JPH0575750B2

JPH0575750B2 -

Info

Publication number: JPH0575750B2
Application number: JP15126888A
Authority: JP
Inventors: Naoto Ito; Tsutayoshi Misawa
Original assignee: Mitsui Toatsu Chemicals Inc
Current assignee: Mitsui Toatsu Chemicals Inc
Priority date: 1988-06-21
Filing date: 1988-06-21
Publication date: 1993-10-21
Also published as: JPH023683A

Description

[Detailed description of the invention]

〔産業上の利用分野〕本発明は、色素の中間体であるアントラキノン
ジカルボン酸無水物の精製法に関する。〔従来の技術及び課題〕１，４−ジアミノアントラキノン−２，３−ジ
カルボン酸無水物の製造方法として、１，４−ジ
アミノ−２，３−ジシアノアントラキノンを加水
分解する下式(A)の方法が“The Chemistry of
Synthetic Dyes，Volume”K.Venkataraman
著；Academic Press刊の414頁に記載されてい
る。 [Industrial Application Field] The present invention relates to a method for purifying anthraquinone dicarboxylic acid anhydride, which is an intermediate for dyes. [Prior art and problems] As a method for producing 1,4-diaminoanthraquinone-2,3-dicarboxylic acid anhydride, the method of the following formula (A) for hydrolyzing 1,4-diamino-2,3-dicyanoanthraquinone “The Chemistry of
Synthetic Dyes，Volume”K.Venkataraman
Author: Academic Press, published on page 414.

【化】しかしながら、式(A)の方法には副反応として下
記式(B)の反応がおこり、[Chem] However, in the method of formula (A), the reaction of formula (B) below occurs as a side reaction,

[Means to solve the problem]

本発明者らは、一般式（） The inventors have proposed the general formula ()

【式】（式（）中、Y¹、Y²、Y³およびY⁴は各々独
立に水素原子、アミノ基及び水酸基を表す。）で示される酸無水物を溶媒中、下記一般式（）[Formula] (In formula (), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom, an amino group, and a hydroxyl group.) In a solvent, an acid anhydride represented by the following general formula ()

〔Example〕

以下、実施例により、本発明を詳しく説明す
る。実施例１粗１，４−ジアミノ−アントラキノン−２，３
−ジカルボン酸無水物（純度60％；薄層クロマト
グラムによる。以下同様）200ｇ、ｎ−ジブチル
アミン125ｇをエチルセロソルブ２中120℃に昇
温し、６時間反応した。反応後、反応液を冷却
し、濾過した後、濾液を減圧濃縮し、下記式で表
される化合物を150ｇ得た。 Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 Crude 1,4-diamino-anthraquinone-2,3
-200 g of dicarboxylic anhydride (purity 60%; as determined by thin layer chromatography; the same applies hereinafter) and 125 g of n-dibutylamine were heated to 120° C. in ethyl cellosolve 2 and reacted for 6 hours. After the reaction, the reaction solution was cooled and filtered, and the filtrate was concentrated under reduced pressure to obtain 150 g of a compound represented by the following formula.

【式】次に上式で示されるアミドカルボン酸100ｇを
10％塩酸水溶液２中で90℃に昇温し、20時間加
水分解したのち、析出した結晶を濾過し、水洗、
乾燥して、１，４−ジアミノアントラキノン−
２，３−ジカルボン酸無水物54ｇを得た。純度は
95％であつた。実施例２粗１−アミノ−４−ヒドロキシアントラキノン
−２，３−ジカルボン酸無水物（純度50％）200
ｇ、ジ−（ｎ−プロピル）アミン120ｇをメチルセ
ロソルブ２還流下６時間反応した。反応液を室
温に冷却し、不溶物を濾別後、溶媒を留去し、下
式で表される化合物を170ｇを得た。[Formula] Next, add 100g of the amide carboxylic acid shown by the above formula.
After heating to 90°C in 10% aqueous hydrochloric acid solution 2 and hydrolyzing for 20 hours, the precipitated crystals were filtered, washed with water,
Dry to give 1,4-diaminoanthraquinone-
54 g of 2,3-dicarboxylic anhydride was obtained. Purity is
It was 95%. Example 2 Crude 1-amino-4-hydroxyanthraquinone-2,3-dicarboxylic anhydride (purity 50%) 200
120 g of di-(n-propyl)amine were reacted for 6 hours under reflux of methyl cellosolve. The reaction solution was cooled to room temperature, insoluble materials were filtered off, and the solvent was distilled off to obtain 170 g of a compound represented by the following formula.

【化】および／又は[ka] and/or

【化】次に上記式で示される化合物100ｇを10％塩酸
水溶液２中で90℃にて20時間加水分解し、結晶
を濾別し、水洗乾して、１−アミノ−４−ヒドロ
キシアントラキノン−２，３−ジカルボン酸無水
物60ｇを得た。純度は96％。であつた。実施例３粗１，４−ジアミノ−５，８−ジヒドロキシア
ントラキノン−２，３−ジカルボン酸無水物（純
度50％）200ｇ、ジエタノールアミン140ｇをエチ
レングリコール２中180℃で反応した。反応液
を室温に冷却し、不溶物を濾別後、水30に排水
し析出した結晶を濾別、乾燥した。下式で表され
る化合物180ｇを得た。[Chemical formula] Next, 100 g of the compound represented by the above formula was hydrolyzed in 10% aqueous hydrochloric acid solution 2 at 90°C for 20 hours, the crystals were separated by filtration, washed with water and dried, and 1-amino-4-hydroxyanthraquinone- 60 g of 2,3-dicarboxylic anhydride was obtained. Purity is 96%. It was hot. Example 3 200 g of crude 1,4-diamino-5,8-dihydroxyanthraquinone-2,3-dicarboxylic anhydride (purity 50%) and 140 g of diethanolamine were reacted in ethylene glycol 2 at 180°C. The reaction solution was cooled to room temperature, and after filtering off insoluble matter, it was drained into 30 ml of water, and the precipitated crystals were filtered off and dried. 180 g of a compound represented by the following formula was obtained.

【式】次に上記式で示される化合物100ｇを10％臭化
水素酸水溶液２中で90℃にて10時間加水分解
し、結晶を濾別し、水洗乾燥して、１，４−ジア
ミノ−４，８−ジヒドロキシアントラキノン−
２，３−ジカルボン酸無水物60ｇを得た。純度は
97％であつた。[Formula] Next, 100 g of the compound represented by the above formula was hydrolyzed in 10% hydrobromic acid aqueous solution 2 at 90°C for 10 hours, the crystals were filtered off, washed with water, dried, and 1,4-diamino- 4,8-dihydroxyanthraquinone-
60 g of 2,3-dicarboxylic anhydride was obtained. Purity is
It was 97%.

Claims

[Claims] 1 An acid represented by the general formula () [Chemical formula] (In the formula (), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a hydrogen atom, an amino group, or a hydroxyl group.) Anhydride in a solvent, the following general formula () [formula] (In the formula (), R ¹ and R ² each independently represent an alkyl group, an alkoxyalkyl group, or a hydroxyalkyl group having 1 to 10 carbon atoms.) By treating with a secondary amine represented by the formula, only the acid anhydride is solubilized as amic acid, the imide form and insoluble matter are filtered out, the amic acid is separated from the filtrate, and then the acid anhydride is treated with an acid. A method for purifying an acid anhydride represented by the formula (), characterized in that the acid anhydride is