JPS59128363A - Preparation of 1-amino-2-phenoxy-4- hydroxyanthraquinone compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a dye, in high purity, quantitatively under mild condition, by reacting the raw material compound with a phenolic compound in an aqueous medium in the presence of an acid acceptor and a quaternary ammonium compound, etc. CONSTITUTION:The objective 1-amino-2-phenoxy-4-hydroxyanthraquinone compound is prepared by reacting (A) 1-amino-2-bromo-4-hydroxyanthraquinone with (B) a phenolic compound of e.g. formula III (R1 and R2 are H, etc.) in an aqueous medium in the presence of an acid acceptor (e.g. NaOH, KOH, K2CO3, etc.) and a quaternary ammonium compound of e.g. formula I (R1 and R2 are 1-24C alkyl, etc; R3 and R4 are 1-10C alkyl; X is anionic residue) (e.g. tetramethylammonium chloride) and/or a quaternary phosphonium compound of formula II(R7-R10 are 1-24C alkyl, etc.) (e.g. tetramethyl-phosphonium chloride).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing ■-amino-2-phenoxy-4-hydroxyanthraquinones.

1-Amino-2-phenoxy-4-hydroxyanthraquinone itself is an important compound as a red disperse dye for polyester fibers, and also as an intermediate for other red disperse dyes.

As a method for producing 1-amino-2-phenoxy-4-hydroxyanthraquinone, 1-amino-2-phenoxy-4-hydroxyanthraquinone is
A method is known in which 2-bromo-4-hydroxyanthraquinone is reacted with phenol in the presence of a deoxidizing agent. Examples of the organic solvent include a method using phenol itself as a solvent (for example, French Patent No. 1478768), a method using a polar solvent such as dimethylformamide, dimethyl sulfoxide, etc. (German Patent Application Publication No. 1444761, Japanese Patent Laid-Open No. 1986-48).
37432), but these methods have the disadvantage that the recovery of the phenol or solvent requires a great deal of effort and energy.

A similar reaction is carried out in an aqueous medium in the presence of a dispersant (Zh, Pr1nkl, Khim. Vol. 49 (1).
976) 4, pp. 904-905] is also known, but the yield of the target product is about 90% at most.

On the other hand, a method is also known in which 1-amino-2-chloro-4-hydroxyanthraquinone is used as a starting material and reacted with phenol in an aqueous medium in the presence of a phase transfer catalyst (
JP-A-55-125156).

However, this method requires high temperatures of 120°C or higher,
Moreover, the synthesis of the starting material is 1-amino-2-bromo-4-
It is less easy and economical than hydroxyanthraquinone. The same reaction conditions were also applied to 1-amino-2-bromo-
Even if it is applied to 4-hydroxyanthraquinone, a dye with a clear hue cannot be obtained.

In order to overcome the above-mentioned drawbacks, the present inventors have proposed that 1-amino-
1-Amino-2-phenoxy-4- with a vivid color using 2-bromo-4-hydroxyanthraquinone as a starting material
As a result of extensive research into methods for producing hydroxyanthraquinones, we found that the reaction was carried out using a relatively high concentration of quaternary chloride in an aqueous medium.
It was discovered that the object could be achieved by carrying out the process in the presence of a quaternary ammonium compound or a quaternary phosphonium compound, and the present invention was completed.

That is, the present invention provides 1-amino-2-bromo-4-hydroxyanthraquinone in an aqueous medium in the presence of a deoxidizing agent.
This is a method for producing 1-amino-2-phenoxy-4-hydroxyanthraquinones, characterized by reacting them with phenols in the presence of a quaternary ammonium compound and/or a quaternary phosphonium compound.

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

(In the formula, R1 and R2 are an alkyl group having 1 to 24 carbon atoms or an optionally substituted benzyl group, R3, R4
represents an alkyl group having 1 to 1 carbon atoms, and X represents an anion residue. ) (In the formula, R5 is an alkyl group having 1 to 24 carbon atoms, R6 is a hydrogen atom or a methyl group, and X has the above meaning.) In the general formula, the anion residues include chlorine, bromine, iodine, and others. , sulfate, phosphate, acetate, methyl sulfate, ethyl sulfate, and hydrogen sulfate residues.

Specific examples of quaternary ammonium compounds 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, dodecyl Tetraalkyl quaternary ammonium compounds such as trimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetracosyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, trioctylmethylammonium chloride.

Benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzylethyldipropylammonium chloride, dodecyldimethylbenzylammonium chloride, 09m or P-methoxybenzyltriethylammonium chloride, o, m, p-chlorobenzyltriethylammonium chloride , octylbenzyldimethylammonium chloride, diethyldibenzylammonium chloride, and other benzyltrialkylammonium compounds and dibenzyldialkylammonium compounds.

