JPH0543806A - Production of anthraquinone dye - Google Patents

Abstract

PURPOSE:To obtain an anthraquinone dye suited for the dyeing of a polyester synthetic fiber in bright greenish blue by alkylating 1-oxo-3-imino-4,7-diamino-5,6- phthaloylisoindoline. CONSTITUTION:An inactive solvent (e.g. dichlorobenzene) is added to 1-oxo-3- imino-4, 7-diamino-5, 6-phthaloy1isoindoline (compound II) in an amount of 1-5 times by weight. If required, an alcohol is added to the mixed solvent in an amount of 1-50wt.%. An acid binder (e.g. sodium carbonate) is then added, followed by an alkylating agent (e.g. an alkyl halide, a sulfuric acid ester, or an organic sulfonic acid ester) in an amount of 1-2 times by mole the amount of the compound II. If necessary, a phase-transfer catalyst (e.g. a quaternary ammonium salt) is further added. The resulting mixture is allowed to react at 50-30 deg.C for 30min to 15hr to thereby obtain an anthraquinone dye represented by formula I (wherein R is an alkyl, an alkoxyalkyl, a cycloalkyl, an aryloxyalkyl, an aralkyl, an aralkyloxyalkyl, a hydroxyalkyl, an alkoxyalkoxyalkyl, or furfuryl).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing anthraquinone dyes. More specifically, the present invention relates to the industrial production of anthraquinone dyes by the alkylation of 1-oxo-3-imino-4,7-diamino-5,6-phthaloylisoindoline (hereinafter abbreviated as iminoisoindoline). Relates to a particularly advantageous manufacturing method.

[0002]

2. Description of the Related Art As a method of alkylating iminoisodrine, a method of using an alkylating agent such as p-toluenesulfonic acid ester or an alkyl halide in an organic solvent in the presence of a deoxidizing agent is known. (For example, Japanese Patent Publication Sho 41
-3712 publication)

[0003]

However, these methods are not always satisfactory in terms of operability in dye production and quality of dyes obtained when they are carried out on an industrial scale. For example, it is sometimes possible to obtain dye crystals that are very difficult to filter, or to obtain dyes that are not satisfactory in various fastnesses.

The present inventors have conducted intensive studies to find a method for industrially advantageously producing a high-quality anthoquinone dye in a high yield, and as a result, completed the present invention.

[0005]

The present invention is directed to 1-oxo-
3-imino-4,7-diamino-5,6-phthaloylisoindoline is reacted with an alkylating agent in the presence of a deoxidizing agent in an inert solvent to give a compound represented by the following general formula (I):

[0006]

[Chemical 2]

In the production of the anthraquinone dye represented by the formula [wherein R has the above meaning], an alkylating agent (i) the following general formula (II) R-X (II) [wherein X Represents chlorine, bromine or iodine atom, and R has the above-mentioned meaning. Halogenated alkyls represented by], (ii) the following general formula (III) or _{(IV) R-OSO 3 H} (III) R-OSO 3 R (IV) [wherein, R has the meaning given above. ] Sulfuric acid ester shown by, (iii) the following general formula (V) [In formula, R has a said meaning. ] Or (iv) the following general formula (VI) A-SO ₃ R (VI) [In the formula, A represents a phenyl group or a tolyl group, and R has the above meaning. ] When the alkylating agent is an alkyl halide, a phosphoric acid ester or an organic sulfonic acid ester represented by the following, the reaction is carried out in the presence of a phase transfer catalyst. Is the way to do it.

The inert solvent used in the present invention is usually an aromatic hydrocarbon such as benzene, toluene, xylenes, ethylbenzene, etc., an aromatic halogenation such as mono-, di- or trichlorobenzene, bromobenzene, chlorotoluene. One or more selected from hydrocarbons and aromatic nitrated hydrocarbons (group A) such as nitrobenzene and nitrotoluene. Of these organic solvents, toluene, xylene, mono- or dichlorobenzene and nitrobenzenes are preferable.

When the alkylating agent is an alkyl halide, a phosphoric acid ester or a sulfuric acid ester, in addition to the above, it has 1 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms. It is also possible to use one or more solvents selected from chain-like or cyclic aliphatic alcohols and glycols having 5 or less carbon atoms (Group B).
As the aliphatic alcohols, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, cyclohexyl alcohol, 2-ethylhexyl alcohol, Examples include n-octyl alcohol, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. Examples of glycols include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, and the like.

The amount of these inert solvents used is not particularly limited, but is usually 1 to 5 relative to iminoisoindoline.
Weight times are appropriate. In the present invention, when organic sulfonates are used as the alkylating agent, it is preferable to use the solvent of group A together with the solvent of group B in order to further improve the performance of the anthraquinone dye.
Also, when phosphoric acid esters or alkyl halides are used as the alkylating agent, the solvent of group A and the solvent of group B may be used together depending on the case. The amount of alcohol used in this case is preferably 1 to 50% by weight in the mixed solvent,
More preferably, it is 5 to 30% by weight. Further, water may be mixed in the inert solvent within a range that does not impair the effects of the present invention.

