JPH0334502B2

JPH0334502B2 -

Info

Publication number: JPH0334502B2
Application number: JP20618782A
Authority: JP
Inventors: Daisaku Matsunaga; Tadashi Matsuo
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 1982-11-26
Filing date: 1982-11-26
Publication date: 1991-05-22
Also published as: JPS5996171A

Description

[Detailed description of the invention]

本発明は、式（式中、R₁は１〜５個の酸素原子によつて中断
されていてもよい直鎖又は枝分れした１〜14個の
炭素原子を有するアルキル、シクロアルキル、炭
素数１〜８のアルキル又は炭素数１〜８のアルコ
キシで置換されていてもよいアリールを表わし、
R₂は水素、弗素、塩素、メチル、エチル、メト
キシ、エトキシ又はシアノを表わし、R₃、R₄は
同一又は相異なる基で、水素、弗素、塩素、メチ
ル、エチル、メトキシ又はエトキシを表わす。
R₅、R₆は同一又は相異なる基で炭素数１〜８の
直鎖又は枝分れしたアルキルを表わし、Q₁、Q₂、
Q₃、は同一又は相異なる基で、水素、弗素、メ
チル、メトキシを表わす。又、Q₂とR₃、Q₃とR₄
がベンゼン環と共にその２及び３位で環成してい
る−CH＝CH−CH＝CH−又は−CH＝CH−CH
＝Ｎ−を表わしてもよい。ｎは０又は１である。）で表わされる桂皮酸エステル誘導体青色アゾ色素
に関するものである。本発明のアゾ色素は次のようにして製造するこ
とができる。（式中、R₁、R₂、Q₁は式(1)におけると同じ意味
を表わす。）で表わされるアミノ桂皮酸誘導体を常法でジアゾ
化し、式（式中、R₃、Q₂は式(1)におけると同じ意味を表
わす。）で表わされる化合物にカツプリングし、次いで加
水分解するか或いは上記ジアゾ化物を式（式中、R₃、Q₂は式(1)におけると同じ意味を表
わす。）で表わされる化合物にカツプリングして、式（式中、R₁、R₂、R₃、Q₁、Q₂は式(1)におけると
同じ意味を表わす。）で表わされるモノアゾ色素を得る。次に式(5)の化
合物をジアゾ化し、式（式中、R₅、R₆は式(1)におけると同じ意味を表
わす。）で表わされる化合物にカツプリングして、
式(1)のｎ＝０に相当する式（式中、R₁、R₂、R₃、R₅、R₆、Q₁、Q₂は式(1)に
おけると同じ意味を表わす）で表わされるジスア
ゾ色素を得る。又、式(5)の化合物をジアゾ化し、式（式中、R₄、Q₃は式(1)におけると同じ意味を表
わす。）で表わされる化合物にカツプリングし、次いで加
水分解するか、或いは上記ジアゾ化物を式（式中、R₄、Q₃は式(1)におけると同じ意味を表
わす。）で表わされる化合物にカツプリングして、式（式中、R₁、R₂、R₃、R₄、Q₁、Q₂、Q₃は式(1)に
おけると同じ意味を表わす。）で表わされるジアゾ色素を得る。次に式(10)の化合
物をジアゾ化し、式(6)で表わされる化合物にカツ
プリングして、式(1)のｎ＝１に相当する式（式中、R₁、R₂、R₃、R₄、R₅、R₆、Q₁、Q₂、
Q₃は式(1)におけると同じ意味を表わす。）で表わ
されるトリスアゾ色素を得る。式(2)で表わされるアミノ桂皮酸誘導体は、公知
の種々の製法があるが、とりわけ次の方法が有利
である。式（式中、R₂、Q₁は式(1)におけると同じ意味を表
わす。）で表わされる化合物と式 CH₂＝CH−COOR₁ （13）（式中、R₁は式(1)におけると同じ意味を表わ
す。）で表わされるアクリル酸エステルとを、パラジウ
ム触媒と塩基の存在下縮合させて、式（式中、R₁、R₂、Q₁は式(1)におけると同じ意味
を表わす。）で表わされる化合物を得、次いでアセチルアミノ
基を加水分解して(2)式の化合物を得る。上記反応
において（13）式のアクリル酸エステルとして最
も一般的なアクリル酸メチルを用いて反応を行い
（14）式のR₁＝CH₃の化合物を得、次いでエステ
ル交換反応で高級アルキルエステル化合物とする
方法も有効である。こうして得られた粗製色素は、通常の染色、着
色等には十分な品質であるが、更に高品質が必要
な場合には再結晶、カラムクロマトグラフイー、
分取高速液体クロマトグラフイー等により精製し
て、所望の品質の色素を得る事ができる。本発明によつて得られる式(1)で表わされる桂皮
酸エステル誘導体青色アゾ色素は、ゲスト・ホス
ト方式カラー表示用液晶着色剤として有用であ
り、ビフエニル系、フエニルシクロヘキサン系、
エステル系、ピリミジン系、シツフ系、アゾ系、
アゾキシ系などのいずれの液晶に対しても優れた
溶解性を有しており、カラー液晶用色素として要
求される二色性、耐久性に優れている。その他、合成樹脂脱着色剤、石油類或いは冷媒
着色剤、合成繊維着色剤としても有用である。実施例１色素１水100部中に、４−アミノ桂皮酸ブチルエステ
ル11部、濃塩酸12部を仕込み溶解し、５℃以下で
亜硝酸ソーダ3.4部を水10部に溶解して滴下しジ
アゾ化し、水50部、ｍ−トルイジン6.4部のカツ
プリング液中に５℃以下で加えた。５℃以下で撹
拌し、反応完結後過し水洗、メタノール洗浄後
乾燥して式で表わされるモノアゾ色素12.5部を得た。次に、このモノアゾ色素10.1部を酢酸100部に
溶解し、濃塩酸6.6部を加え、５℃以下で亜硝酸
ソーダ2.1部を水6.5部に溶かした液を滴下しジア
ゾ化した。更にｍ−トルイジン3.7部を酢酸20部
に溶解し、ジアゾ溶液中に10℃以下で滴下した。
10℃以下で撹拌し、反応終了後水50部を加え過
し水洗メタノール洗浄後乾燥して式で表わされるジスアゾ色素11.6部を得た。更にこ
のジスアゾ色素11.6部をジメチルホルムアミド
100部に溶解し、濃塩酸5.6部を加え、５℃以下で
亜硝酸ソーダ1.8部を水5.5部に溶かした液を滴下
しジアゾ化した。次に、２，２−ジメチル−２，
３−ジヒドロペリミジン5.6部を酢酸30部に溶解
して、ジアゾ溶液中に10℃以下で滴下した。10℃
以下で撹拌し、反応終了後水150部、10％苛性ソ
ーダ水溶液25部を加え30分間撹拌後過し水洗、
