JPH03161484A - Ether-based dioxane derivative - Google Patents
Ether-based dioxane derivativeInfo
- Publication number
- JPH03161484A JPH03161484A JP29950889A JP29950889A JPH03161484A JP H03161484 A JPH03161484 A JP H03161484A JP 29950889 A JP29950889 A JP 29950889A JP 29950889 A JP29950889 A JP 29950889A JP H03161484 A JPH03161484 A JP H03161484A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- liquid crystal
- compound shown
- value
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title 2
- 150000002012 dioxanes Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 10
- 239000004988 Nematic liquid crystal Substances 0.000 abstract description 7
- 238000010992 reflux Methods 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000004210 ether based solvent Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000004973 liquid crystal related substance Substances 0.000 description 25
- -1 lithium aluminum hydride Chemical compound 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- MYUPCEIJNBAAFL-UHFFFAOYSA-N 2-fluoro-4-formylbenzonitrile Chemical group FC1=CC(C=O)=CC=C1C#N MYUPCEIJNBAAFL-UHFFFAOYSA-N 0.000 description 1
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical group O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CLWLSXFPGZCOBC-UHFFFAOYSA-N phenylmethanesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)CC1=CC=CC=C1 CLWLSXFPGZCOBC-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電気光学的表示材料、更に詳しくは液晶表示装
置に有用な新規な化合物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel compounds useful in electro-optic display materials, and more particularly in liquid crystal display devices.
液晶表示セルの代表的なものにエム・シャット（ Ｍ
− Ｓｃｈａｄｔ）等［ＡＰＰＬＩＥＤ ＰＨＹＳＩＣ
Ｓ ＬＥＴＴＥＲＳ １８Ｌ１２７〜１２８ （１９７
１） ］によって提案された電界効果型セル（フィール
ド・エフェクト・モード・セル）又はジー・エイチ・ハ
イルマイマー（ Ｇ−ＨＨｅｉｌｍｅｉｅｒ）等（ Ｐ
ＲＯＣＥＥＤＩＮＧ ＯＦ ＴＨＥＩ． Ｅ． Ｅ．
Ｅ．国 １１６２〜１１７１ （１９６８） ）によっ
て提案された動的光散型セル（ダイミック・スキャッタ
リング・モード・セル）又はジー・エイチ・ハイルマイ
ヤー（ Ｇ−Ｈ −Ｈｅｉｌｍｅｉｅｒ）等（ＡＰＰＬ
ＩＥＤ ＰＨＹＳＩＣＳ ＬＥＴＴＥＲＳ１３ ， ９
１ （１９６８））あるいはディー・エル・ホワイト
（ Ｄ−Ｌ −一ｈｉｔｅ）等 （ ＪＯＵＲＮＡＬ
ＯＦ ＡＰＰＬＩＥＤＰＨＹＳＩＣＳ並， ４７
１８（１９７４） ）によって提案されたゲスト・ホス
ト型セルなどがある。A typical liquid crystal display cell is M-Shut (M
- Schadt) etc. [APPLIED PHYSIC
S LETTERS 18L127~128 (197
1)] or the field effect mode cell proposed by G-H Heilmeier et al. (P
ROCEEDING OF THEI. E. E.
E. 1162-1171 (1968)) or the dynamic scattering mode cell proposed by G-H Heilmeier et al. (APPL).
IED PHYSICS LETTERS13, 9
1 (1968)) or D. L. White
(D-L-ichihite) etc. (JOURNAL
OF APPLIEDPHYSICS, 47
18 (1974)), etc.
これらの液晶表示セルの中で現在主流をなすものは、電
界効果型セルの一種のＴＮ型セルである。Among these liquid crystal display cells, the one currently mainstream is a TN type cell, which is a type of field effect cell.