The deoxidizer used in the present invention is, for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, potassium carbonate, sodium carbonate, lithium carbonate, sodium acetate. Alkali metal hydroxides such as potassium acetate, sodium phosphate, potassium phosphate, sodium (di) hydrogen phosphate, potassium (di) hydrogen phosphate, bicarbonates, carbonates, acetates, phosphates and Alkaline earth metal carbonates, acetates, phosphates, hydrogen phosphates and oxides such as hydrogen phosphate, calcium carbonate, magnesium carbonate, magnesium acetate, calcium phosphate, magnesium hydrogen phosphate, magnesium oxide and calcium oxide. , Triethylamine, tributylamine, N-methylpiperidine, dimethy Aliphatic tertiary amines such as cyclohexylamine, N, N-dimethylaniline, N, N
-One or more selected from aromatic tertiary amines having no ring nitrogen atom such as diethylaniline and N, N-dimethylbenzylamine.

When the alkylating agent is an alkyl halide or a phosphoric acid ester, a deoxidizing agent such as sodium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, lithium carbonate, potassium carbonate, potassium hydrogen carbonate or an alkali metal is used. Acetates, phosphates and hydrogen phosphates, alkaline earth metal carbonates, acetates, phosphates, hydrogen phosphates and oxides, and aliphatic and aromatic tertiary hydrocarbons without ring nitrogen atoms. It is preferable to use one or more selected from primary amines.

When the alkylating agent is a sulfuric acid ester, as a deoxidizing agent, sodium hydroxide, lithium hydroxide, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, Use one or more selected from lithium carbonate, alkali metal acetates, phosphates and hydrogen phosphates, alkaline earth metal carbonates, acetates, phosphates, hydrogen phosphates and oxides. Is preferred.

When the alkylating agent is an organic sulfonic acid ester, as a deoxidizing agent, sodium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, lithium carbonate, alkali metal acetates, phosphates and hydrogen phosphates, Use one or more selected from alkaline earth metal carbonates, acetates, phosphates, hydrogen phosphates and oxides, and aliphatic and aromatic tertiary amines having no ring nitrogen atom. Is preferred. The amount of the deoxidizer used is preferably 0.5 to 2 mol ratio with respect to iminoisoindoline.

Examples of the halogenated alkyl represented by the general formula (II) include alkyl chloride, alkyl bromide and alkyl iodide which have the above-mentioned substituents as R. Formula (III) or (I
Examples of the sulfate ester represented by V) include dialkyl sulfates and monoalkyl sulfates having the above-mentioned substituents as R. Examples of the phosphoric acid ester represented by the general formula (V) include phosphoric acid esters having the above-mentioned substituent as R. Examples of the organic sulfonic acid ester compound represented by the general formula (VI) include benzenesulfonic acid having the above-mentioned substituent as R or p
-Toluenesulfonic acid ester compounds may be mentioned. The amount of these alkylating agents to be used is preferably 1 to 2 molar ratio, more preferably 1.2, relative to iminoisoindoline.
~ 1.6 molar ratio.

In the general formula (I), the saturated alkyl group represented by R is a linear or branched C ₁ -C ₁₂ alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl. Examples of unsaturated alkyl groups include vinyl, allyl, butenyl,
Examples thereof include C ₂ -C ₈ alkenyl groups such as octenyl. As the alkoxyalkyl group, a C ₁ -C ₈ alkoxy C ₁ -C ₄ alkyl group such as methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, octyloxyethyl, methoxypropyl, ethoxypropyl, and methoxybutyl is a cycloalkyl group. Examples thereof include cyclohexyl and the like, and examples of the aryloxyalkyl group include phenoxyethyl and other aryloxy C ₁ -C ₄
Alkyl groups include benzyl and phenethyl as aralkyl groups, benzyloxyethyl and aralkyloxy C ₁ -C ₄ alkyl groups such as phenethyloxyethyl as aralkyloxyalkyl groups, and hydroxyethyl and hydroxypropyl as hydroxyalkyl groups. , A hydroxy C ₁ -C ₄ alkyl group such as hydroxybutyl, and the alkoxy alkoxyalkyl group as a C ₁ -C ₄ alkoxy C ₁ -such as methoxyethoxyethyl, ethoxyethoxyethyl, butoxyethoxyethyl, etc.
Examples are C ₄ alkoxy C ₁ -C ₄ alkyl groups. R may further be a furfuryl group.

The phase transfer catalyst used in the present invention is not particularly limited and may be any known one.
Quaternary ammonium compounds, quaternary phosphonium compounds and polyalkylene glycol compounds are preferred. The quaternary ammonium compound can be represented by, for example, the following general formula (VII) or (VIII).

