JPS6089455A - Production of anthraquinone compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound having a good hue, by reacting an anthraquinone compound with an alcohol or phenol in the presence of an acid binder and a quaternary ammonium compound and/or quaternary phosphonium compound in an aqueous medium. CONSTITUTION:An anthraquinone compound expressed by formula I (X is Cl or Br; Y1 and Y2 are H or Cl) is reacted with a compound expressed by the formula HO-A-R (R is H, OH, etc.; A is straight chain or branched chain alkylene or phenylene which may have a substituent group) in the presence of an acid binder, e.g. sodium hydroxide, and a quaternary ammonium compound, e.g. tetramethylammonium chloride, and/or quaternary phosphonium compound, e.g. tetramethylphosphonium chloride, in an aqueous medium to give the aimed compound expressed by formula II having a bright hue in high yield. USE:Violet disperse dyes for polyester fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing an anthraquinone compound represented by the following general formula (I).

[In the formula, further represents a lower alkyl group, a lower alkoxy group, a hydroxyl group, a phenylene group which may have a halogen atom, and R is a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an aryl group, a furyl group, or a hydroxyl group, Al optionally substituted with a halogen atom, a cyano group, an alkoxy group, an aryl group, an aryloxy group, or a furyl group (2 is a hydroxyl group, an amino group, an optionally substituted monoalkylamino group, a dialkylamino group, an alkoxy or a cycloalkoxy group). ] The anthraquinone compound represented by the general formula (1) is an important compound as a purple disperse dye for polyester fibers. Conventionally, these compounds have been produced by heating and reacting an anthraquinone compound represented by the general formula with phenols or alcohols represented by the general formula (for example, Japanese Patent Publication No. 44-28898,
Special Publication No. 47-29470).

(In the formula, chlorine atom or bromine atom, Y, Y2 represents a hydrogen atom or a chlorine atom.) ■ o-A-R (III
) At that time, as a solvent, a large amount of the phenol or alcohol itself represented by the general formula (III) is used, or an organic solvent inert to the reaction (chlorobenzene,
Dimethyl (formamide, etc.) is used.

However, these methods require a great deal of labor and energy to recover the phenols, alcohols, or organic solvents, and the reaction requires high temperatures (120°C or higher), resulting in many by-products and the production of vivid hues. It has the disadvantage that purification is required to obtain the target product, resulting in a lower yield.

In order to overcome the above-mentioned drawbacks, the present inventors conducted intensive studies on a method for obtaining a target product with a clear hue using a small amount of phenols or alcohols, and as a result, the present inventors conducted a reaction 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 an anthraquinone compound represented by the general formula 1) in an aqueous medium in the presence of an acid binder and a quaternary ammonium compound and/or a quaternary phosphonium compound. This is a method for producing an anthraquinone compound represented by the general formula, which comprises reacting with a phenol or an alcohol represented by the following formula.

The anthraquinone compound represented by the general formula (II) used in the present invention includes (1), 4-diamino-2.
8-dichloroanthraquinone, l.

4-diamino-2,8-dibrogaanthraquinone, 1.
4-diamino-2,8,5-)lichloranthraquinone, 1,4-diamino-2,3゜5,8-tetrachloroanthraquinone, l,4-diamino-2,3-dibromo-
5-chloroanthraquinone, etc., and mixtures thereof.

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

(In the formula, R1 and R2 are an alkyl group having 1 to 24 carbon atoms or an optionally substituted benzyl group, R3, R,
represents an alkyl group having 1 to 10 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, 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 chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride,
Tetraalkyl quaternary ammonium compounds such as tetracosyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, trioctylmethylammonium chloride.