このＴＮ型セルにおいては、Ｇ． Ｂａｕｅｒによって
Ｍｏｌ． Ｃｒｙｓｔ． Ｌｉｑ． Ｃｒｙｓｔ． ６
３ ． ４５（１９８１）に報告されているように、セ
ル外観を損う原因となるセル表面での干渉縞の発生を防
止するために、セルに充填される液晶材料の屈折率の異
方性（Δｎ）とセルにおける液晶層の厚さ（ｄ）μｍの
積を或る特定の値に設定する必要がある。実用的に使用
される液晶表示セルでは、Δｎ−ｄの値が０６５、１．
０，１．６又は２．２のいずれかに設定されている．通
常、Δｎ−ｄの値を０．５に設定した場合、視角特性が
良くなるという特徴があり、Δｎ−ｄの値を１．０、１
．６又は２．２に設定した場合、正面からのコントラス
トが良くなるという特徴がある。従って、どの方向から
も見やすい視角特性を重視する液晶表示セルの場合は、
Δｎ−ｄの値を０．５に設定し、特に正面からのコント
ラストを重視する液晶表示セルの場合は、Δｎ・ｄの値
を１．０，１６６又は２．２に設定するのが普通である
。In this TN type cell, G. Mol. Bauer. Cryst. Liq. Cryst. 6
3. 45 (1981), the refractive index anisotropy (Δn ) and the thickness (d) of the liquid crystal layer in the cell (μm) must be set to a certain value. In practically used liquid crystal display cells, the value of Δn-d is 065, 1.
It is set to either 0, 1.6 or 2.2. Usually, when the value of Δn-d is set to 0.5, the viewing angle characteristics are improved, and the value of Δn-d is set to 1.0, 1
．． When set to 6 or 2.2, the contrast from the front is improved. Therefore, for liquid crystal display cells that emphasize viewing angle characteristics that are easy to see from any direction,
The value of Δn-d is set to 0.5, and in the case of a liquid crystal display cell where contrast from the front is particularly important, the value of Δn-d is usually set to 1.0, 166 or 2.2. be.
一方、実用的に使用されている液晶表示セルにおける液
晶層の厚さは、通常、６〜１０μｍの限定された範囲で
或る値に設定されるため、Δｎ・ｄの値を０．５に設定
する場合は、Δｎの値の小さな液晶材料が必要となり、
Δｎ−ｄの値を１．０、１６又は２．２に設定する場合
は、逆に、Δｎの値の大きな液晶材料が必要となる。こ
のように、液晶表示セルの表示特性に応じてΔｎの値が
小さい液晶材料とΔｎの値が大きい液晶材料が必要とさ
れる。On the other hand, the thickness of the liquid crystal layer in practically used liquid crystal display cells is usually set to a certain value within a limited range of 6 to 10 μm, so the value of Δn・d is set to 0.5. When setting, a liquid crystal material with a small value of Δn is required,
Conversely, when the value of Δn-d is set to 1.0, 16, or 2.2, a liquid crystal material with a large value of Δn is required. Thus, depending on the display characteristics of the liquid crystal display cell, a liquid crystal material with a small value of Δn and a liquid crystal material with a large value of Δn are required.
また、ＴＮ型セルにおいては混合液晶の誘電率異方性（
Δε）が正である必要があるためΔεの値が大きく、し
きい値電圧が低いネマチック液晶化合物が必要とされて
いる。In addition, in a TN cell, the dielectric anisotropy of the mixed liquid crystal (
Since Δε) needs to be positive, a nematic liquid crystal compound with a large Δε value and a low threshold voltage is required.
Δｎの値が比較的小さく、大きい正のΔεを有で表わさ
れる化合物（式中、Ｒはアルキル基を表わす。以下、Ｄ
Ｐという。）が知られているが、本発明が解決しようと
する課題は、Δｎの値がＤＰと同程度に小さく、ＤＰよ
りΔεが大きく、しきい値電圧の低いネマチック液晶化
合物を提供することにある。A compound having a relatively small value of Δn and a large positive Δε (in the formula, R represents an alkyl group. Hereinafter, D
It's called P. ) is known, but the problem to be solved by the present invention is to provide a nematic liquid crystal compound in which the value of Δn is as small as DP, Δε is larger than DP, and the threshold voltage is low. .