[0018]

[Chemical 3]

[Wherein, R ₁ and R ₂ are each independently an alkyl group having 1 to 24 carbon atoms or an optionally substituted phenyl or benzyl group, and R ₃ and R ₄ are each independently 1 to 10 carbon atoms. And an X represents an anion residue. ]

[0020]

[Chemical 4]

[In the formula, R ₅ represents an alkyl group having 1 to 24 carbon atoms or an optionally substituted benzyl group, R ₆ represents a hydrogen atom or a methyl group, and X has the above meaning. The quaternary phosphonium compound can be represented by, for example, the following general formula (IX).

[0022]

[Chemical 5]

[Wherein R₇Is alkyl having 1 to 24 carbon atoms
Group, phenyl group or benzyl group, R ₈, R₉, R_TenIs
Each independently an alkyl group having 1 to 24 carbon atoms or a phenyl group
Nyl group, X₁Represents an anion residue. ]

The polyalkylene glycol compound can be represented by, for example, the following general formula (X).

[Chemical 6]

[In the formula, A represents a divalent aliphatic saturated hydrocarbon residue having 2 to 4 carbon atoms, and n represents a number of 5 to 150. ]

X in the general formulas (VII) and (VIII)
The anion residue represented by, in addition to chlorine, bromine, iodine, sulfate, phosphate, acetate, methyl sulfate, ethyl sulfate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, Residues of carbonates, hydrogen carbonates, sulfites, bisulfites, cyanates, cyanates, thiocyanates, nitrates, and hydroxyl groups are included.

Specific examples of the quaternary ammonium compound include the following compounds. Tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride, tetramethylammonium methylsulfate, tetraethylammonium ethylsulfate, triethylpropylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethyl Tetraalkylammonium compounds such as ammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetracosyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, diheptadecyldimethylammonium chloride, trioctylmethylammonium chloride.

Benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzylethyldipropylammonium chloride, dodecyldimethylbenzylammonium chloride, o, m or p-methoxybenzyltriethylammonium chloride, o, m,
p-chlorobenzyltriethylammonium chloride,
Benzyltrialkylammonium compounds such as octylbenzyldimethylammonium chloride, diethylbenzylammonium chloride, dimethylbenzylphenylammonium chloride, dibenzyldialkylammonium compounds and dialkylbenzylphenylammonium compounds.

N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium chloride, N-dodecylpyridinium chloride, N-octadecylpyridinium chloride, N-methyl or butylpicolinium chloride, N-dodecylpicolinium chloride, etc. N-alkylpyridinium compounds and N-
Alkylpicolinium compounds and N-benzylpyridinium compounds.

And bromide, iodide, hydroxide, sulfate, phosphate, hydrogen sulfate, acetate, methyl sulfate, ethyl sulfate, hydrogen phosphate, dihydrogen phosphate, carbonic acid corresponding to these chlorides. Salts, hydrogen carbonates, sulfites, bisulfites, cyanates, cyanates, thiocyanates, nitrates, or mixtures thereof.

Industrially, benzyltrialkylammonium compounds such as benzyltrimethylammonium chloride and benzyltriethylammonium chloride and tetraalkylammonium compounds such as tetra-n-butylammonium bromide and tetramethylammonium chloride are preferably used.

Examples of the anion residue represented by X ₁ in the general formula (IX) include chlorine, bromine and iodine, as well as sulfates, phosphates, acetates, hydrogensulfates, hydrogenphosphates and diphosphates. Residues of hydrogen salts, carbonates, hydrogen carbonates, sulfites, bisulfites, cyanates, cyanates, thiocyanates, nitrates, and hydroxyl groups can be mentioned.

Specific examples of the quaternary phosphonium compound include tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrabutylphosphonium chloride, octyltriethylphosphonium chloride, hexadecyltriethylphosphohaum chloride, hexadecyltributylphosphonium chloride, dodecyltrimethylphosphonium chloride, Tetraalkylphosphonium compounds such as trioctylethylphosphonium chloride and tetracosyltriethylphosphonium chloride, and benzyltrialkylphosphonium compounds such as benzyltriethylphosphonium chloride and benzyltributylphosphonium chloride. Alkyltriphenylphosphonium compounds such as methyltriphenylphosphonium chloride and ethyltriphenylphosphonium.

Tetraphenylphosphonium chloride and bromides, iodides corresponding to these chlorides,
Hydroxide, sulfate, phosphate, acetate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, sulfite, hydrogen sulfite, cyanide salt, thiocyanate Examples thereof include acid salts, nitrates, and mixtures thereof.

The divalent residue represented by A in the general formula (X) is an ethylene group, a propylene group, a trimethylene group, a tetramethylene group or the like, preferably an ethylene group or a propylene group. Moreover, n is preferably a number of 5 to 20.