Benzyl 1-limethylammonium chloride, penzyltriethylammonium chloride, benzyltripropylammonium chloride, henzyldipropylammonium chloride, dodecyldimethylhensylammonium chloride, o, m or p-methoxyhensyltriethylammonium chloride, Q benzyltrialkylammonium compounds and dibenzylonalkylammonium compounds such as , m, p-tetralopendyltrienal ammonium chloride, octylhensyldimethylammonium chloride, and diethyldibenzylammonium chloride.

N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium chloride, N-
N-alkylpyridinium compounds and N-alkylpicolinium compounds such as dodecylpyridinium chloride, N-octadecylpyridinium chloride, N-methylvicolini, um chloride, N-butylpicolinium chloride, N-dodecylpicolinium chloride, and corresponding to these chlorides Promid, iodide, hydroxide, sulfate, phosphate, hydrogen sulfate, acetate,
Methyl sulfate, ethyl sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, sulfite, hydrogen sulfate, cyanide, cyanate, thiocyanate, nitrate or mixtures thereof . Industrially, benzyltrialkyl ammonium compounds such as benzyltrimethylammonium chloride and benzyltriethylammonium chloride, and tetraalkyl quaternary ammonium compounds such as tetrabutylammonium bromide and tributylethylammonium chloride are preferably used.

The amount of the quaternary ammonium compound used varies depending on the quaternary ammonium compound used, but is generally 2 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, 1O-
9ON amount%, preferably 20-80% by weight in the case of benzyltrialkylammonium compounds 5-85% by weight, preferably 10-80% by weight in the case of N-alkylpyridinium compounds or N-alkylpicolinium compounds is 5-60% by weight, preferably 5-50% by weight.

For example, in the case of benzyltriethylammonium chloride, 10-85% by weight, preferably 2 (1-80% by weight)
It is. 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 compounds used in the present invention include quaternary phosphonium compounds generally represented by ⑯.

(In the formula, R7+ Rs + R9, Rho has 1 carbon number
-24 alkyl group or phenyl group, and R7
may be a benzyl group, and X represents an anionic residue. ) In addition to chlorine, bromine, and iodine, the anion residues in the general formula include sulfate, phosphate, acetate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, and hydrogen carbonate. , sulfite, bisulfite, cyanide, cyanate, thionanate, nitrate residues, and hydroxyl groups.

Specific examples of quaternary phosphonium compounds include tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrabutylphosphonium chloride, octyltriethylphosphonium chloride, hexadecyltriethylphosphonium chloride, hexadecyltributylphosphonium chloride, dodecyltrimethylphosphonium chloride, trioctylethylphosphonium chloride,
Tetraalkylphosphonium compounds such as tetracosyltriethylphosphonium chloride.

Hensyltrialkylphosphonium compounds such as penzyltriethylphosphonium chloride and pennyltributylphosphonium chloride; alkyltriphenylphosphonium compounds such as methyltriphenylphosphonium chloride and ethyltriphenylphosphonium chloride; tetraphenylphosphonium chloride and bromides corresponding to these chlorides; iodide, hydroxide, sulfate, phosphate, acetate, hydrogen sulfate, hydrogen phosphate,
Dihydrogen phosphates, carbonates, bicarbonates, sulfites, bisulfites, cyanates, cyanates, thiocyanates, nitrates, or mixtures thereof.

The amount of the quaternary phosphonium compound to be used varies depending on the quaternary phosphonium compound used, but in general, the ratio of the quaternary phosphonium compound to the total of the quaternary phosphonium compound and the aqueous medium is 10-80% by weight, 20-80% by weight in the case of tetraalkylphosphonium compounds, preferably 25-75% by weight, and 15-75% in the case of benzyltrialkylphosphonium compounds.
% by weight, preferably 20-70% by weight, 10-60% by weight in the case of alkyltriphenylphosphonium compounds
, preferably 15-50 wt.

For example, in the case of methyltriphenylphosphonium bromide, it is 20-50% by weight, preferably 25-45% 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, 10-40% by weight is preferable; It is preferable to use more than this.

