JPS6128554A - Preparation of 1-amino-2-phenoxy-4-hydroxyanthraquinone - Google Patents

Abstract

PURPOSE:To obtain the titled dye of vivid color and of high purity in high yields, by reacting 1-amino-2-halogeno-4-hydroxyanthraquinone with a phenol in a polar aprotic solvent in the presence of a specified compound. CONSTITUTION:A 1-amino-2-halogene-4-hydroxyanthraquinone compound (e.g. 1- amino-2-bromo-4-hydroxyanthraquinone) is reacted with a phenol in a polar aprotic solvent (e.g. N-methylpyrrolidone) in the presence of both an acid binding agent and a quaternary ammonium (e.g. tetra-n-butylammonium) and/or phosphonium compound (e.g. tetramethylphosphonium chloride). A phenol, a quaternary compound, and an acid binding agent each can be in a small amount; the reaction selectivity is improved; and the titled compound of vivid color and of high purity can be obtained in nearly quantitative yields.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 1-amino-2-phenoxy-4-hydroxyanthraquinones.

1-72-no-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-halogeno-4-hydroxyanthraquinone is reacted with phenol in the presence of an acid binder.

As an organic solvent, a method using phenol itself as a solvent (
For example, French Patent No. 1478768), methods using polar solvents such as dimethylformamide and dimethyl sulfoxide (German Patent Application Publication No. 1444761, JP-A No.
-87482), but the former requires a great deal of effort and energy to recover the phenol, and the latter has insufficient stability of the solvent at high temperatures, producing many by-products and creating a brightly colored dye. It has the disadvantage that it cannot be obtained in good yield.

A method for carrying out a similar reaction in an aqueous medium in the presence of a dispersant (Zh, Pr1nkl, Khim, vol. 49 (
1976) 4. 904-906] is also known, but the yield of the target product is about 90% at most.

There is also a known method in which l-amino-2-chloro-4-hydroxyanthraquino is used as a starting material and reacted with phenol in an aqueous medium in the presence of a phase transfer catalyst (Japanese Patent Application Laid-Open No. 125156/1983). However, this method requires 12
Since the reaction is carried out at a high temperature of 0°C or higher, a pressure-resistant device is required, and the starting materials are limited to 1-i) and 2-chloro-4-hydroxyanthraquinone (same reaction conditions can be applied to 1-amino-2- Even when applied to bromo-4-hydroxyanthraquinone, a dye with a clear hue cannot be obtained.

Furthermore, a method in which a similar reaction is carried out in a nonpolar organic solvent in the presence of a phase transfer catalyst has been published (Japanese Patent Laid-Open No. 58-27752), but the yield of the target product is only about 90%, and the catalyst The amount required is also quite large (1
5% by weight or more) is a drawback.

In order to overcome the above-mentioned drawbacks, the present inventors have proposed that 1-amino-
1-Amino-2-phenoxy-4 with vivid color using 2-halogeno-4-hydroxyanthraquinone as a starting material
-As a result of intensive studies on a method for producing hydroxyanthraquinones in good yield, we conducted the reaction in a polar aprotic solvent using a small amount of quaternary ammonium compound and/or quaternary ammonium compound.
The present invention was completed by discovering that the object could be achieved by carrying out the process in the presence of a class phosphonium compound.

That is, the present invention provides a method for converting 1-amino-2-halogeno-4-hydroxyanthraquinone into phenol in a polar aprotic solvent in the presence of an acid binder and in the presence of a quaternary ammonium compound and/or a quaternary phosphonium compound. The 1-amino-2-phenoxy-4-hydroxyanthraquinone used in the present invention is a method for producing 1-amino-2-phenoxy-4-hydroxyanthraquinone, which is characterized by reacting with 1-amino-2-phenoxy-4-hydroxyanthraquinone. −
2-bromo-4-hydroxyanthraquinone and! −
Amino-2-chloro-4-hydroxyanthraquinone is mentioned.

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

N,N-dimethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-
N,N-di01 of C1-C8-carboxylic acids such as dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylpropionic acid amide, N,N-diethylpropionic acid amide, etc. ~
C8-alkylamides.

Cyclic N-alkylcarbonamides 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.