Specific examples of the polyalkylene glycol compound include the following compounds. Hexaethylene glycol, polyethylene glycol 200, 300, 400, 600, 1000, 150
0, 2000, 4000, 6000, etc. polyethylene glycols and mixtures thereof. Polypropylene glycols such as polypropylene glycol 400 and 1000, and mixtures thereof. Copolymer of ethylene oxide and propylene oxide. A mixture of the above exemplified compounds.

Industrially preferably used are polyethylene glycols having an average molecular weight of about 200 to 600, such as polyethylene glycol 200, 300, 400, 600, etc., mainly for economical reasons.

These phase transfer catalysts may be used alone or in combination of two or more. Further, the amount used is appropriately 0.1 to 20% by weight with respect to iminoisoindoline.

In the present invention, the reaction temperature of the iminoisoindoline and the alkylating agent is preferably 50 to 130.
C., more preferably 60 to 120.degree. The reaction time is generally 30 minutes to 15 hours, usually 1 to 8 hours, with stirring. After the completion of the reaction, the target dye can be isolated by cooling and, as it is, or by diluting with a solvent such as methanol and then filtering. The anthraquinone dye obtained by the present invention is suitable for dyeing synthetic fibers, especially polyester synthetic fibers, in a vivid green-blue color by a usual method.
According to the present invention, a high-quality anthraquinone dye excellent in various dye performances such as dyeability, hue, vividness, fastness and stain resistance can be obtained in high yield. Further, the method of the present invention is excellent in operability such that the dye can be smoothly filtered when it is carried out on an industrial scale, and further, when an alkyl halide is used as an alkylating agent, the wastewater load is reduced. You can also measure. Hereinafter, the present invention will be specifically described with reference to examples. In the examples, "part" means "part by weight" and "%" means "% by weight".

[0040]

【Example】

Example 1 10 parts of iminoisoindoline, 25 dichlorobenzene
Part, β-phenoxyethyl bromite 10 parts, sodium carbonate 6.1 parts, sodium iodide 2 parts, and benzyltriethylammonium chloride 0.7 parts are reacted at 100 ° C. for 2 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained.
The wet cake is washed with methanol, washed with water and dried. 13.6 parts of a dye of the following structural formula are obtained.

[0041]

[Chemical 7]

This dye is capable of dyeing synthetic fibers in a vivid greenish blue color, and the dyeings obtained have good fastnesses.

Example 2 10 parts of iminoisoindoline, 20 parts of dichlorobenzene
Parts, methanol 2 parts, β-methoxypropyl chloride 5.
3 parts, sodium carbonate 6.1 parts, sodium iodide 2 parts,
A mixture of 0.7 parts of benzyltrimethylammonium chloride is reacted at 100 ° C. for 2 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. 11.8 parts of dye of the following structural formula are obtained.

[0044]

[Chemical 8]

This dye is capable of dyeing synthetic fibers in a clear greenish blue color, and the resulting dyed product has good fastnesses.

Example 3 10 parts of iminoisoindoline, 20 parts of dichlorobenzene
Part, 2 parts of methanol, 10.8 parts of β-n-propoxyethyl iodide, 7.9 parts of potassium carbonate and 1.0 part of tetrabutylammonium bromide are reacted at 100 ° C. for 2 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. 13.2 parts of a dye of the structural formula below are obtained.

[0047]

[Chemical 9]

This dye is capable of dyeing synthetic fibers in a vivid greenish blue color, and the dyeings obtained have good fastnesses.

Example 4 10 parts of iminoisoindoline, 20 parts of chlorobenzene,
A mixture of 2.8 parts of potassium hydroxide and 0.3 part of a 30% aqueous solution of baidyltriethylammonium chloride is heated to 50 ° C. with sufficient stirring, and 4.8 parts of dimethylsulfate is heated to 50 ° C.
After dropping at 60 ° C, the temperature is kept at 60 ° C for 2 hours.
The reaction mixture is then diluted with 20 parts of methanol and then filtered, the wet cake is thoroughly washed with methanol and then with warm water and dried. 10.5 parts of a dye of the following structural formula are obtained.

[0050]

[Chemical 10]

This dye is capable of dyeing synthetic fibers in a vivid greenish blue color, and the dyed product obtained has good fastnesses.

Example 5 10 parts of iminoisoindoline, 20 parts of dichlorobenzene
Parts, ethanol 2 parts, diethyl sulfate 9.5 parts, sodium carbonate 6.1 parts, benzyltrimethylammonium chloride
0.7 part of the mixture is reacted at 80 ° C. for 5 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The wet cake is washed with methanol, then with warm water and dried. 11.8 parts of dye of the following structural formula are obtained.

[0053]

[Chemical 11]

This dye is capable of dyeing synthetic fibers in a vivid green-blue color, and the resulting dyed product has good fastnesses.