メタノール洗浄後乾燥して粗製色素16.4部を得
た。粗製色素をキシレンに溶解し、不溶解物を別
した後シリカゲルカラムクロマトグラフイーにか
け、キシレン次いでキシレン−酢酸エチル混合溶
媒で展開して精製分取し、溶媒を濃縮後析出した
結晶を過乾燥して黒褐色の色素１を得た。融点 211〜213℃ この色素のアセトン溶解色は青色である。 λmax 583nｍこの色素を次の４種類の液晶化合物の混合物であるB.D.H.Chemicals Ltd.社の液晶
Ｅ−７に1.5％添加し、ホモジニアス配向処理を
施した２枚の透明ガラス電極基板を約10μｍの間
隔で対向せしめたセル中に封入し、電圧をオン、
オフするとその二色性比は12であつた。実施例２色素２水100部中に、４−アミノ桂皮酸−2′−エチル
ヘキシルエステル138部、濃塩酸12部を仕込み、
５℃以下で亜硝酸ソーダ3.4部を水10部に溶解し
て滴下しジアゾ化した。次にＮ−メチルアニリン
−ω−スルホン酸ソーダ12.5部を水110部に溶解
し、５℃以下でジアゾ溶液中に加えた。５℃以下で撹拌し、酢酸ソーダ8.2部を加え反
応を完結させた。反応完了後過し水洗した。得
られた結晶を水300部に懸濁し80℃に加熱して10
％苛性ソーダ溶液40部を滴下した。更に１時間80
℃で反応させ冷却後過、水洗、乾燥して式で表わされるモノアゾ色素16.5部を得た。次に、このモノアゾ色素1.5部を酢酸220部中に
溶解し、濃塩酸9.6部を加え、５℃以下で亜硝酸
ソーダ3.0部を水10部に溶解して滴下しジアゾ化
した。更に、２−メチル−２−ペンチル−２，３
−ジヒドロペリミジン12.2部を酢酸50部に溶解し
て10℃以下でジアゾ溶液中に滴下した。10℃以下
で撹拌し、酢酸ソーダ7.8部を加え反応を完結さ
せた。反応終了後過し、水洗、メタノール洗浄
後乾燥して粗製色素23.5部を得た。実施例１で行
つたのと同様な方法でカラムクロマトグラフイー
にかけ精製し、黒褐色の色素２を得た。融点 124〜126℃ この色素のアセトン溶解色は青色である。 λmax 575nｍこの色素を液晶Ｅ−７に２％添加し、実施例１
と同様なセル中に封入し、電圧をオン、オフする
とその二色性比は11.5であつた。本発明の式(1)で表わされるその他の色素は実施
例１、２に準じて合成することができる。表−１
に代表的な色素の構造ならびにアセトン溶解色を
記載する。 The present invention is based on the formula (wherein R ₁ is straight-chain or branched alkyl having 1 to 14 carbon atoms, cycloalkyl having 1 to 8 carbon atoms, optionally interrupted by 1 to 5 oxygen atoms) represents an aryl optionally substituted with alkyl or alkoxy having 1 to 8 carbon atoms,
R ₂ represents hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy or cyano, and R ₃ and R ₄ are the same or different groups and represent hydrogen, fluorine, chlorine, methyl, ethyl, methoxy or ethoxy.
R ₅ and R ₆ are the same or different groups and represent a straight chain or branched alkyl having 1 to 8 carbon atoms, and Q ₁ , Q ₂ ,
Q ₃ is the same or different group and represents hydrogen, fluorine, methyl, or methoxy. Also, Q ₂ and R ₃ , Q ₃ and R ₄
-CH=CH-CH=CH- or -CH=CH-CH formed with benzene ring at its 2nd and 3rd positions
=N- may also be represented. n is 0 or 1. ) This relates to a cinnamic acid ester derivative blue azo dye represented by: The azo dye of the present invention can be produced as follows. (In the formula, R ₁ , R ₂ , and Q ₁ have the same meanings as in formula (1).) The aminocinnamic acid derivative represented by the formula is diazotized by a conventional method to obtain the formula (In the formula, R ₃ and Q ₂ have the same meanings as in formula (1).) (In the formula, R ₃ and Q ₂ have the same meanings as in formula (1).) (In the formula, R ₁ , R ₂ , R ₃ , Q ₁ , and Q ₂ have the same meanings as in formula (1).) A monoazo dye represented by the following is obtained. Next, the compound of formula (5) is diazotized, and the compound of formula (5) is (In the formula, R ₅ and R ₆ have the same meanings as in formula (1).)