The amount of these solvents used is usually 1.5 to 10% relative to 1-amino-2-halogeno-4-hydroxyanthraquinone.
Double weight is appropriate.

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

(In the formula, 'R,, R2 is an alkyl group having 1 to 24 carbon atoms or an optionally substituted benzyl group, R3, R
4 carbon ji'ii number 1 t o) y'alkyl group, x represents an anion residue. ) (In the formula, R6 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, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, sulfite, hydrogen sulfite, cyanide , cyanate, thiocyanate, nitrate residues, and hydroxyl groups.

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, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetracosyltrimethylammonium chloride, dioctadecyldimethylammonium Tetraalkyl quaternary ammonium compounds such as chloride, dioctadecyldimethylammonium chloride, and trioctylmethylammonium chloride.

Benzyltrimethylammonium chloride, penzyltriethylammonium chloride, penzyltriflopylammonium chloride, benzylethyldipropylammonium chloride, dodecyldimethylbenzylammonium chloride, o, m or p-methoxybenzyltriethylammonium chloride, o, m, Benzyltrialkylammonium compounds and dibenzyldialkyl ammonium compounds such as p-chlorobenzyltriethylammonium chloride, octylbenzyldimethylammonium chloride, diethyldibenzylammonium chloride, etc. N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium 11 chloride, N
N-alkylpyridinium compounds and N-alkylpicolinium compounds such as -dodecylpyridinium chloride, N-octadecylpyridinium chloride, N-methylpicolinium chloride, N-butylpicolinium chloride, and N-dodecylpicolinium chloride.

and corresponding bromides, iodides, hydroxides, sulfates, phosphates, hydrogen sulfates, acetates, methyl sulfates, ethyl sulfates, hydrogen phosphates, dihydrogen phosphates, carbonates, and carbonates corresponding to these chlorides. Hydrogen salts, sulfites,
Bisulfite, cyanide, cyanate, thiocyanate,
Nitrates or mixtures thereof.

The quaternary phosphonium compound used in the present invention includes a quaternary phosphonium compound represented by the general formula (m).

(In the formula, Rt, Rs, R9, Rzo represent an alkyl group having 1 to 24 carbon atoms or a phenyl group, R7. may be a benzyl group, and X represents an anion residue.) Hydrogen sulfate , hydrogen phosphate, dihydrogen phosphate, carbonate,
Examples include residues of hydrogen carbonate, sulfite, bisulfite, cyanide, cyanate, thiocyanate, nitrate, and hydroxyl groups.

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 penzyltriethylphosphonium chloride and benzyltributylphosphonium chloride; Alkyltriphenylphosphonium compounds such as methyltriphenylphosphonium chloride and ethyltriphenylphosphonium chloride; tetraphenylphosphonium chloride; and bromide and iodide hydrogen corresponding to these chlorides. salt, charcoal-salt, bicarbonate,
Sulfites, bisulfites, nitrates, cyanates, thiocyanates, nitrates, or mixtures thereof.

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

The amount of quaternary ammonium or phosphonium compound used can vary within fairly wide ranges, but is generally from 0.01 to 50% by weight, based on 1-amino-2-halogeno-4-hydroxyanthraquinone, preferably 0. .1
~15% by weight.

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

Acid binders used in the present invention include alkali metal or alkaline earth metal hydroxides, carbonates, phosphates, hydrogen phosphates, hydrogen carbonates, or acetates. Specific examples of the acid binder (7) include sodium hydroxide, potassium hydroxide, potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, sodium phosphate,
Examples include sodium acetate, calcium hydroxide, magnesium hydroxide, sodium hydrogen carbonate, potassium hydrogen phosphate, and the like. 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 equivalent to the starting material.

The phenols used in the present invention are expressed by the following formula (
IV).

(In the formula, R1 and R2 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a Ct-C47J
It represents an L/koxy group or a 01 to C6 cyanoalkyl group, and may also be an aralkyloxy group, an allyloxyalkoxy group, an alkylcarbonyloxy group, an arylcarbonyloxyalkyl group, or an alkoxycarbonyloxy group. ) - The A side of JLts includes phenol, hydroquinone, resorcinol, catechol, 〇-1m-1p
-cresol, 0-1m-1p-methoxyphenol,
Examples include 0-1p-chlorophenol, 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 8 molar ratio to -1-amino-2'-halogeno-4-hydroxyanthraquinone.