Example 6 10 parts of iminoisoindoline, 20 of dichlorobenzene
Parts, methanol 2 parts, dipropyl sulfate 10.2 parts, sodium carbonate 6.1 parts, tetramethylammonium chloride 0.7
The mixture of parts is reacted at 80 ° C. for 4 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The wet cake is washed with methanol, then with warm water and dried. 10.8 parts of a dye of the following structural formula is obtained.

[0056]

[Chemical formula 12]

This dye is capable of dyeing synthetic fibers in a vivid greenish blue color, and the resulting dyed product has good fastnesses.

Example 7 10 parts of iminoisoindoline, 20 parts of chlorobenzene,
Tri-β-butoxybutyl phosphate 19.5 parts, sodium carbonate 6.1 parts, benzyltributylammonium bromide
1.0 part of the mixture is reacted at 110 ° C. for 6 hours. The reaction mixture is then cooled and diluted with 20 parts of methanol,
Filter. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. The dye of the following structural formula
You get 11.1 copies.

[0059]

[Chemical 13]

This dye is capable of dyeing synthetic fibers in a vivid greenish blue color, and the resulting dyed product has good fastnesses.

Example 8 10 parts of iminoisoindoline, 20 of dichlorobenzene
Part, tri-β-phenoxypropyl phosphate (18.5 parts), potassium carbonate (7.9 parts) and benzyltrimethylammonium bromide (0.9 parts) are reacted at 120 ° C. for 3 hours.
The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. 10.2 parts of a dye of the following structural formula are obtained.

[0062]

[Chemical 14]

This dye is capable of dyeing synthetic fibers in a vivid green-blue color, and the resulting dyed product has good fastnesses.

Example 9 10 parts of iminoisoindoline, 20 parts of dichlorobenzene
Parts, methanol 2 parts, p-toluenesulfonic acid-β-ethoxyethyl ester 11.2 parts, sodium carbonate 6.1 parts,
A mixture of 0.7 parts of benzyltriethylammonium chloride is reacted at 100 ° C. for 2 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. Wash this wet cake with methanol,
Wash with water and dry. 12.1 parts of the dye of the following structural formula (yield 9
8.0%) obtained.

[0065]

[Chemical 15]

This dye can dye synthetic fibers in a vivid green-blue color, and the resulting dyed product has good fastnesses.

Example 10 10 parts of iminoisoindoline, 20 parts of nitrobenzene,
Ethanol 1.5 parts, p-toluenesulfonic acid-β-phenoxyethyl ester 12.4 parts, sodium carbonate 5.2 parts,
A mixture of 0.4 parts of benzyltrimethylammonium hydroxide is reacted at 95 ° C. for 2 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered.
The filtration is smooth and a wet cake of high solid content is obtained. Then, it is washed with methanol, washed with water and dried. 13.7 parts (yield 98.6%) of the dye having the following structural formula is obtained.

[0068]

[Chemical 16]

This dye can dye synthetic fibers in a vivid green-blue color, and the resulting dyed product has good fastnesses.

Example 11 10 parts of iminoisoindoline, 30 monochlorobenzene
Parts, methanol 2 parts, p-toluenesulfonic acid-β-butoxyethyl ester 12.5 parts, sodium carbonate 4.6 parts,
8 parts of a mixture of 0.4 parts of tetrabutylammonium bromide
React at 0 ° C. for 4 hours. The reaction mixture is then cooled and diluted with 20 parts of methanol, then filtered, washed with methanol, washed with water and dried. 13.0 parts (yield 98.0%) of the dye having the following structural formula is obtained.

[0071]

[Chemical 17]

This dye is capable of dyeing synthetic fibers in a vivid green-blue color, and the dyeings obtained have good fastnesses. Similar results are obtained when the same amount of tetramethylammonium chloride is used instead of tetrabutylammonium bromide.

Example 12 10 parts of iminoisoindoline, 20 parts of nitrobenzene,
Water 1.5 parts, p-toluenesulfonic acid butyl ester 11.2
Part, lithium carbonate 3.7 parts, polyethylene glycol 40
0 0.7 parts of the mixture are reacted at 90 ° C. for 3 hours. The reaction mixture is then cooled and diluted with 20 parts of methanol, then filtered, washed with methanol, washed with water and dried. A dye of the following structural formula is obtained.

[0074]

[Chemical 18]

This dye can dye synthetic fibers in a vivid green-blue color, and the resulting dyed product has good fastnesses.

Examples 13 to 17 In the above Example 2, the alcohols or / and water added to dichlorobenzene as the inert solvent, the deoxidizing agent, the phase transfer catalyst and the alkylating agent were changed to those shown in the following table. The dyes shown in the following table are obtained by reacting in the same manner. In the table, the amounts of alcohol and water used are shown in parentheses. The same molar ratio as in Example 2 is used for the deoxidizing agent and the alkylating agent, and the same weight is used for the phase transfer catalyst.