N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium chloride, N-
Dodecylpyridinium chloride, N-octadecylpyridinium chloride, N-methylpicolinium chloride,
N-alkylpyridinium compounds and N-alkylpicolinium compounds such as N-butylpicolinium chloride and N-dodecylpicolinium chloride.

and the corresponding bromides, iodides, sulfates, phosphates, hydrogen sulfates, acetates, methyl sulfates, ethyl sulfates, or mixtures thereof.

Industrially, benzyltrimethylammonium chloride,
Benzyltrialkylammonium compounds such as benzyltriethylammonium chloride are preferably used.

The amount of the quaternary ammonium compound used varies depending on the quaternary ammonium compound used, but is generally 10 to 90% by weight as a proportion of the quaternary ammonium compound to the total of the quaternary ammonium compound and the aqueous medium. In the case of tetraalkylammonium compounds, 30 to
90% by weight, preferably 40-80% by weight, in the case of benzyltrialkylammonium compounds 10-85% by weight, preferably 15-80% by weight in the case of N-alkylpyridinium compounds or N-alkylpicolinium compounds is 10 to 60% by weight, preferably 10 to 50% by weight. For example, in the case of benzyltriethylammonium chloride, 20 to 85% by weight, preferably 30 to 8%
It is 0% by weight. When the lipophilicity of the quaternary ammonium compound is stronger than this, the amount used may be even smaller, and on the other hand, when the lipophilicity is weaker, it is preferable to use more than this.

Examples of the quaternary phosphonium compound used in the present invention include those represented by the general formula +1).

(In the formula, k7 JR8tkg 1 R10 has 1 carbon number
~24 alkyl group or phenyl group, and also 7
may be a benzyl group<, Xθ represents an anion residue. ) Examples of the anion residue in the general formula include chlorine, bromine, and iodine, as well as sulfate, phosphate, acetate, and hydrogen sulfate residues.

Specific examples of quaternary phosphonium compounds include tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrabutylphosphonium chloride, octyltriethylphosphonium chloride, hexadecyltriethylphosphonium chloride, hexadecyltriethylphosphonium chloride, dodecyltrimethylphosphonium chloride, trioctylethylphosphonium chloride,
Tetraalkylphosphoniums such as tetracosyltriethylphosphonium chloride; benzyltrialkylphosphonium compounds such as benzyltriethylphosphonium chloride and benzyltributylphosphonium chloride;

Alkyltriphenylphosphonium compounds such as methyltrinoenylphosphonium chloride and ethyltriphenylphosphonium chloride.

Tetraphenylphosphonium chloride and the corresponding bromides, iodides, sulfates, phosphates, acetates, hydrogen sulfates or mixtures thereof.

The amount of the quaternary phosphonium compound to be used varies depending on the quaternary phosphonium compound used, but is generally 10 to 80% by weight as a proportion of the quaternary phosphonium compound to the total of the quaternary phosphonium compound and the aqueous medium. , 20 in the case of tetra,alkylphosphonium compounds
~80% by weight, preferably 25-75% by weight, and 15-75% in place of the benzyltrialkylphosphonium compound.
% by weight, preferably 20-70% by weight, 10-60% by weight in the case of alkyltriphenylphosphonium compounds
, preferably 15 to 50 weight.

For example, in the case of methyltriphenylphosphonium bromide, it is 20 to 50% by weight, preferably 25 to 45% by weight. When the lipophilicity of the quaternary phosphonium compound is stronger than this, the amount added may be even smaller; for example, in the case of tetraphenylphosphonium chloride, 10 to 40% by weight is preferable, and conversely, when the lipophilicity is weak, It is preferable to use more than this amount.

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

The amount of the aqueous medium containing the quaternary ammonium compound and/or quaternary phosphonium compound is 1-amino-
A suitable amount is 2 to 30 times the weight of 2-bromo-4-hydroxy-anthraquinones.

The phenols used in the present invention are expressed by the following formula (
Examples include compounds where I=).

(In the formula, kl # k2 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a 60-C4 alkyl group, a C-C
It represents a 4-alkoxy group or a C□-C6 cyanoalkyl group, and may also be an aralkyloxy group, an allyloxyalkoxy group, an alkylcarbonyloxy group, an arylcarbonyloxyalkyl group, or an alkoxycarbonyloxy group. ) Examples of the four phenols are phenol, hydroquinone, resorcinol, catechol, 〇-1m-1P-cresol, 〇-1m-1P
-Methoxyphenol, o-, p-ri0/l/
Examples include phenol, 0-1P-bromophenol, xylenols, 4-ethylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-methyl-4-cyanoethylphenol, and the like. The amount used is at least 1 molar ratio, preferably 1°1 to 3 molar ratio to 1-amino-2-bromo-4-hydroxyanthraquinone.

