JPH0452261B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 1,4-diamino-2,3-diphenoxyanthraquinone.

1,4-diamino-2,3 diphenoxyanthraquinone is an important compound as a purple disperse dye for polyester fibers. Conventionally, this compound has been produced by subjecting 1,4-diamino-2,3-dichloroanthraquinone to a heating reaction in a phenol solvent in the presence of a deoxidizing agent (for example,
PB Report No. 86139).

However, this method has the disadvantage that a large amount of phenol is used and its recovery requires a great deal of labor and energy.

In order to overcome the above-mentioned drawbacks, the inventors of the present invention have conducted intensive studies on a method for obtaining a desired product with a clear hue in a high yield using a small amount of phenol. The present invention was completed based on the discovery that this can be done.

That is, the present invention provides that in a polar aprotic solvent,
1,4-diamino-
This is a method for producing 1,4-diamino-2,3-diphenoxyanthraquinone, which is characterized by reacting 2,3-dihalogenoanthraquinone with phenol.

1,4-diamino- used in the present invention
As 2,3-dihalogenoanthraquinone,
Examples include 1,4-diamino-2,3-dichloroanthraquinone and 1,4-diamino-2,3-dibromanthraquinone.

Examples of polar aprotic solvents used in the present invention include the following.

N,N-dimethylformamide, N,N-dimethylformamide, N,N-dipropylformamide, N,N-dimethylacetamide, N,N-
Diethylacetamide, N,N-dipropylacetamide, N,N-dimethylpropionic acid amide, N,N-diethylpropionic acid amide, etc.
N,N-di-C1 _- C3-alkylamides of _{C1 - C3} -carboxylic acids.

Cyclic N-alkylcarboxylic acid amides such as N-methylpyrrolidone.

Cyclic N-formyl compounds such as N-formylmorpholine and N-formylpiperidine.

Hexaalkyl phosphate triamides such as hexamethyl phosphate triamide.

Sulfoxides such as dimethyl sulfoxide and tetramethylene sulfoxide.

Tetraalkylureas such as tetramethylurea.

Preferred are sulfolanes such as sulfolane and methylsulfolane.

The appropriate amount of solvent to be used is 1.5 to 10 times the weight of 1,4-diamino-2,3-dihalogenoanthraquinone.

The acid binder used in the present invention includes alkali metal or alkaline earth metal hydroxides,
carbonate, phosphate, hydrogen phosphate, hydrogen carbonate,
Alternatively, acetate may be mentioned. Specific examples of acid binders include sodium hydroxide, potassium hydroxide,
potassium carbonate, potassium phosphate, potassium acetate,
Sodium carbonate, sodium phosphate, sodium acetate, calcium hydroxide, magnesium hydroxide,
Examples include sodium hydrogen carbonate and potassium hydrogen phosphate. Among these, alkali metal hydroxides, carbonates, or phosphates such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium phosphate, and sodium phosphate are preferably used industrially.

The amount used is at least 2 equivalents based on the starting material.

In the present invention, the amount of phenol used is 1,4
-diamino-2,3-dihalogenoanthraquinone in at least a 2 molar ratio, preferably from 2.2 to 6 molar ratio.

In the present invention, a quaternary ammonium compound or a quaternary phosphonium compound is added as a catalyst.

Examples of the quaternary ammonium compound used in the present invention include those represented by the general formula () or ().

(In the formula, R ₁ and R ₂ are an alkyl group having 1 to 24 carbon atoms or an optionally substituted benzyl group,
R ₃ and R ₄ represent an alkyl group having 1 to 10 carbon atoms, and X represents an anion residue. ) (In the formula, R ₅ is an alkyl group having 1 to 24 carbon atoms, R ₆
is a hydrogen atom or a methyl group, and X has the above meaning. ) In addition to chlorine, bromine, and iodine, the anion residues in the general formula include sulfate, phosphate, acetate, methyl sulfate, ethyl sulfate, hydrogen sulfate, hydrogen phosphate, and dihydrogen phosphate. salt, carbonate, bicarbonate,
sulfites, bisulfites, cyanates, cyanates,
These include thiocyanate, nitrate residues, and hydroxyl groups.

Specific examples of quaternary ammonium compounds include:
Examples include the following compounds:

Tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride, tetramethylammonium methyl sulfate, tetraethylammonium ethyl sulfate, triethylpropylammonium chloride, octyltrimethylammonium chloride,
Tetraalkyl quaternary ammonium compounds such as dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetracosyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, diheptadecyldimethylammonium chloride, trioctylmethylammonium chloride.

Benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzylethyldipropylammonium chloride, dodecylmethylbenzylammonium chloride, o, m
or benzyltrialkylammonium compounds and benzyldialkyl ammonium compounds such as p-methoxybenzyltriethylammonium chloride, o,m,p-chlorobenzyltriethylammonium chloride, octylbenzyldimethylammonium chloride, diethyldibenzylammonium chloride.

N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium chloride, N-dodecylpyridinium chloride,
N-alkylpyridinium compounds such as N-octadecylpyridinium chloride, N-methylpicolinium chloride, N-butylpicolinium chloride, N-dodecylpicolinium chloride;
-Alkylpicolinium compounds.

and bromide, iodide, hydroxide, sulfate, phosphate, hydrogen sulfate, acetate, methyl sulfate, ethyl sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, carbonic acid corresponding to these chlorides. Hydrogen salts, sulfites, bisulfites, cyanates, cyanates, thiocyanates, nitrates or mixtures thereof.