In the present invention, the reaction temperature is 50°C or higher, preferably 70°C or higher.
°C to 180 °C.

The reaction usually completes in 2 to 80 hours.

In order to isolate the target product from the mixture after the completion of the reaction, the resulting product is diluted with a lower aliphatic alcohol such as methanol or ethanol, or preferably with water or dilute alkaline water. The precipitate can be separated by furnace.

According to the method of the present invention, the amounts of phenol, quaternary compound, and acid binder used are significantly lower, and the selectivity of the reaction is improved, resulting in 1-amino-2-phenoxy-4- The purity of hydroxyanthraquinone is high and the yield is almost quantitative. Furthermore, the hue of the obtained dye is the same or yellowish and clearer than that 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 I 1-amino-2- in 54.6 parts of N-methylpyrrolidone
Bromo-4-hydroxyanthraquinone (purity 97.8
%) 20.0 parts, potassium carbonate 6.2 parts, phenol 11
．． 8 parts and 0.6 parts of tetra-n-butylammonium bromide were charged, and the temperature was raised to 100°C with thorough stirring, and the mixture was stirred at the same temperature until the starting material completely disappeared by chromatography. Next, 80 parts of methanol was added to the reaction mixture, and the precipitated crystals were separated in a furnace, washed with methanol and warm water in that order, and dried to give a reddish-purple crystalline powder 1.
9.8 parts were obtained. The purity of 1-amino-2-phenoxy-4-hydroxyanthraquinone was 98.5% and the yield was 96.2%.

When polyester fibers were dyed using this product, a dyed product with a brighter yellow hue was obtained compared to the dyed product using a known method.6 Comparative Example 1 Tetra-n-butylammonium bromide was not used. Other than that, the same operation as in Example 1 was carried out, and the following results were obtained.

Product yield 16.6 parts, 1-amino-2-phenoxy-
4-Hydroxyanthraquinone purity 97.2%, yield 79.6%.

When polyester fiber was dyed using this material,
Compared to the known method, a darker dyed product was obtained.

Example 2 18.2 parts of 1-amino-2-chloro-4-hydroxyanthraquinone (purity 92.0%) and 5.2 parts of potassium phosphate (1,2
7.67 parts (1.8 molar ratio) of phenolation, and 0.6 parts of triphenylmethylphosphonium bromide were charged, and the temperature was raised to 120°C with thorough stirring, and the starting material was determined by chromatography. Completely disappear → 1.
Next, 60 parts of water was added to the reaction mixture, and the precipitated crystals were separated in a furnace, washed with dilute caustic soda water and warm water in that order, and dried to give a reddish-purple crystalline powder 19 .9 copies were obtained. The purity of 1-amino-2-phenoxy-4-hydroxyanthraquinone is 98.9%
The yield was 97.1%.

Examples 8 to 9 In Example 1, in place of tetrabutylammonium bromide, quaternary ammonium compounds or quaternary ammonium compounds shown in the following table were used.
The same operation was carried out except that a class phosphonium compound was used to obtain 1-amino-2-phenoxy-4-hydroxyanthraquinone in the yield and purity shown in the table.

Examples 10 to 15 The same operations as in Example 1 were performed except that the solvent shown in the table below was used in place of N-methylpyrrolidone, and 1-amino-2-phenoxy-4- with the yield and purity shown in the table was obtained. Hydroxyanthraquinone was obtained.

Examples 16 to 19 The same procedure as in Example 1 was performed except that phenols shown in the table below were used in place of 11.8 parts of phenol, and the corresponding 1-amino-2-phenoxy-4-hydroxyanthraquinones were shown in the table. obtained with high purity and yield.

Claims (1)

[Claims] Reacting 1-amino-2-halogeno-4-hydroxyanthraquinone with phenols in a polar aprotic solvent in the presence of an acid binder and in the presence of a quaternary ammonium compound and/or a quaternary phosphonium compound. A method for producing 1-amino-2-phenoxy-4-hydroxyanthraquinones, characterized by: