JPH0848891A - Production of dianthraquinone-n,n'-dihydroazine - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject compound useful as a blue vat dye and a pigment in high yield and high quality by reacting aminoanthraquinone with an alkaline condensing agent in the presence of a new aprotic polar solvent. CONSTITUTION:This method for producing the compound is to react 1- aminoanthraquinone with an alkaline condensing agent (e.g. potassium hydroxide or sodium methoxide) in the presence of 1.3,6-trimethylhexahydro-1,3,6-triazocine 2-one, preferably at 50-150 deg.C. Furthermore, 1.3,6-trimethylhexahydro-1,3,6- triazocine-2-one and the alkaline condensing agent are used in 1-20 weight ratio and 0.8-5 molar ratio, respectively based on 1-aminoanthraquinone. Furthermore, the reaction is preferably carried out in the presence of the air or oxygen which is an oxidizing agent in order to smoothly advance the reaction.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to 1-aminoanthraquinone, which is a condensate thereof, dianthraquinone-N, N '.
-A method for producing dihydroazine.

[0002]

The object compound of the present invention, dianthraquinone-
N, N'-dihydroazine (6,15-dihydro-5,
9,14,18-anthrazine tetron; trade name Ind
anthrene Blue RS, Mikethre
n Blue RS) has long been well known as a blue vat dye having excellent light resistance, and high-purity one can dye cotton or the like in a reddish bright blue color. Also,
It is an important compound that is also used as a pigment, and is also an important compound as a production intermediate of 3,3′-dichlorodianthraquinone-N, N′-dihydroazine.

Various methods have been disclosed so far for producing the dianthraquinone-N, N'-dihydroazine. Generally, BIOS987 and F
As described in IAT1313, a method of condensing 2-aminoanthraquinone by melting it in the presence of an oxidizing agent by alkali melting has long been known. According to this method, dianthraquinone-N, N'-dihydroazine can be produced without using a solvent, using only 2-aminoanthraquinone as a raw material, an oxidizing agent and an alkaline condensing agent.

On the other hand, however, the yield is low, and moreover, many impurities are contained in the obtained product. Therefore, in order to use it as a dye or a pigment, avoid refining operations such as hydrosulfite treatment. I can't. Therefore, the yield of the target product, dianthraquinone-N, N'-dihydroazine, is extremely poor, and it cannot be said that the method is industrially suitable.

Also known is a method of condensing 1-aminoanthraquinone in an organic solvent in a dissolved or suspended state. One is, as described in JP-A-51-17222, alkaline in organic phosphorus oxides or organic nitrogen oxides such as hexamethylphosphorotriamide or pyridine-N-oxide and quinoline-N-oxide. A method of condensing with a condensing agent, and a method of condensing with an alkaline condensing agent in the presence of a primary amine in an organic sulfone or sulfoxide compound as described in JP-B-40-1280. Is. However, when an additional test of the examples in these prior arts is carried out, dianthraquinone-N, N'-dihydroazine can be produced, but both are 70 to 80%.
The yield is low, and it cannot be said that the method is industrially suitable.

The dianthraquinone-N, N'-dihydroazines obtained by these conventional techniques all contain various impurities of unknown structure which cause the dark color, and therefore, such as hydrosulfite treatment. It was necessary to carry out a purification operation.

As a method of solving these problems of the prior art, the applicant of the present invention reacts 1-aminoanthraquinone with an alkaline condensing agent in the presence of 1,3-dimethyl-2-imidazolidinone to obtain the desired dianthraquinone-N. , N'-dihydroazine has already been filed for an improved production method for producing high yield and high quality (JP-A-60-1169 and JP-A-62-25167). By this method, the yield of dianthraquinone-N, N'-dihydroazine is dramatically improved and, in comparison with the dianthraquinone-N, N'-dihydroazine produced by the above-mentioned prior art, has a much higher quality. You can get things.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a method for further improving these conventional techniques to obtain a high-yield and high-quality dianthraquinone-N, N'-dihydroazine.