Formula corresponding to n=0 in formula (1) A disazo dye represented by the formula (wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , Q ₁ and Q ₂ have the same meanings as in formula (1)) is obtained. Alternatively, the compound of formula (5) is diazotized to form the formula (In the formula, R ₄ and Q ₃ have the same meanings as in formula (1).) (In the formula, R ₄ and Q ₃ have the same meanings as in formula (1).) (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , Q ₁ , Q ₂ and Q ₃ have the same meanings as in formula (1).) A diazo dye represented by the following is obtained. Next, the compound of formula (10) is diazotized and coupled to the compound represented by formula (6), resulting in a formula corresponding to n=1 in formula (1). (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , Q ₁ , Q ₂ ,
Q ₃ represents the same meaning as in formula (1). ) is obtained. Although there are various known methods for producing the aminocinnamic acid derivative represented by formula (2), the following method is particularly advantageous. formula (In the formula, R ₂ and Q ₁ have the same meanings as in formula (1).) A compound represented by _the formula CH ₂ =CH−COOR ₁ (13) ) is condensed with an acrylic ester represented by the formula in the presence of a palladium catalyst and a base. (In the formula, R ₁ , R ₂ and Q ₁ have the same meanings as in formula (1).) A compound represented by the following formula is obtained, and then the acetylamino group is hydrolyzed to obtain a compound of formula (2). In the above reaction, methyl acrylate, which is the most common acrylic ester of formula (13), is reacted to obtain a compound of formula (14) where R ₁ = CH ₃ , and then a higher alkyl ester compound is obtained by transesterification. This method is also effective. The crude pigment thus obtained is of sufficient quality for ordinary dyeing, coloring, etc., but if higher quality is required, recrystallization, column chromatography, etc.
A dye of desired quality can be obtained by purification by preparative high performance liquid chromatography or the like. The cinnamic acid ester derivative blue azo dye represented by the formula (1) obtained by the present invention is useful as a liquid crystal coloring agent for guest-host color display, and includes biphenyl-based, phenylcyclohexane-based,
Ester type, pyrimidine type, Schiff type, azo type,
