′−シアノベンゼン、４−（（Ｅ
）−３−ペンテニルオキシ）ペンゾイルオキシー３′−
７口ロー４′−シアノベンゼン、４−（（Ｅ）−２−へ
キセニルオキシ）ペンゾイルオキシ−３′−フロロー４
′−シアノベンゼン、４−（（Ｅ）−３−ヘキセニルオ
キシ）ペンゾイルオキシ−３７−フロロ−４′−シアノ
ベンゼン、４−（（Ｅ）−４−ヘキセニルオキシ）ペン
ゾイルオキシー３′−フロロー４′−シアノベンゼン、
４−（５−へキセニルオキシ）ペンゾイルオキシ−３′
一フロロー４′−シアノベンゼン、
４−（（Ｅｌ２−ヘプテニルオキシ）ペンゾイルオキシ
−３′−７口ロー４′−シアノベンゼン、４−（（Ｅ）
−３−ヘプテニルオキシ）ペンゾイルオキシ−３′−フ
ロロー４′−シアノベンゼン、４−（（Ｅ）−４−ヘプ
テニルオキシ）ペンゾイルオキシ−３′−フロロー４′
−シアノベンゼン、４−（ＴＥＩ−５−ヘプテニルオキ
シ）ペンゾイルオキシ−３′−フロロー４′−シアノベ
ンゼン、４−（６−ヘプテニルオキシ）ペンゾイルオキ
シ−３′ーフロロー４′−シアノベンゼン、
４−（（Ｅ）−２−オクテニルオキシ）ペンゾイルオキ
シー３′−フロロー４′−シアノベンゼン、４−（（Ｅ
ｌ−３−オクテニルオキシ）ペンゾイルオキシー３′−
フロロー４′−シアノベンゼン、４−（（Ｅ）−４−オ
クテニルオキシ）ペンゾイルオキシ−３′−７口ロー４
′−シアノベンゼン、４−（（Ｅ）−５−オクテニルオ
キシ）ペンゾイルオキシー３′−フロロー４′−シアノ
ベンゼン、４−（（Ｅ）−６−オクテニルオキシ）ペン
ゾイルオキシー３′−フロロ．−４′−シアノベンゼン
、４−（７−オクテニルオキシ）ペンゾイルオキシー３
′−フロロー４′−シアノベンゼン
実施例３
ネマチツク液晶組成物Ａ
に実施例１に示した４−（４−ペンテニルオキシ）ペン
ゾイルオキシー３′−フロロー４７−シアノベンゼン１
５重量部を添加した。その結果、Δεは１１．０から１
３．３に上昇し、しきい値電圧は１．７８（Ｖ：ｌから
１．４４（Ｖ）Ｋ低下し、Δｎは０． １ ３ ７から
０．１４２に上昇した。4-allyloxybenzoyloxy-3'-fluoro-4
'-cyanobenzene, 4-((E)-2-butenyloxy)penzoyloxy-3'-fluoro4'-cyanobenzene, 4-(3-butenyloxy)penzoyloxy-3'-
Fluoro-4'-cyanobenzene (CI point: 41°C, NI
point = 11°C), 4-((E)-2-pentenyloxy)penzoyloxy-3'-fluoro4'-cyanobenzene, 4-((E)
)-3-pentenyloxy)penzoyloxy-3'-
7-mouth rho 4'-cyanobenzene, 4-((E)-2-hexenyloxy)penzoyloxy-3'-fluoro 4
'-cyanobenzene, 4-((E)-3-hexenyloxy)penzoyloxy-37-fluoro-4'-cyanobenzene, 4-((E)-4-hexenyloxy)penzoyloxy-3'-fluoro4' -cyanobenzene,
4-(5-hexenyloxy)penzoyloxy-3'
4-((E)
-3-heptenyloxy)penzoyloxy-3'-fluoro4'-cyanobenzene, 4-((E)-4-heptenyloxy)penzoyloxy-3'-fluoro4'
-cyanobenzene, 4-(TEI-5-heptenyloxy)penzoyloxy-3'-fluoro4'-cyanobenzene, 4-(6-heptenyloxy)penzoyloxy-3'-fluoro4'-cyanobenzene, 4-((E )-2-octenyloxy)penzoyloxy-3'-fluoro4'-cyanobenzene, 4-((E
l-3-octenyloxy)penzoyloxy-3'-
Fluoro 4'-Cyanobenzene, 4-((E)-4-octenyloxy)penzoyloxy-3'-7-Ro4
'-cyanobenzene, 4-((E)-5-octenyloxy)penzoyloxy-3'-fluoro4'-cyanobenzene, 4-((E)-6-octenyloxy)penzoyloxy-3'-fluoro. -4'-cyanobenzene, 4-(7-octenyloxy)penzoyloxy-3
'-Fluoro-4'-cyanobenzene Example 3 Nematic liquid crystal composition A 4-(4-pentenyloxy)penzoyloxy-3'-fluoro-47-cyanobenzene 1 shown in Example 1
5 parts by weight were added. As a result, Δε is from 11.0 to 1
3.3, the threshold voltage decreased by 1.44 (V)K from 1.78 (V:l), and Δn increased from 0.137 to 0.142.