[0009]

The present inventors have completed the present invention as a result of extensive studies to solve the above problems.

That is, according to the present invention, 1-aminoanthraquinone is reacted with an alkaline condensing agent to form dianthraquinone-
In the method for producing N, N'-dihydroazine,
A method for producing dianthraquinone-N, N'-dihydroazine, which comprises reacting in the presence of 1,3,6-trimethylhexahydro-1,3,6-triazocin-2-one.

The present invention will be described in detail below. The process of the present invention is a novel aprotic polar solvent, 1,3,6-trimethylhexahydro-1,3,6-triazocine-2.
By using -one, dianthraquinone-N, N'-dihydroazine, which is an industrially important compound, can be produced in high yield and high quality.

1,3,6- used in the method of the present invention
Trimethylhexahydro-1,3,6-triazocine-
2-one is usually 0.01 to 30.0 weight ratio to 1-aminoanthraquinone, preferably 1.0 to 20.
Used in the range of 0 weight ratio. If the amount used is extremely large, the amount of by-products tends to increase. 1,3,6-Trimethylhexahydro-1,3,6-triazocine-2
The -one is usually used alone, but there is no problem in using two or more kinds of solvents in combination as long as it is inert to the raw material and the product.

As the alkaline condensing agent used in the method of the present invention, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, or alkali metal salts such as potassium carbonate and sodium carbonate and potassium tert-butoxide and sodium methoxide. , Alkali metal alkoxides such as potassium isopropoxide, and the like. These are used in the form of solids or solutions in inert solvents.

The amount of the alkaline condensing agent used in the method of the present invention is 0.1 to 40.0 mol ratio with respect to 1-aminoanthraquinone, preferably 0.5 to 10.
The molar ratio is 0, more preferably 0.8 to 5.0. If the amount of the alkaline condensing agent used is extremely small, the reaction rate tends to be slow, and the quality may be deteriorated.

In the method of the present invention, an oxidizing agent such as air, oxygen, perborate, nitrate or chlorate is used in order to make the reaction proceed smoothly. Especially, air and oxygen are preferable because they are easy to handle.

The specific method for carrying out the method of the present invention will be described. In 1,3,6-trimethylhexahydro-1,3,6-triazocin-2-one in which 1-aminoanthraquinone is dissolved or suspended. In addition, a method in which a predetermined amount of a simple substance or an aqueous solution of an alkali condensing agent is added dropwise and reacted under an air stream can be used. However, the order of charging the raw materials is not limited to this, and any order may be used.

The reaction is carried out at 20 to 200 ° C., preferably 40
~ 180 ° C, more preferably 50 to 150 ° C. If the reaction temperature is too low, the reaction rate tends to be slow, and if it is too high, the reaction rate increases, but a side reaction or a decomposition reaction of 1-aminoanthraquinone occurs, and conversely dianthraquinone-N, N'-dihydroazine It tends to lead to yield and quality deterioration.

The reaction time depends on the reaction temperature and is not uniquely determined, but usually the reaction is completed within 20 hours and dianthraquinone-N, N'-dihydroazine is obtained in high yield.

[0019]

The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, the term "yield" in the text means the yield with respect to 1-aminoanthraquinone.

The dyeing and judging method is as follows. 1. The obtained dye compound is dissolved in water, sodium hydroxide and hydrosulfite are added, and the mixture is left standing at 65 ° C. for 15 minutes for reduction. Add more water and bring to room temperature.
(Dye concentration is about 2% by weight / solution) 1. A cotton thread is dipped in this solution, heated to 60 ° C., and kept at this temperature for dyeing. (1g of dye solution for 1g of yarn)
00g ratio) 3. Take out the cotton thread, squeeze it, and process it in the order of oxidation → washing with water → soaping → drying. 4. Judgment is made by comparison with a yarn dyed with a dianthraquinone-N, N'-dihydroazine compound synthesized by the method shown in Comparative Examples below as a standard. However, regarding the dianthraquinone-N, N′-dihydroazine compound, a highly pure one shows a reddish bright blue color, and a compound containing a large amount of impurities shows a greenish dark blue color.