It has excellent solubility in any type of liquid crystal such as azoxy-based liquid crystals, and has excellent dichroism and durability required as a dye for color liquid crystals. In addition, it is useful as a synthetic resin decoloring agent, a petroleum or refrigerant coloring agent, and a synthetic fiber coloring agent. Example 1 Dye 1 11 parts of 4-aminocinnamic acid butyl ester and 12 parts of concentrated hydrochloric acid were dissolved in 100 parts of water, and 3.4 parts of sodium nitrite dissolved in 10 parts of water was added dropwise at 5°C or lower to diazotize the mixture, followed by 50 parts of water. , m-toluidine was added to a coupling solution containing 6.4 parts at 5°C or lower. Stir at 5℃ or below, filter after completion of reaction, wash with water, wash with methanol, and dry. 12.5 parts of a monoazo dye represented by was obtained. Next, 10.1 parts of this monoazo dye was dissolved in 100 parts of acetic acid, 6.6 parts of concentrated hydrochloric acid was added, and a solution prepared by dissolving 2.1 parts of sodium nitrite in 6.5 parts of water was added dropwise at 5° C. or below to effect diazotization. Further, 3.7 parts of m-toluidine was dissolved in 20 parts of acetic acid, and the solution was added dropwise to the diazo solution at 10°C or lower.
Stir at 10℃ or below, add 50 parts of water after the reaction is complete, filter, wash with water, wash with methanol, and dry. 11.6 parts of a disazo dye represented by was obtained. Furthermore, 11.6 parts of this disazo dye was added to dimethylformamide.
100 parts of the solution was dissolved, 5.6 parts of concentrated hydrochloric acid was added thereto, and a solution prepared by dissolving 1.8 parts of sodium nitrite in 5.5 parts of water was added dropwise at 5° C. or lower to diazotize the mixture. Next, 2,2-dimethyl-2,
5.6 parts of 3-dihydroperimidine was dissolved in 30 parts of acetic acid and added dropwise to the diazo solution at 10°C or lower. 10℃
After the reaction is complete, add 150 parts of water and 25 parts of 10% caustic soda aqueous solution, stir for 30 minutes, filter and wash with water.
After washing with methanol and drying, 16.4 parts of a crude dye was obtained. The crude dye was dissolved in xylene, and after separating the insoluble matter, it was subjected to silica gel column chromatography, developed with xylene and then a mixed solvent of xylene and ethyl acetate, and purified and fractionated. After concentrating the solvent, the precipitated crystals were overdried. A dark brown dye 1 was obtained. Melting point: 211-213°C The color of this dye dissolved in acetone is blue. λmax 583nm This dye is combined with the following four types of liquid crystal compounds. 1.5% liquid crystal E-7 from BDH Chemicals Ltd., which is a mixture of ,
When turned off, its dichroic ratio was 12. Example 2 Dye 2 138 parts of 4-aminocinnamic acid-2'-ethylhexyl ester and 12 parts of concentrated hydrochloric acid were added to 100 parts of water.