The deoxidizing agent used in the present invention includes alkali metal or alkaline earth metal hydroxides, carbonates, phosphates, hydrogen phosphates, hydrogen carbonates, or acetates. Specific examples of the deoxidizing agent include thorium hydroxide, potassium hydroxide, potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, sodium phosphate, sodium acetate, calcium hydroxide, magnesium hydroxide, sodium hydrogen carbonate, Examples include 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 of these used is at least 1 equivalent per 1-amino-2-bromo-4-hydroxyanthraquinone.

In the present invention, the reaction temperature is 60°C or higher, preferably 70°C or higher.
~120°C. The reaction usually completes in 2 to 40 hours.

The target product can be isolated by filtering the mixture after the reaction is heated or after cooling.

According to the method of the present invention, the amounts of phenol and deoxidizing agent used are quite small, the reaction conditions are also mild, and the steepness of the pure 1-amino-2-phenoxy-4-hydroxyanthraquinone obtained is The yield is almost quantitative.

Furthermore, the hue of the dye obtained is yellowish and clearer than that obtained by known methods.

The $ quaternary ammonium compound or quaternary phosphonium compound used in the present invention can be obtained by using an alkali from Oki liquid! 'l Extract and separate as a quaternary ammonium compound or a quaternary phosphonium compound as it is, or as a quaternary ammonium hydroxide or a quaternary phosphonium hydroxide by extraction and separation using an organic solvent group, and then back-extracting with acidic water. Afterwards, it can be recovered and reused without waste by back-extracting it with acidic water.

As described above, the effects brought about by the present invention are great, and its industrial value is enormous.

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 1-Amino-2-bromo-4 was added to a mixture of 68.3 parts of benzyltriethylammonium chloride and 34.6 parts of water.
-Hydroxyanthraquinone (purity 98.7%) 9.6
7 parts, 4.9 parts of potassium hydroxide aqueous solution (48%), and 3.95 parts of phenol, and stirred thoroughly.
The temperature was raised to 5°C, and the mixture was stirred at the same temperature until the starting material disappeared by chromatography. The reaction mixture was then filtered hot, washed thoroughly with warm water and dried to form a dark red cake9.
Obtained 82 copies. The purity of 1-amino-2-phenoxy-4-hydroxyanthraquinone was 99%, and the yield was 98%.

When polyester fiber was dyed using this material,
A dyed product with a clearer yellow tint was obtained compared to the dyed product produced by the known method.

Similar results were obtained when the corresponding bromides and iodides were used in place of benzyltriethylammonium chloride.

Example 2 1-Amino-2-bromo-4 was added to a mixture of 77.1 parts of benzyltrimethylammonium chloride and 25.7 parts of water.
-Hydroxyanthraquinone (purity 96.0%) 9.
94 parts, potassium carbonate 5.2 parts, and phenol 6.2 parts
The mixture was heated to 115° C. with thorough stirring until the starting material disappeared by chromatography. Next, the same treatment as in Example 1 was carried out to obtain dark red cake 9.
．． Got 9 copies. The purity of 1-amino-2-phenoxy-4-hydroxyanthraquinone is 98.5%, the yield is 98.
．． It was 2%.

When polyester fiber was dyed using this material,
A dyed product with a yellowish tinge and clear hue was obtained compared to those obtained by the known method.

5.3 parts of potassium phosphate instead of 5.2 parts of potassium carbonate
Similar results were obtained using 3.0 parts of sodium hydroxide or 3.0 parts of sodium hydroxide.

Examples 3 to 9 The same operations as in Example 1 were performed except that a quaternary ammonium compound or a quaternary phosphonium compound shown in the following table was used instead of benzyltriethylammonium chloride, and the yield and purity shown in the table were obtained. 1-amino-2-phenoxy-4-hydroxyanthraquinone was obtained.

Examples 10-13 The same procedure as in Example 1 was performed except that phenols shown in the table below were used in place of 3.95 parts of phenol, and the corresponding 1-amino-2-phenoxy-4-hydroxyanthraquinone was prepared. Obtained with the purity and expropriation shown in the table.

\ \ \ \ ゝ＼、 +,,,,,,,,,,,:l<,knee'...) Ma

Claims (2)

[Claims] (1) 1-Amino-2-bromo-4-hydroxyanthraquinone is reacted with phenols in an aqueous medium in the presence of a deoxidizing agent and in the presence of a quaternary ammonium compound and/or a quaternary phosphonium compound. 1. A method for producing 1-amino-2-phenoxy-4-hydroxyanthraquinones, characterized by: (2) A patent claim characterized in that the amount of the quaternary ammonium compound or quaternary phosphonium compound used is 10% by weight or more as a proportion of the quaternary compound to the total of the aqueous medium and the quaternary compound. The manufacturing method described in Scope 1.