JPH0517219B2 - - Google Patents

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 (). [In the formula, X is a chlorine atom or a bromine atom, Y ₁ and Y ₂ are each independently a hydrogen atom or a chlorine atom,
A represents a linear or branched alkylene group, or a phenylene group which may be further substituted with lower alkyl, lower alkoxy, hydroxy or halogen in addition to the substituent represented by R in the general formula (), and R is a hydrogen atom, a hydroxyl group, a halogen atom, a phenyl group, a tetrahydrofuryl group, an alkoxy group optionally substituted with hydroxy, halogeno, cyano, lower alkoxy or phenyl, a phenoxy group optionally substituted with lower alkyl or lower alkoxy; Cyanoethyl group or the following general formula (Z represents a hydroxyl group, an amino group, a mono-lower alkylamino group, a di-lower alkylamino group, a lower alkoxy group or a cyclohexyloxy group). ] The anthraquinone compound represented by the general formula () is an important compound as a purple disperse dye for polyester fibers. Conventionally, these compounds have been produced by heating an anthraquinone compound represented by the following general formula () and phenols or alcohols represented by the following general formula ( ,
Tokuko Sho 47-29470). (In the formula, X represents a chlorine atom or a bromine atom, and Y ₁ and Y ₂ represent a hydrogen atom or a chlorine atom.) HO-A-R () [In the formula, A and R have the above meanings] At that time, the solvent For example, use a large amount of the phenols or alcohols represented by the general formula (), or use an organic solvent inert to the reaction (chlorobenzene, dimethylformamide, etc.).
is used. However, these methods require a great deal of labor and energy to recover the phenols, alcohols, or organic solvents, and also produce many byproducts because the reaction requires high temperatures (120°C or higher).
Purification is necessary to obtain a target product with a clear hue, resulting in a disadvantage in that the yield decreases. In order to overcome the above drawbacks, the present inventors used a small amount of phenols or alcohols to
As a result of intensive investigation into a method for obtaining a target product with a clear hue in good yield, it was discovered that the target could be achieved by carrying out the reaction in an aqueous medium in the presence of a quaternary ammonium compound or a quaternary phosphonium compound. The invention has been completed. That is, the present invention provides an anthraquinone compound represented by the general formula () in an aqueous medium in the presence of an acid binder, and a quaternary compound selected from a quaternary ammonium compound and a quaternary phosphonium compound in an aqueous medium. For the sum of medium and quaternary compounds
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 general formula () in an amount of 10% by weight or more. The anthraquinone compounds represented by the general formula () used in the present invention include 1,4-diamino-2,3-dichloroanthraquinone, 1,4
-diamino-2,3-dibromoanthraquinone,
1,4-diamino-2,3,5-trichloroanthraquinone, 1,4-diamino-2,3,5,8
-tetrachloroanthraquinone, 1,4-diamino-2,3-dibromo-5-chloroanthraquinone, and mixtures thereof. 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 the general formula, the anion residues include chlorine, bromine, and iodine. Others: sulfate, phosphate, acetate, methyl sulfate, ethyl sulfate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate,
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, totethylpropylammonium chloride, tri-n-butylethyl ammonium 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, dodecyldimethylbenzylammonium chloride, o,
Benzyltrialkylammonium compounds and benzyldialkyl ammonium compounds such as m- or 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 bromides, iodides, hydroxides, sulfates, phosphates, hydrogen sulfates, acetates, methyl sulfates, ethyl sulfates, hydrogen phosphates, dihydrogen phosphates corresponding to these chlorides salts, carbonates, bicarbonates, sulfites, bisulfites, cyanates, cyanates, thiocyanates, sulfates or mixtures thereof. Industrially, benzyltrialkylammonium compounds such as benzyltrimethylammonium chloride and benzyltriethylammonium chloride, or tetrabutylammonium bromide,
Tetraalkyl quaternary ammonium compounds such as tributylethylammonium chloride are preferably used. The amount of quaternary ammonium compound used varies depending on the quaternary ammonium compound used, but
Generally, the proportion of the quaternary ammonium compound relative to the sum of the quaternary ammonium compound and the aqueous medium is 2-90% by weight, in the case of tetraalkylammonium compounds 10-90% by weight, preferably 20-80% by weight. , 5-85% by weight in the case of benzyltrialkylammonium compounds, preferably
10-80% by weight, 5-60% by weight in the case of N-alkylpyridinium compounds or N-alkylpicolinium compounds, preferably 5-50% by weight. For example, in the case of benzyltriethylammonium chloride, it is 10-85% by weight, preferably 20-80% 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 (). (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, phosphate, acetate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, and hydrogen carbonate. , sulfite, bisulfite, cyanide, cyanate, thiocyanate, 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. 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, phosphate, acetate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, sulfite, bisulfite, cyanide, cyanate, thiocyanate salts, nitrates, or mixtures thereof. The amount of the quaternary phosphonium compound used varies depending on the quaternary phosphonium compound used, but