Examples of the quaternary phosphonium compound used in the present invention include those represented by the general formula ().

(In the formula, R ₇ , R ₈ , R ₉ , and R ₁₀ represent an alkyl group having 1 to 24 carbon atoms or a phenyl group, R ₇ may be a benzyl group, and X represents an anion residue. ) In addition to chlorine, bromine, and iodine, the anion residues in the general formula include sulfate, methyl sulfate, ethyl sulfate, phosphate, acetate, hydrogen sulfate, hydrogen phosphate, and dihydrogen phosphate. salt, carbonate, bicarbonate,
sulfites, bisulfites, cyanates, cyanates,
These include thiocyanate, nitrate residues, and hydroxyl groups.

Specific examples of quaternary phosphonium compounds include the following compounds.

Tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrabutylphosphonium chloride, octyltriethylphosphonium chloride, hexadecyltriethylphosphonium chloride, hexadecyltributylphosphonium chloride, dodecyltrimethylphosphonium chloride, trioctylethylphosphonium chloride, tetracosyltriethylphosphonium chloride, etc. Tetraalkylphosphonium compounds.

Benzyltrialkylphosphonium compounds such as benzyltriethylphosphonium chloride and benzyltributylphosphonium chloride; Alkyltriphenylphosphonium compounds such as methyltriphenylphosphonium chloride and ethyltriphenylphosphonium chloride; tetraphenylphosphonium chloride and bromides, iodides, and hydrochlorides corresponding to these chlorides. Oxide, sulfate, methyl sulfate, ethyl sulfate, phosphate, acetate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, sulfite, hydrogen sulfite, hydrocyanic acid salts, cyanates, thiocyanates, nitrates, or mixtures thereof.

Among these quaternary compounds, those which are preferably used industrially are tetra-based compounds such as tetra-n-butylammonium bromide, tri-n-butylethylammonium chloride, trioctylmethylammonium chloride, and tetrabutylphosphonium bromide. Alkylammonium or phosphonium compounds, benzyltrialkylammonium compounds such as benzyltrimethylammonium hydroxide, or triphenylalkylphosphonium compounds such as triphenylmethylphosphonium bromide.

The amount of quaternary ammonium or phosphonium compound used can vary within a fairly wide range, but is generally between 0.01 and 50% by weight relative to 1,4-diamino-2,3-dihalogenoanthraquinone.
Preferably it is 0.1 to 15% by weight.

A quaternary phosphonium compound and a quaternary ammonium compound can also be used together.

In the present invention, the reaction temperature is 120° to 230°C, preferably 140° to 200°C. The reaction usually completes in 2-48 hours.

In order to isolate the target product from the mixture after the completion of the reaction, the resulting precipitate is diluted with a lower aliphatic alcohol such as methanol or ethanol, or preferably with water or dilute alkaline water. All you have to do is separate them.

According to the method of the invention, the amounts of phenol and deoxidizing agent used are considerably smaller and the yield of 1,4-diamino-2,3-diphenoxyanthoquinone obtained is almost quantitative.

Furthermore, the hue of the dye obtained is reddish and clear compared to those obtained by known methods.

Next, the present invention will be explained in detail with reference to Examples.
In the text, parts represent parts by weight, and % represents weight %.

Example 1 20 parts of 1,4-diamino-2,3-dichloroanthraquinone, 35 parts of sulfolane, 24.5 parts of phenol
Trioctylmethylammonium chloride
A mixture of 0.2 parts of potassium hydroxide and 8.8 parts of potassium hydroxide was heated to 165° C. with thorough stirring, and heated at the same temperature for 5 hours.

After confirming the disappearance of the starting material by chromatography, the reaction mixture was diluted with 50 parts of water, and the precipitated crystals were separated. The cake was thoroughly washed with dilute alkaline water and then with warm water and dried to form 1,4-diamino-2,3-diphenoxyanthraquinone.
Got 26.1 copies. Yield 95%.

When polyester fibers were dyed using this product, a dyed product with a brighter reddish hue was obtained compared to the conventional method.

Similar results were obtained when tetra-n-butylammonium bromide or triphenylmethylphosphonium bromide was used instead of trioctylmethylammonium chloride.

Example 2 A mixture of 25.8 parts of 1,4-diamino-2,3-dibromanthraquinone, 60 parts of N-methylpyrrolidone, 18.4 parts of phenol, 0.39 parts of benzyltriethylammonium chloride and 11.0 parts of potassium phosphate was stirred thoroughly. The temperature was raised to 160°C and kept at the same temperature for 3 hours. Chromatography showed that the starting material had disappeared. The reaction mixture was then diluted with 40 parts of methanol, and the precipitated crystals were filtered off. The cake was further washed with cold methanol and dried to yield 26.1 parts of 1,4-diamino-2,3-diphenoxyanthraquinone. Yield: 94.2% When polyester fibers were dyed using this product, a dyed product with a brighter reddish hue was obtained compared to the conventional method.

Similar results were obtained when N,N-dimethylacetamide, dimethylsulfoxide, or hexamethylphosphoric triamide was used instead of N-methylpyrrolidone.

Claims (1)

[Claims] 1 In a polar aprotic solvent, in the presence of an acid binder, in the presence of a quaternary compound selected from a quaternary ammonium compound and a quaternary phosphonium compound, 1,4-diamino-2,3-dihalogen A method for producing 1,4-diamino-2,3-diphenoxyanthraquinone, which comprises reacting anthraquinone with phenol.