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

The appropriate amount of the aqueous medium containing the quaternary ammonium compound and/or quaternary phosphonium compound to be used is 2 to 30 times the weight of the starting material. Examples of metal hydroxides include sodium 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 used is at least 1 equivalent based on the starting material.

Compounds of general formula (III) used in the present invention include phenol, resorcinol, catechol, hydroquinone, o+, m+, p-cresol, o-, m-,
p-methoxyphenol, o-, m+, p-ethoxyphenol, 0-2p-chlorophenol, o-, p-bromophenol, β-(4-oxyphenyl)-propionitrile, β-(4-oxyphenyl) )-propionic acid, β-(4-oxyphenyl)-propioamide, β
-(4-oxyphenyl)-propion alkylamide, β-(4-oxyphenyl)-propion dialkyl amide, β-(4-oxyphenylpropion aralkyno5amide, β-(4-oxyphenyl)-propionate alkyl , β-(4-oxyphenyl)-cycloalkyl propionate, β-(4-oxyphenyl)-propatur, β-(3-methyl-4-oxyphenyl)-
Propionitrile, β-(2-methoxy-4-oxyphenyl)-propionitrile, β-(3-chloro-4-
oxyphenyl)-propionitrile, β-(2-oxy-4-oxyphenyl)-propionitrile, β-(
8,5-dimethyl-4-oxyphenyl)-fropionitrile, β-(8-methyl-4-oxyphenyl)-propionic acid, β-(2-methyl-4-oxyphenyl)
-propionamide, β-(2-ethoxy-4-oxyphenyl)-propionmethylamide, β-(4-oxyphenyl)-propionbenzylamide, β-(4-
(oxyphenyl)-propion dimethylamide, 5-C
methyl a-methyl-4-oxyphenyl)-propionate, ethyl β-(8-from-4-:tldiphenyl)-propionate, cyclohexyl β-(3-methyl-4-oxyphenyl)-propionate, etc. Phenols,
Or 1-phthanol, amyl alcohol, 1-hexanol, 1-heptatool, l-octatool, decyl alcohol, lauryl alcohol, stearyl alcohol, palmityl alcohol, 2-ethyl-1-hexanol, benzyl alcohol, 2-phenylethano Mil, 8-phenylpropertool, ethylene glycol, 1
, 2-propylene glycol, 1, 3-propylene glycol, 1I 3-butanediol, 1-4-butanediol, 8-methyl 1,8-butanediol, 1, 5-bentanediol, 1,6-hexanediol, 1 , 8-
Octanediol, neopentyl glycol, 2-phenoxyethanol, O-, fTI-2 or p-flexyethanol, 3-phenoxydibrobanol, m+,
or p-flexypropanol, 2,2-diethyl-1,8-propanediol, 2-ethyl-2-n-phthyl, 3-propanediol, 2,2-dimethyl-
1,6-hexanediol, 2,2゜4-trimethyl-
1,5-bentanediol, 2,2-di-n-butyl-
1,8-propanediol, 2-methyl-2-propyl-1,3-propanediol, 3-methyl-1,5-hentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, or triethylene glycol monomethyl ether, ethylene cyanohydrin, ethylene chlorohydrin, ethylene bromohydrin, tetrahydrofurfuryl alcohol, ethylene glycol monophenylethyl ether, ethylene Glycol monocyanoethyl ether, ethylene glycol monochloroethyl ether, 2
-(4'-methoxyphenoxy)-ethanol, 2-
Examples include alcohols such as (4'-methoxycarbonylphenoxy)-ethanol, 2-(4'-cyanoethylphenoxy)-ethanol, and 2-(4'-oxyphenoxy)-ethanol, and mixtures thereof. The amount of these compounds to be used is at least 1 molar ratio, preferably 1.1 to 2.5 molar relative to the starting material represented by general formula (I).
It is a molar ratio.