In general, the proportion of the quaternary phosphonium compound relative to the sum of the quaternary phosphonium compound and the aqueous medium is 10-80% by weight, in the case of tetraalkylphosphonium compounds 20-80% by weight, preferably 25-75% by weight. , 15-75% by weight in the case of benzyltrialkylphosphonium compounds, preferably
20-70% by weight, 10-60% by weight in case of alkyltriphenylphosphonium compounds, preferably 15
−50% by weight. 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. Quaternary ammonium compounds and/or quaternary
The appropriate amount of the aqueous medium containing the class phosphonium compound to be used is 2 to 30 times the weight of the starting material. 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. These usage amounts are
At least 1 equivalent based on the starting material. Compounds of general formula () used in the present invention include phenol, resorcinol, catechol, hydroquinone, o-, m-, p-cresol, o-, m-, p-methoxyphenol, o-
-, m-, p-ethoxyphenol, o-, p-
Chlorphenol, 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-oxyphenyl)-alkyl propionate, β-(4-oxyphenyl)
-cycloalkyl propionate, 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-
(3,5-dimethyl-4-oxyphenyl)-propionitrile, β-(3-methyl-4-oxyphenyl)-propionic acid, β-(2-methyl-4-
oxyphenyl)-propionamide, β-(2-
Ethoxy-4-oxyphenyl)-propion methylamide, β-(4-oxyphenyl)-propion dimethylamide, β-(3-methyl-4-oxyphenyl)-methyl propionate, β-(3-
Ethyl bromo-4-oxyphenyl)-propionate, β-(3-methyl-4-oxyphenyl)-
Phenols such as cyclohexyl propionate,
Or 1-butanol, amyl alcohol, 1
-hexanol, 1-heptanol, 1-octanol, decyl alcohol, lauryl alcohol, stearyl alcohol, palmityl alcohol, 2-ethyl-1-hexanol, benzyl alcohol, 2-phenylethanol, 3-phenylpropanol, ethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 8-octanediol, neopentyl glycol, 2-phenoxyethanol,
o-, m-, or p-cresoxyethanol, 3
-phenoxypropanol, m-, or p-cresoxypropanol, 2,2-diethyl-1,
3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2,2-dimethyl-1,6-hexanediol, 2,2,4-
Trimethyl-1,5-pentanediol, 2,2
-di-n-butyl-1,3-propanediol,
2-Methyl-2-propyl-1,3-propanediol, 3-methyl-1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Hexyl ether, ethylene chlorohydrin, ethylene bromohydrin, tetrahydrofurfuryl alcohol, ethylene glycol monophenyl ethyl ether,
ethylene glycol monocyanoethyl ether,
ethylene glycol monochloroethyl ether,
2-(4'-methoxyphenoxy)-ethanol, 2
Examples include alcohols such as -(4'-methoxycarbonylphenoxy)-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 ratio to the starting material represented by the general formula (). In the present invention, the reaction temperature is 60°C or higher, preferably 70°C to 140°C, more preferably 80°C to 120°C. The reaction is usually complete in 2-48 hours. According to the method of the present invention, the amounts of the compound of general formula () and acid binder used are quite small, the reaction conditions are also mild, and the purity of the compound of general formula () obtained is high. The rate 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 a liquid, or as a quaternary ammonium hydroxide or a quaternary phosphonium compound. After extraction and separation with an organic solvent as phosphonium hydroxide,
By back-extracting with acidic water, it can be recovered and reused without waste. 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 Benzyltriethylammonium chloride
1,4-
Diamino-2,3-dichloroanthraquinone 3.07
parts, 1.76 parts of 47% potassium hydroxide aqueous solution and β-
3.23 parts of (4-oxyphenyl)-propionitrile was charged, and the temperature was raised to 95°C with sufficient stirring, and the mixture was 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 filtering, the cake was thoroughly washed with dilute alkaline water and then with warm water and dried to give 1,4-diamino-2-(4-cyanoethylphenoxy)-3- 3.97 parts of chloranthraquinone were obtained. When polyester fibers were dyed using this product, a dyed product with a brighter reddish hue was obtained compared to that obtained using the conventional method. Instead of benzyltriethylammonium chloride, tetrabutylammonium bromide, octyltrimethylammonium chloride, or N-
Similar results were obtained when butylpyridinium chloride was used. Example 2 Methyltriphenylphosphonium bromide 19.8
and 19.8 parts of water, 3.96 parts of 1,4-diamino-2,3-dibromoanthraquinone, 1.04 parts of potassium phosphate, and β-(3-methyl-4
-Oxyphenyl)-propionitrile (3.5 parts) was charged, the temperature was raised to 95°C with sufficient stirring, and the mixture was heated at the same temperature for 3 hours. Starting material had completely disappeared according to thin layer chromatography. Next, the same post-treatment as in Example 1 was carried out to obtain 1,4
-Diamino-2-(2-methyl-4-cyanoethylphenoxy)-3-bromoanthraquinone 5.0 parts were 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.