本発明は、上記課題を解決するために、一般式（１） Ｘ （式中、 Ｒは炭素原子数１〜５の直鎖状アルキルは、 トランス配置を表わす。 In order to solve the above problems, the present invention provides general formula (1) X (In the formula, R is a straight chain alkyl having 1 to 5 carbon atoms, Represents the transformer arrangement.
） で表わされる化合物を提供とする。) A compound represented by is provided.
本発明に係わる式（１） の化合物は次の製造方 法に従って製造することができる。Formula (1) according to the present invention The compound is manufactured by the following method. It can be manufactured in accordance with the law.
／
乙７）
／
λ
（上記反応式におけるＲ及びＸは夫々、式（１）におけ
るＲ及びＸと同じ意味をもち、ＹはＢｒ又はＣ／！を表
わす。）
第１段１１！ − マロン酸ジエチルエステルヲ無水
エタノール中でナトリウムエトキシドの存在下に、式（
ｎ）の化合物と還流温度で反応させて、式（ＩＩＩ）の
化合物を製造する。/ Otsu 7) / λ (R and X in the above reaction formula have the same meanings as R and X in formula (1), respectively, and Y represents Br or C/!) 1st stage 11! - Malonic acid diethyl ester was prepared with the formula (
n) at reflux temperature to produce a compound of formula (III).
第２段階 一 式（ＩＩ［）の化合物を無水テトラヒド
口フラン（以下、ＴＨＦという。）の如きエーテル系溶
媒中で、水素化リチウムアルミニウム（以下、ＬｉＡ
Ｉ Ｈ４という，）で還元して、式（ＩＶ）の化合物を
製造する。Second Step 1 The compound of formula (II[) is added to lithium aluminum hydride (hereinafter referred to as LiA
IH4, ) to produce the compound of formula (IV).
第３段階 一 式（ＩＶ）の化合物をトルエン中で、Ｐ
一トルエンスルホン酸・１水和物の如き酸性触媒の存在
下に、式（Ｖ）の化合物と還流温度で反応させて脱水し
て、本発明に係わる式（Ｉ）の化合物を製造する。Third step 1. In toluene, the compound of formula (IV) is dissolved in P
The compound of formula (I) according to the present invention is prepared by reacting with the compound of formula (V) at reflux temperature and dehydrating it in the presence of an acidic catalyst such as monotoluenesulfonic acid monohydrate.
斯くして製造された本発明に係わる式（１）の化合物の
中で、代表的な化合物の相転移温度を第１表に掲げる。Among the compounds of formula (1) according to the present invention thus produced, the phase transition temperatures of representative compounds are listed in Table 1.
どＤ
，／
／
第
１
表
（表中、Ｃは結晶相、Ｎはネマチック相、■は等方性液
体相を夫々表わす。）
本発明に係る式（１）の化合物は、正の誘電率の異方性
を有するネマチック液晶化合物であり、従って例えば、
負の誘電率の異方性を有する他のネマチック液晶化合物
との混合物の状態で動的光散乱型表示セルの材料として
使用することができ、また正又は負の誘電率の異方性を
有する他のネマチック液晶化合物との混合物の状態で電
界効果型表示セルの材料として使用することができる。D , / / Table 1 (In the table, C represents a crystalline phase, N represents a nematic phase, and ■ represents an isotropic liquid phase.) The compound of formula (1) according to the present invention has a positive dielectric constant. It is a nematic liquid crystal compound with anisotropy of
It can be used as a material for dynamic light scattering display cells in a mixture with other nematic liquid crystal compounds that have negative dielectric constant anisotropy, and also have positive or negative dielectric constant anisotropy. It can be used as a material for field effect display cells in the form of a mixture with other nematic liquid crystal compounds.
このように、式（Ｉ）の化合物と混合して使用すること
のできる好ましい代表例としては、例えば４一置換安息
香酸４′一置換フエニルエステル、４一置換シクロヘキ
サンカルボン酸４′一置換フェニルエステル、４一置換
シクロヘキサンカルポ７酸４’−Ｉｎビフェニルエステ
ル、４−（４−１１シクロヘキサン力ルポニルオキシ）
安息香酸４′一置換フェニルエステル、４−（４一置換
シクロヘキシル）安息香酸４′一置換フエニルエステル
、４−（４一置換シクロヘキシル）安息香酸４’−置ａ
シクロヘキシルエステル、４−Ｉ換４’一置換ビフエニ
ル、４−置換フエニルー４’−１換シクロヘキサン、４
一置換４＃一置換ターフエニル、４−１ｍｍビフエニル
４′一置換シクロヘキサン、２−（４一置換フェニル）
−５一置換ビリミジンなどを挙げることができる。Thus, preferred representative examples which can be used in admixture with compounds of formula (I) include, for example, 4-monosubstituted benzoic acid 4'-monosubstituted phenyl ester, 4-monosubstituted cyclohexanecarboxylic acid 4'-monosubstituted phenyl ester, Ester, 4-mono-substituted cyclohexanecarpo7ic acid 4'-In biphenyl ester, 4-(4-11 cyclohexanecarponyloxy)
Benzoic acid 4'-monosubstituted phenyl ester, 4-(4-monosubstituted cyclohexyl)benzoic acid 4'-monosubstituted phenyl ester, 4-(4-monosubstituted cyclohexyl)benzoic acid 4'-a
Cyclohexyl ester, 4-I-substituted 4'-monosubstituted biphenyl, 4-substituted phenyl-4'-1-substituted cyclohexane, 4
Monosubstituted 4# monosubstituted terphenyl, 4-1mm biphenyl 4' monosubstituted cyclohexane, 2-(4 monosubstituted phenyl)
-5 monosubstituted pyrimidine and the like can be mentioned.
第２表はネマチック液晶材料として現在母体液晶として
汎用されている混合液晶（Ａ）の７０重量％と第１表に
示した式（Ｉ）の化合物ＮＯ．１とＮｏ．２及びＮｏ．
ｌと類似の化学構造を有し、Δｎが比較的低く、大き
い正のΔεを有する化合物（ａ）の各々の３０重量％と
から戒る各混合液晶について測定されたΔｎとΔεとし
きい値電圧を掲示し、比較のために混合液晶（Ａ）自体
について測定されたΔｎとΔεを掲示したものである。Table 2 shows 70% by weight of mixed liquid crystal (A), which is currently widely used as a base liquid crystal as a nematic liquid crystal material, and compound NO. of formula (I) shown in Table 1. 1 and no. 2 and no.
Δn, Δε, and threshold voltage measured for each mixed liquid crystal containing 30% by weight of each compound (a) having a chemical structure similar to that of Δn, relatively low Δn, and large positive Δε. , and Δn and Δε measured for the mixed liquid crystal (A) itself for comparison.
尚、混合液晶（Ａ）は、
から成るものであり、化合物（ａ）は、次式で表わされ
るものである。The mixed liquid crystal (A) consists of the following, and the compound (a) is represented by the following formula.
第
２
表
第２表に掲示したデータから、式（１）の化合物は負の
誘電率異方性を有する混合液晶（Ａ）に加えた時、Δｎ
を低下させ、かつ、誘電率異方性を増加させることがで
きる。本発明の化合物は、本発明の化合物を構造類似の
ＤＰ系の化合物（ａ）と比較すると、混合液晶のΔｎが
同程度に小さく、誘電率異方性の増加効果は非常に大き
く、しきい値電圧の低下効果がより大きいことが明確で
ある。Table 2 From the data posted in Table 2, when the compound of formula (1) is added to the mixed liquid crystal (A) having negative dielectric constant anisotropy, Δn
It is possible to reduce the dielectric constant anisotropy and increase the dielectric anisotropy. Comparing the compound of the present invention with the structurally similar DP compound (a), the Δn of the mixed liquid crystal is similarly small, the effect of increasing dielectric anisotropy is very large, and the threshold It is clear that the effect of lowering the value voltage is greater.
実施例ｌ
無水エタノール６５ｍｊ！と金属ナトリウム３．０５ｇ
（０．１３３グラム原子）より調製したＮａＯＣｚＨｓ
の溶液に、マロン酸ジエチルエステル２１．２ｇ（０．
１ ３ ３モル）と式ＣＬＯ− （ＣＨｚ） ｚ−Ｃ
Ｉ．で表わされる化合物１３．１ ｇ （０．１ ２
１モル）を攪拌しながら４８〜５０゜Ｃで加えた後、
還流温度で７時間反応させた。反応混合物を冷却した後
、反応混合物を冷却した飽和塩化アンモニウム水溶液中
に加え、反応生戒物を酢酸エチルで抽出した。抽出液を
水洗、乾燥した後、溶媒を留去して得られた粗生底物を
高真空下に蒸留して精製し、下記化合物１６．８ｇ （
０．０７２４モル）を得た。（収率６０％）次に、無水
ＴＨＦ中にＬｉＡｊ２Ｈ４４． ６ ｇ （０．１２モ
ル）を加えた後、これらを攪拌しながら、前段階で得ら
れた化合物１ ４． ３ ｇ （０．０６１６モル）の
無水ＴＨＦ溶液３０■ｌを、１０〜２０゜Ｃで滴下した
後、室温で７時間、さらに還流温度で７時間反応させた
。Example 1 Absolute ethanol 65mj! and 3.05g of metallic sodium
(0.133 gram atom) of NaOCzHs prepared from
21.2 g (0.0 g) of diethyl malonate was added to a solution of
1 3 3 mol) and the formula CLO- (CHz) z-C
I. 13.1 g of the compound represented by (0.1 2
1 mol) at 48-50°C with stirring,
The reaction was carried out at reflux temperature for 7 hours. After the reaction mixture was cooled, it was added to a cooled saturated aqueous ammonium chloride solution, and the reaction mixture was extracted with ethyl acetate. After washing the extract with water and drying, the solvent was distilled off, and the resulting crude bottom material was purified by distillation under high vacuum to obtain 16.8 g of the following compound (
0.0724 mol) was obtained. (Yield 60%) Next, LiAj2H44. After adding 6 g (0.12 mol), while stirring these, compound 1 obtained in the previous step 4. 3 g (0.0616 mol) of anhydrous THF solution (30 μl) was added dropwise at 10 to 20° C., followed by reaction at room temperature for 7 hours and then at reflux temperature for 7 hours.
反応混合物冷却した後、反応混合物に水２ ｍｌとＴＨ
Ｆ８ｍｆの混合溶液を１０〜２０゛Ｃで滴下して、残余
の水素化物を分解した後、さらに５％水酸化ナトリウム
水溶１’ｆ！１０ｍｌを加えて２時間還流した。After cooling the reaction mixture, add 2 ml of water and TH to the reaction mixture.
A mixed solution of F8mf was added dropwise at 10 to 20°C to decompose the remaining hydride, and then 5% sodium hydroxide aqueous solution 1'f! 10 ml was added and refluxed for 2 hours.
反応混合物を５〜１０’Ｃに冷却した後、生じた水酸化
物を濾過し、溶媒を留去して粗生成物を得た。これを、
高真空下に蒸留して精製し、下記化合＠ｌｆｆ６． ７
ｇ （０．０４５イル）を得た。（収率７３％）＼。After cooling the reaction mixture to 5-10'C, the resulting hydroxide was filtered and the solvent was distilled off to obtain the crude product. this,
It was purified by distillation under high vacuum and the following compound @lff6. 7
g (0.045 yl) was obtained. (Yield 73%)\.