[0077]

[Table 1]

Examples 18 to 20 In the above-mentioned Example 6, the alcohols and / or water added to dichlorobenzene as an inert solvent, the deoxidizing agent, the phase transfer catalyst and the alkylating agent were changed to those shown in the following table. The dyes shown in the following table are obtained by reacting in the same manner. In the table, the amounts of alcohol and water used are shown in parentheses. The same molar ratio as in Example 6 is used for the deoxidizing agent and the alkylating agent, and the same weight is used for the phase transfer catalyst.

[0079]

[Table 2]

Examples 21 to 23 In the above Example 8, the alcohols or / and water added to dichlorobenzene as the inert solvent, the deoxidizing agent, the phase transfer catalyst and the alkylating agent were changed to those shown in the following table. The dyes shown in the following table are obtained by reacting in the same manner. In the table, the amounts of alcohol and water used are shown in parentheses. Further, the same molar ratio as in Example 8 is used for the deoxidizing agent and the alkylating agent, and the same weight is used for the phase transfer catalyst.

[0081]

[Table 3]

Examples 24 to 32 In the above Example 9, the alcohols and / or water added to dichlorobenzene as an inert solvent, the deoxidizing agent, the phase transfer catalyst and the alkylating agent were changed to those in the following table. The dyes shown in the following table are obtained by reacting in the same manner. In the table, the amounts of alcohol and water used are shown in parentheses. Further, the same molar ratio as in Example 9 is used for the deoxidizing agent and the alkylating agent, and the same weight is used for the phase transfer catalyst.

[0083]

[Table 4]

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[Procedure amendment]

[Submission date] August 24, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[In the formula, R is saturated or unsaturated alkyl
Group, alkoxyalkyl group, cycloalkyl group, aryl
Roxyalkyl group, aralkyl group, aralkyloxy
Alkyl group, hydroxyalkyl group, alkoxy alcohol
Represents a xyalkyl group or a furfuryl group. As an alkylating agent for producing an anthraquinone dye represented by the following formula: (i) General formula (II) R-X (II) [wherein, X represents a chlorine, bromine or iodine atom, and R represents the above-mentioned formula] Has meaning. Halogenated alkyls represented by], (ii) the following general formula (III) or _{(IV) R-OSO 3 H} (III) R-OSO 3 R (IV) [wherein, R has the meaning given above. ] Sulfuric acid ester shown by, (iii) the following general formula (V) [In formula, R has a said meaning. ] Or (iV) the following general formula (VI) A-SO ₃ R (VI) [In the formula, A represents a phenyl group or a tolyl group, and R has the above meaning. ] When the alkylating agent is an alkyl halide, a phosphoric acid ester or an organic sulfonic acid ester represented by the following, the reaction is carried out in the presence of a phase transfer catalyst. Is the way to do it.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The amount of these inert solvents used is not particularly limited, but is usually 1 to 5 relative to iminoisoindoline.
Weight times are appropriate. In the present invention, when an organic sulfonic acid ester is used as the alkylating agent, in order to further improve the performance of the anthraquinone dye, the solvent of group A may be used, but the solvent of group A may be the solvent of group B. It is preferable to use in combination. Also, sulfuric acid as an alkylating agent
When using an ester, a phosphoric acid ester, or an alkyl halide, the solvent of group A and the solvent of group B may be used together depending on the case. In this case, the amount of the group B solvent used is
The content in the mixed solvent is preferably 1 to 50% by weight, more preferably 5 to 30% by weight. Further, water may be mixed in the inert solvent within a range that does not impair the effects of the present invention.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

In the general formula (I), the satiety represented by R
Examples of the sum alkyl group include methyl, ethyl, propyl and butyl.
Such as chill, pentyl, hexyl, octyl, dodecyl
Straight or branched C₁~ C₁₂An alkyl group is exemplified,
Unsaturated alkyl groups include vinyl, allyl, butenyl
C such as le and octenyl_Two~ C₈Examples include alkenyl groups
Shown. As an alkoxyalkyl group, methoxy
Chill, ethoxyethyl, propoxyethyl, butoxye
Chill, octyloxyethyl, methoxypropyl, eth
C such as xypropyl and methoxybutyl₁~ C₈Arco
Kishi C₁~ C_FourAlkyl group as a cycloalkyl group
Is cyclohexyl, etc. _C 3 -C ₆ cycloalkyl group
However, as an aryloxyalkyl group, phenoxyethyl
Aryloxy C such as le₁~ C_FourThe alkyl group is
Examples of rualkyl groups include benzyl and phenethyl.
Benzyloxyethyl as a killoxyalkyl group,
Aralkyloxy C such as phenethyloxyethyl₁~
C_FourThe alkyl group is a hydroxyalkyl group
Roxyethyl, hydroxypropyl, hydroxybutyl
Hydroxy C such as₁~ C_FourAlkyl group is alkoxy
Methoxyethoxyethyl as the alkoxyalkyl group
, Ethoxyethoxyethyl, butoxyethoxyethyl
Such as C₁~ C_FourAlkoxy C₁~ C_FourAlkoxy C₁
~ C_FourAn alkyl group is illustrated respectively. R is further
It may be a furfuryl group.