Example 1 40.0 g (0.179 mol) of 1-aminoanthraquinone was added to 1,3,6-trimethylhexahydro-1,3.
Suspended in 113 g of 6-triazocin-2-one, 50
% Potassium hydroxide aqueous solution 1.3 g (0.012 mol) was added. This is heated to 98 to 100 ° C., and while passing air, 50% potassium hydroxide aqueous solution 38.0 g (0.3
(39 mol) was added dropwise over 2 hours. 129 after completion of dropping
The temperature was raised to ˜130 ° C., and the reaction was continued for 14 hours while distilling off some water in the system. After cooling to 68 to 70 ° C., 150 g of warm water was charged into the reaction mixture, and the crystal part was collected by filtration and washed with water. The filter cake is dried to give the desired dianthraquinone-N, N'-dihydroazine 3
8.3 g was obtained. The yield was 96% based on 1-aminoanthraquinone. As a result of the dyeing test, it was dyed in a reddish bright blue color as compared with the dianthraquinone-N, N′-dihydroazine obtained in Comparative Example.

Example 2 40.0 g (0.179 mol) of 1-aminoanthraquinone was added to 1,3,6-trimethylhexahydro-1,3.
Suspended in 113 g of 6-triazocin-2-one, 98
% Potassium hydroxide 20.0 g (0.350 mol) was added. This was heated to 98 to 100 ° C. and reacted for 4 hours while passing air. After cooling to 68 to 70 ° C., 150 g of warm water was charged into the reaction mixture, and the crystal part was collected by filtration and washed with water. The filter cake was dried to obtain 36.8 g of the target dianthraquinone-N, N'-dihydroazine. The yield was 93% based on 1-aminoanthraquinone.
As a result of the dyeing test, the dianthraquinone obtained in Comparative Example
It was dyed in a bright reddish blue color as compared with N, N'-dihydroazine.

Example 3 222 g of 1,3,6-trimethylhexahydro-1,3,6-triazocin-2-one, 20.0 g of potassium tert-butoxide (0.1 g instead of potassium hydroxide)
79 mol) and was heated to 80 to 82 ° C. and reacted for 6 hours, except that the target dianthraquinone-N, N′-dihydroazine was 3%.
6.6 g was obtained. The yield was 92% based on 1-aminoanthraquinone. As a result of the dyeing test, it was dyed in a reddish bright blue color as compared with the dianthraquinone-N, N′-dihydroazine obtained in Comparative Example.

Comparative Example 1,3-dimethyl-2 instead of 1,3,6-trimethylhexahydro-1,3,6-triazocin-2-one
-The same operation as in Example 1 was carried out except that 113 g of imidazolidinone was used, and the desired dianthraquinone-
35.8 g of N, N'-dihydroazine was obtained. The yield was 90% based on 1-aminoanthraquinone.

[0025]

According to the method of the present invention, dianthraquinone-N, N'-dihydroazine, which is a compound industrially extremely useful as a blue vat dye and a pigment, is obtained from 1-aminoanthraquinone in high yield and high quality. Can be obtained at The obtained dianthraquinone-N, N'-dihydroazine can be easily isolated without performing a complicated purification operation,
Moreover, it is of high quality. That is, the present invention is capable of reacting 1-aminoanthraquinone with an alkaline condensing agent to obtain the desired dianthraquinone-N, N'-dihydroazine with high yield and high quality, which is industrially efficient and extremely valuable. There is a method.

Claims (1)

[Claims] 1. A method for producing dianthraquinone-N, N'-dihydroazine by reacting 1-aminoanthraquinone with an alkaline condensing agent, which comprises 1,3,6-trimethylhexahydro-1,3,6-triazocine- A method for producing dianthraquinone-N, N′-dihydroazine, which comprises reacting in the presence of 2-one.