In the present invention, the reaction temperature is 60°C or higher, preferably 70°C or higher.
0°C to 140°C, more preferably 80”C to 120°C
It is. The reaction usually completes in 2-48 hours.

According to the method of the present invention, the amounts of the compound of general formula a) and the acid binder used are considerably small, the reaction conditions are also mild, and the purity of the compound of general formula (I) obtained is high; The yield is almost quantitative.

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

The quaternary ammonium compound or quaternary phosphonium compound used in the present invention can be used as it is as a quaternary ammonium compound or quaternary phosphonium compound by using an alkali from the P solution, or as a quaternary ammonium hydroxide or a quaternary phosphonium compound. After extraction and separation using an organic solvent as grade phosphonium hydroxide, it can be recovered and reused without waste by back-extracting with acidic water.

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

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 1,4-diamino-
3.07 parts of 2,3-dichloroanthraquinone, 1.76 parts of 47% potassium hydroxide aqueous solution and 8.28 parts of β-(4-oxyphenyl)-propionitrile were charged and heated to 95°C with thorough stirring. and heated at the same temperature for 6 hours. Chromatography showed that the starting material had completely disappeared. The reaction mixture was then cooled to 50°C and after filtration, the cake was thoroughly washed with dilute alkaline water and then with warm water and dried to give 1,4-diamino-2-(4-cyanoethylphenoxy)-8- Chloranthraquinone 8.9
I got 7 copies.

When polyester fiber was dyed using this material,
A dyed product with a brighter red hue than that obtained by the conventional method was obtained.

Similar results were obtained when tetrabutylammonium bromide, octyltrimethylammonium chloride, or N-butylpyridinium chloride was used instead of benzyltriethylammonium chloride.

Example 2 To a mixture of 19.8 parts of methyltriphenylphosphonium bromide and 19.8 parts of water was added l.

4-Diamino-2,8-dibromanthraquinone 8.9
6 parts, 1.04 parts of potassium phosphate, and 8.5 parts of β-(8-methyl-4-oxyphenyl)-propionitrile.
After stirring thoroughly, the mixture was heated to 95°C and heated at the same temperature for 3 hours. Starting material had completely disappeared according to thin layer chromatography.

Then, the same post-treatment as in Example 1 was carried out to obtain l.

5.0 parts of 4-diamino-2-(2-methyl-4-cyanoethylphenoxy)-3-bromoanthraquinone was obtained.

Similar results were obtained when tetrabutylphosphonium bromide or tetraphenylphosphonium chloride was used instead of methyltriphenylphosphonium bromide.

Examples 3 to 8 The same reactions as in Example 1 were carried out under various conditions, and the results shown in Tables 1 and 2 were obtained.

Claims (1)

[Claims] General formula (1) [wherein, X is a chlorine atom or a bromine atom, Y]. Y2 represents a hydrogen atom or a chlorine atom. ] In an aqueous medium, in the presence of an acid binder, in the presence of a quaternary ammonium compound and/or a quaternary phosphonium compound, an anthraquinone compound represented by the general formula (fl[) HO-mu几 (1) [In the formula, 几 is substituted with a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an aryl group, a furyl group, or a halogen atom, a cyano group, an alkoxy group, an aryl group, an aryloxy group, or a furyl group; an alkoxy group or an aryloxy group, or a cyanoethyl group,
represents a hydroxyethyl group or a substituent represented by -(2 represents a hydroxyl group, an amino group, an optionally substituted monoalkylamino group, a dialkylamino group, an alkoxy group, or a cycloalkyl group), and A represents a substituent represented by It represents a linear or branched alkylene group, or a phenylene group which may further have a lower alkyl group, a lower alkoxy group, a hydroxyl group, or a halogen atom in addition to the substituent represented by 几 in the general formula (lll). ] General formula (1) characterized by reacting with a compound represented by [wherein, Xe Yl * Y2 * Ae R has the above-mentioned meaning. ] A method for producing an anthraquinone compound.