ＨＺＯＨ
次に、この化合物３． ４ ｇ （０．０２３モル）及
び４−シアノベンズアルデヒド３． ０ ｇ （０．０
２３モル）に、トルエン４０ｔａｌ及びＰ一トルエンス
ルホン酸・１水和物４ ４ｍｇ （ｄ． ２ ３ミリモ
ル）を加えた後、これらを攪拌しながら還流温度で１．
５時間脱水反応を行なった。反応混合物を室温まで冷却
した後、トルエン層を分離した後、トルエン層を飽和炭
酸水素ナトリウム水溶液及び飽和食塩水で洗浄し、次い
で乾燥した後、トルエンを留去して粗生戒物を得た。こ
の粗生成物をシリカゲルカラムクロマトグラフィーを用
いて精製した後、エタノールから再結晶させて精製し、
下記化合物２．５ｇ（０．００９６モル）を得た。（収
率４２％）転移温度
７４゜ＣＣＣ−＞Ｔ）
４５’Ｃ（Ｉ→Ｎ）
実施例２
実施例１において、４−シアノベンズアルデヒドに代え
て、３−フルオロー４−シアノベンズアルデヒド３．
４ ｇ （０．０２３モル）を用いた以外は実施例１と
同様にして下記化合物を得た。HZOH Next, this compound 3. 4 g (0.023 mol) and 4-cyanobenzaldehyde3. 0 g (0.0
After adding 40 tal of toluene and 44 mg (d. 23 mmol) of P-toluenesulfonic acid monohydrate to 23 mol), the mixture was heated at reflux temperature with stirring for 1.
The dehydration reaction was carried out for 5 hours. After cooling the reaction mixture to room temperature, the toluene layer was separated, and the toluene layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, then dried, and the toluene was distilled off to obtain a crude product. . This crude product was purified using silica gel column chromatography, and then purified by recrystallization from ethanol.
2.5 g (0.0096 mol) of the following compound was obtained. (Yield 42%) Transition temperature 74° CCC->T) 45'C (I→N) Example 2 In Example 1, 4-cyanobenzaldehyde was replaced with 3-fluoro-4-cyanobenzaldehyde 3.
The following compound was obtained in the same manner as in Example 1 except that 4 g (0.023 mol) was used.
ト
転移温度
５２゜Ｃ （Ｃ→■）
５゜Ｃ（ＩＣＮ）
〔発明の効果］
本発明に係わる式（１）の化合物は、一般的な混合液晶
に添加した場合、混合液晶の誘電率異方性を上昇させ、
しきい値電圧を効果的に低下せしめ、尚かつ屈折率の異
方性が比較的小さいという特色をもっている。Transition temperature: 52°C (C→■) 5°C (ICN) [Effects of the invention] When the compound of formula (1) according to the present invention is added to a general mixed liquid crystal, the dielectric constant difference of the mixed liquid crystal increases. increase directionality,
It has the characteristics of effectively lowering the threshold voltage and having relatively small anisotropy of refractive index.
従って、本発明に係わる式（１）の化合物は視角特性の
よい低電圧駆動の液晶表示セルを製作するための材料と
して極めて有用である。Therefore, the compound of formula (1) according to the present invention is extremely useful as a material for manufacturing a low voltage driven liquid crystal display cell with good viewing angle characteristics.
Claims (1)
わし、ＸはＨ又はＦを表わし、▲数式、化学式、表等が
あります▼はトランス配置を表わす。） で表わされる化合物。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a linear alkyl group having 1 to 5 carbon atoms, X represents H or F, ▲ There are mathematical formulas, chemical formulas, tables, etc. (▼ represents the trans configuration.) A compound represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29950889A JP2830213B2 (en) | 1989-11-20 | 1989-11-20 | Ether dioxane derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29950889A JP2830213B2 (en) | 1989-11-20 | 1989-11-20 | Ether dioxane derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03161484A true JPH03161484A (en) | 1991-07-11 |
| JP2830213B2 JP2830213B2 (en) | 1998-12-02 |
Family
ID=17873492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29950889A Expired - Fee Related JP2830213B2 (en) | 1989-11-20 | 1989-11-20 | Ether dioxane derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2830213B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5314962A (en) * | 1987-04-07 | 1994-05-24 | Mitsubishi Petrochemical Company Limited | ABA type block copolymers |
-
1989
- 1989-11-20 JP JP29950889A patent/JP2830213B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5314962A (en) * | 1987-04-07 | 1994-05-24 | Mitsubishi Petrochemical Company Limited | ABA type block copolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2830213B2 (en) | 1998-12-02 |
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