実施例４
ネマチツク液晶組成物Ａ１００重量部に４−（３一ブテ
ニルオキシ）ペンゾイルオキシー３′−７口ロー４′−
シアノベンゼンを１５重量部を加えて液晶組成物を得た
。その物性値を表１に示す。Example 4 100 parts by weight of nematic liquid crystal composition A was added with 4-(3-butenyloxy)penzoyloxy-3'-7-4'-
A liquid crystal composition was obtained by adding 15 parts by weight of cyanobenzene. The physical property values are shown in Table 1.
実施例５
ネマチック液晶組成物ＡＩＯＯ重量部に４−（５ーへキ
セニルオキシ）ペンゾイルオキシ−３′−フロロー４′
−シアノベンゼンを１５重量部を加えて液晶組成物を得
た。その物性値を表ＩＫ示す。Example 5 4-(5-hexenyloxy)penzoyloxy-3'-fluoro 4' is added to parts by weight of nematic liquid crystal composition AIOO.
- 15 parts by weight of cyanobenzene was added to obtain a liquid crystal composition. Its physical property values are shown in Table IK.
表 １
させることができる。また、比較的大きなΔｎを有する
ことによシ、セル厚ｄを小さくできるためよシ応答速度
が速い液晶表示素子を作製できる。Table 1 Further, by having a relatively large Δn, the cell thickness d can be made small, so that a liquid crystal display element with a faster response speed can be manufactured.
さらに、液晶相を持ちやすく、相溶性に優れているため
種々の液晶表示素子に使用される液晶組成物に使用でき
る。Furthermore, since it easily has a liquid crystal phase and has excellent compatibility, it can be used in liquid crystal compositions used in various liquid crystal display elements.
以上that's all
Claims (1)
示されるアルケニルエーテルであることを特徴とする液
晶性化合物。 ２）少なくとも一種の構成成分が特許請求の範囲第１項
記載のアルケニルエーテル化合物であることを特徴とす
る液晶組成物。[Claims] 1) An alkenyl ether represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc.▼‥‥[I] (In the formula, R represents an alkenyl group having 2 to 7 carbon atoms) A liquid crystal compound characterized by: 2) A liquid crystal composition characterized in that at least one constituent component is an alkenyl ether compound according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1053403A JP2789345B2 (en) | 1989-03-06 | 1989-03-06 | Liquid crystalline alkenyl ether compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1053403A JP2789345B2 (en) | 1989-03-06 | 1989-03-06 | Liquid crystalline alkenyl ether compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02233656A true JPH02233656A (en) | 1990-09-17 |
| JP2789345B2 JP2789345B2 (en) | 1998-08-20 |
Family
ID=12941863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1053403A Expired - Lifetime JP2789345B2 (en) | 1989-03-06 | 1989-03-06 | Liquid crystalline alkenyl ether compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2789345B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363336C (en) * | 2006-01-06 | 2008-01-23 | 青岛科技大学 | Novel liquid crystal compound——3-[4-(2-methylpropoxy-1)phenyl]acrylic acid-2-fluoro-4-hydroxybenzonitrile ester and its preparation method |
| JP2009108321A (en) * | 1996-10-31 | 2009-05-21 | Merck Patent Gmbh | Dope |
| CN109897644A (en) * | 2017-12-07 | 2019-06-18 | 北京大学 | A kind of high contrast, low voltage drive and quick response electrically-controlled liquid crystal light modulation film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6366229A (en) * | 1986-06-25 | 1988-03-24 | ザ ゼネラル エレクトリツク カンパニ−，ピ−．エル．シ− | Liquid crystal polymer |
| JPH02225444A (en) * | 1989-02-28 | 1990-09-07 | Seimi Chem Kk | Alkenyl compound and liquid crystal composition containing same |
-
1989
- 1989-03-06 JP JP1053403A patent/JP2789345B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6366229A (en) * | 1986-06-25 | 1988-03-24 | ザ ゼネラル エレクトリツク カンパニ−，ピ−．エル．シ− | Liquid crystal polymer |
| JPH02225444A (en) * | 1989-02-28 | 1990-09-07 | Seimi Chem Kk | Alkenyl compound and liquid crystal composition containing same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009108321A (en) * | 1996-10-31 | 2009-05-21 | Merck Patent Gmbh | Dope |
| CN100363336C (en) * | 2006-01-06 | 2008-01-23 | 青岛科技大学 | Novel liquid crystal compound——3-[4-(2-methylpropoxy-1)phenyl]acrylic acid-2-fluoro-4-hydroxybenzonitrile ester and its preparation method |
| CN109897644A (en) * | 2017-12-07 | 2019-06-18 | 北京大学 | A kind of high contrast, low voltage drive and quick response electrically-controlled liquid crystal light modulation film and preparation method thereof |
| CN109897644B (en) * | 2017-12-07 | 2020-09-18 | 北京大学 | A high-contrast, low-voltage driving and fast-response electronically controlled liquid crystal dimming film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2789345B2 (en) | 1998-08-20 |
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