[Procedure amendment 4]

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[Correction target item name] 0024

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The polyalkylene glycol compound can be represented by, for example, the following general formula (X).

[Chemical 6]

[Procedure Amendment 5]

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[Name of item to be corrected] 0025

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[In the formula, A ′ represents a divalent aliphatic saturated hydrocarbon residue having 2 to 4 carbon atoms, and n represents a number of 5 to 150. ]

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The quaternary tetramethyl phosphonium chloride Specific examples of the phosphonium compound, tetraethyl phosphonium chloride, tetrabutyl phosphonium chloride, octyl triethyl phosphonium chloride, hexadecyl triethyl phosphonium two Umukurorido, hexadecyl tributyl phosphonium chloride, dodecyl trimethyl phosphonium chloride, Tetraalkylphosphonium compounds such as trioctylethylphosphonium chloride and tetracosyltriethylphosphonium chloride, and benzyltrialkylphosphonium compounds such as benzyltriethylphosphonium chloride and benzyltributylphosphonium chloride. Triphenylphosphonium chloride, alkyl triphenyl phosphonium compounds such as ethyltriphenylphosphonium chloride.

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[Item name to be corrected] 0040

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[0040]

EXAMPLE 1 iminoisoindoline 10 parts dichloroethane Le benzene 25
Parts, beta-phenoxyethyl bromide My de 10 parts, 6.1 parts of sodium carbonate, 2 parts of sodium iodide, the mixture of benzyltriethylammonium chloride 0.7 parts 100
React for 2 hours at ℃. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. 13.6 parts of dye of the following structural formula are obtained.

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[0043] Example 2 iminoisoindoline 10 parts dichloroethane Le benzene 20
Parts, methanol 2 parts, β-methoxypropyl chloride 5.3 parts, sodium carbonate 6.1 parts, sodium iodide 2 parts, benzyltrimethylammonium chloride 0.7.
The mixture of parts is reacted at 100 ° C. for 2 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. Dye of the following structural formula is 1
1.8 copies are obtained.

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[0046] Example 3 iminoisoindoline 10 parts dichloroethane Le benzene 20
Part, 2 parts of methanol, 10.8 parts of β-n- propoxyethyl iodide, 7.9 parts of potassium carbonate, and 1.0 part of tetrabutylammonium bromide are reacted at 100 ° C. for 2 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained.
The wet cake is washed with methanol, washed with water and dried. 13.2 parts of a dye of the following structural formula are obtained.

[Procedure Amendment 10]

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[Correction target item name] 0049

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Example 4 10 parts of iminoisoindoline, 20 parts of chlorobenzene,
2.8 parts of potassium hydroxide, the temperature was raised sufficiently stirring 50 ° C. The mixture of base down Jill triethylammonium chloride 30% aqueous solution of 0.3 parts of 4.8 parts of dimethyl sulfate 5
After dropping at 0 ° C to 60 ° C, the temperature is kept at 60 ° C for 2 hours. The reaction mixture is then diluted with 20 parts of methanol and then filtered, the wet cake is thoroughly washed with methanol and then with warm water and dried. The dye of the following structural formula is 10.
You get 5 copies.

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[0052] Example 5 iminoisoindoline 10 parts dichloroethane Le benzene 20
Part, ethanol 2 parts, diethylsulfate 9.5 parts, sodium carbonate 6.1 parts, and benzyltrimethylammonium chloride 0.7 parts are reacted at 80 ° C. for 5 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The wet cake is washed with methanol, then with warm water and dried. 11.8 parts of dye of the following structural formula are obtained.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0055

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[0055] Example 6 iminoisoindoline 10 parts dichloroethane Le benzene 20
Part, 2 parts of methanol, 10.2 parts of dipropylsulfate , 6.1 parts of sodium carbonate and 0.7 parts of tetramethylammonium chloride are reacted at 80 ° C. for 4 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The wet cake is washed with methanol, then with warm water and dried. 10.8 parts of a dye of the following structural formula is obtained.

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[0058] Example 7 iminoisoindoline 10 parts, black Le benzene 20 parts,
Phosphorus Santo Re -β- butoxybutyl 19.5 parts, 6.1 parts of sodium carbonate is reacted for 6 hours a mixture of 1.0 parts of benzyl tributyl ammonium bromide at 110 ° C..
The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be carried out smoothly, and a wet cake having a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. 11.1 parts of a dye of the following structural formula are obtained.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0061

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[0061] Example 8 iminoisoindoline 10 parts dichloroethane Le benzene 20
Parts, 18.5 parts of phosphoric Santo Re -β- phenoxypropyl,
A mixture of 7.9 parts of potassium carbonate and 0.9 part of benzyltrimethylammonium bromide is reacted at 120 ° C. for 3 hours. The reaction mixture is then cooled, diluted with 20 parts of methanol and then filtered. The filtration can be done smoothly,
A wet cake with a high solid content is obtained. The wet cake is washed with methanol, washed with water and dried. 10.2 parts of a dye of the following structural formula are obtained.