3.4 parts of sodium nitrite dissolved in 10 parts of water was added dropwise at 5° C. or lower to diazotize the solution. Next, 12.5 parts of sodium N-methylaniline-ω-sulfonate was dissolved in 110 parts of water and added to the diazo solution at 5°C or lower. The mixture was stirred at 5°C or below, and 8.2 parts of sodium acetate was added to complete the reaction. After the reaction was completed, it was filtered and washed with water. The obtained crystals were suspended in 300 parts of water and heated to 80°C for 10
% caustic soda solution was added dropwise. Another hour 80
React at ℃, cool, filter, wash with water, and dry. 16.5 parts of a monoazo dye represented by was obtained. Next, 1.5 parts of this monoazo dye was dissolved in 220 parts of acetic acid, 9.6 parts of concentrated hydrochloric acid was added, and 3.0 parts of sodium nitrite dissolved in 10 parts of water was added dropwise at 5° C. or lower to diazotize. Furthermore, 2-methyl-2-pentyl-2,3
-12.2 parts of dihydroperimidine was dissolved in 50 parts of acetic acid and added dropwise to the diazo solution at 10°C or lower. The mixture was stirred at 10°C or lower, and 7.8 parts of sodium acetate was added to complete the reaction. After the reaction was completed, it was filtered, washed with water, washed with methanol, and dried to obtain 23.5 parts of a crude dye. The product was purified by column chromatography in the same manner as in Example 1 to obtain blackish brown pigment 2. Melting point: 124-126°C The color of this dye dissolved in acetone is blue. λmax 575nm 2% of this dye was added to liquid crystal E-7 and Example 1
The dichroic ratio was 11.5 when the cell was sealed in a cell similar to the one shown in Figure 1 and the voltage was turned on and off. Other dyes represented by formula (1) of the present invention can be synthesized according to Examples 1 and 2. Table-1
The structures and acetone-soluble colors of typical dyes are described below.

【表】【table】

【table】

Claims

[Claims] 1 formula (wherein R ₁ is straight-chain or branched alkyl having 1 to 14 carbon atoms, cycloalkyl having 1 to 8 carbon atoms, optionally interrupted by 1 to 5 oxygen atoms) represents an aryl optionally substituted with alkyl or alkoxy having 1 to 8 carbon atoms,
R ₂ represents hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy or cyano, and R ₃ and R ₄ are the same or different groups and represent hydrogen, fluorine, chlorine, methyl, ethyl, methoxy or ethoxy.
R ₅ and R ₆ are the same or different groups and have 1 to 8 carbon atoms.
represents a straight-chain or branched alkyl, Q ₁ ,
Q ₂ and Q ₃ are the same or different groups, hydrogen, fluorine,
Represents methyl and methoxy. Also, Q ₂ and R ₃ , Q ₃ and
-CH=CH-CH=CH- or -CH= where R ₄ forms a ring with the benzene ring at its 2nd and 3rd positions
It may also represent CH-CH=N-. n is 0 or 1. ) A cinnamate ester derivative blue azo dye.