【table】

【table】

[Table] Examples 9 to 15 β-(4-oxyphenyl)- described in Example 1
The same reaction as in Example 1 was carried out using the phenols shown in the table below in place of 3.23 parts of propionitrile, and the corresponding desired products were obtained in the amounts shown in the table below. When polyester fibers were dyed using these materials, dyed products with a brighter red hue than those obtained using conventional methods were obtained.

【table】

[Table] Examples 16-26 2-phenoxyethanol described in Example 7
The same reaction as in Example 7 was carried out using the alcohols shown in the table below in place of 2.76 parts, and the corresponding desired products were obtained in the amounts shown in the table below.

【table】

【table】

Claims (1)

[Claims] 1 General formula () [In the formula, X represents a chlorine atom or a bromine atom, and Y ₁ and Y ₂ independently represent a hydrogen atom or a chlorine atom. ] An anthraquinone compound represented by the above in an aqueous medium in the presence of an acid binder, and a quaternary compound selected from a quaternary ammonium compound and a quaternary phosphonium compound, in the sum of the aqueous medium and the quaternary compound. of the general formula () HO-AR () [wherein, R is a hydrogen atom, a hydroxyl group, a halogen atom,
Phenyl group, tetrahydrofuryl group, hydroxy, halogeno, cyano, lower alkoxy or lower alkoxy group optionally substituted with phenyl, phenoxy group optionally substituted with lower alkyl or lower alkoxy, cyanoethyl group or the following general formula (Z represents a hydroxyl group, an amino group, a mono-lower alkylamino group, a di-lower alkylamino group, a lower alkoxy group, or a cyclohexyloxy group); A represents a linear or branched alkylene group; Alternatively, it represents a phenylene group which may be further substituted with lower alkyl, lower alkoxy, hydroxy or halogeno in addition to the substituent represented by R in the general formula (). ] General formula () characterized by reacting with a compound represented by [In the formula, X, Y ₁ , Y ₂ , A and R have the above-mentioned meanings. ] A method for producing an anthraquinone compound.