[Procedure Amendment 15]

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[0077]

[Table 1]

[Procedure 16]

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[0083]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Akira Murata Akira Murata 3-98 Kasugade, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Takaharu Ikeda 3-chome, Kasugade, Konohana-ku, Osaka No. 98 Sumitomo Chemical Co., Ltd.

Claims (13)

[Claims] 1. A 1-oxo-3-imino-4,7-diamino-5,6-phthaloylisoindoline is reacted with an alkylating agent in the presence of a deoxidizing agent in an inert solvent to give the following: General formula (I): [In the formula, R is a saturated or unsaturated alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryloxyalkyl group, an aralkyl group, an aralkyloxyalkyl group,
It represents a hydroxyalkyl group, an alkoxyalkoxyalkyl group or a furfuryl group. In the production of the anthraquinone dye represented by the formula (1) as an alkylating agent (i) the following general formula (II) R-X (II) [wherein, X represents a chlorine, bromine or iodine atom, and R Has the meaning given above. Halogenated alkyls represented by], (ii) the following general formula (III) or _{(IV) R-OSO 3 H} (III) R-OSO 3 R (IV) [wherein, R has the meaning given above. ] Sulfate ester represented by: (iii) the following general formula (V) [In formula, R has a said meaning. ] Or (iv) the following general formula (VI) A-SO ₃ R (VI) [In the formula, A represents a phenyl group or a tolyl group, and R has the above meaning. ] When the alkylating agent is an alkyl halide, a phosphoric acid ester or an organic sulfonic acid ester represented by the following, the reaction is carried out in the presence of a phase transfer catalyst. how to. 2. An alkylating agent is an alkyl halide or a phosphoric acid ester, and the deoxidizing agent is sodium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, lithium carbonate, potassium carbonate, potassium hydrogen carbonate, or an alkali metal. Acetates, phosphates and hydrogen phosphates, alkaline earth metal carbonates, acetates, phosphates, hydrogen phosphates and oxides, and aliphatic and aromatic tertiary hydrocarbons without ring nitrogen atoms. The method according to claim 1, wherein one or more kinds selected from primary amines are used. 3. The alkylating agent is a sulfate ester,
As a deoxidizing agent, sodium hydroxide, lithium hydroxide, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate,
Use one or more selected from lithium carbonate, alkali metal acetates, phosphates and hydrogen phosphates, alkaline earth metal carbonates, acetates, phosphates, hydrogen phosphates and oxides. The method of claim 1. 4. An alkylating agent is an organic sulfonic acid ester, and as a deoxidizing agent, sodium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, lithium carbonate, alkali metal acetates, phosphates and hydrogen phosphates. , One or more selected from alkaline earth metal carbonates, acetates, phosphates, hydrogen phosphates and oxides, and aliphatic and aromatic tertiary amines having no ring nitrogen atom. The method according to claim 1, which is used. 5. The method according to claim 1, wherein the phase transfer catalyst is one or more selected from quaternary ammonium compounds, quaternary phosphonium compounds and polyalkylene glycol compounds. 6. A phase transfer catalyst is 1-oxo-3-imino-
The method according to claim 1, wherein 0.1 to 20% by weight is used with respect to 4,7-diamino-5,6-phthaloylisoindoline. 7. An inert solvent is used as 1-oxo-3-imino-
The method according to claim 1, wherein 1 to 5 times by weight of 4,7-diamino-5,6-phthaloylisoindoline is used. 8. The method according to claim 1, wherein one or more organic solvents selected from aromatic hydrocarbons, aromatic halogenated hydrocarbons and aromatic nitrated hydrocarbons are used as the inert solvent. the method of. 9. A mixed solvent of an alcohol and one or more kinds of organic solvents selected from aromatic hydrocarbons, aromatic halogenated hydrocarbons and aromatic nitrated hydrocarbons is used as the inert solvent. The method according to claim 1, 4 or 7. 10. The one or more organic solvent selected from aromatic hydrocarbons, aromatic halogenated hydrocarbons, aromatic nitrated hydrocarbons and alcohols is used as the inert solvent. The method according to 3 or 7. 11. A deoxidizing agent is 1-oxo-3-imino-4,
The method according to claim 1, wherein 0.5 to 2 mol is used with respect to 1 mol of 7-diamino-5,6-phthaloylisoindoline. 12. The method according to claim 1, wherein the alkylating agent is used in an amount of 1 to 2 mol per 1 mol of 1-oxo-3-imino-4,7-diamino-5,6-phthaloylisoindoline. 13. The method according to claim 1, wherein the reaction is carried out at 50 to 130 ° C.