CS219960B1 - Method of preparation of the azocondenzation pigment of yellow shade - Google Patents

Description

The invention relates to a process for the preparation of acocondensation pigments of yellow shades by condensation of dicarboxylic acid dichlorides, preferably containing two azo groups per molecule, with aromatic amines not containing solubilizing groups. The yellow-colored azo condensation pigments prepared by the process of the invention have the general formula I '

COCH3

R — NHCO — B — N = N — CHCONH — A—

COCl 3 —NHGOCH — N = N — B — CONH — R (I) where is

R is aryl optionally substituted with one to three groups selected from chlorine or bromine, methyl, methoxy, ethoxy, phenoxy, trifluoromethyl, nitro, carbomethoxy, cyano, acylamino, arylamino, alkylcarbamoyl, alkylcarbamoyl, alkylcarbamoyl

A arylene, optionally substituted with one or two substituents selected from the group consisting of chloro, methyl, methoxy, ethoxy, trifluoromethyl, and cyano,

B is a benzene group optionally substituted by a chlorine atom, a methyl group, a methoxy group, a trifluoromethyl group, a nitro group or a carbomethoxy group.

The prior art process for preparing these pigments consists in heating the dicarboxylic acid dichlorides of formula II

COCHs

C1OC — Β — N = N — CHCONH — A—

COCH3 —N.HCOCH — N = N — B — COCl (II) with aromatic amines of formula III

R-NH2 (III) having the meanings given above for A, B and R, in an environment of above-boiling organic solvents, either in the absence of catalysts or with the addition of bases which bind hydrogen chloride formed by the reaction.

Typically, the basic catalyst used is pyridine in an amount of 65 to 170% by mol, based on the dicarboxylic acid dichloride. Under these conditions and at a reaction temperature of 135-145 ° C, the condensation takes 12 hours. In this case, pyridine not only acts as a base to bind the resulting hydrogen chloride, but also has a catalytic effect according to the literature.

It has now been found that, in contrast to the base-catalyzed or non-catalyzed reaction, the condensation reaction between the compounds of the formulas I and II proceeds faster when the bifunctional catalysts of an acid nature are used. A process for the condensation of dicarboxylic acid dichlorides of the formula I wherein A is an arylene radical optionally further substituted by one or two chlorine atoms, methyl, methoxy, ethoxy, trifluoromethyl, or cyano and B is a benzene radical optionally substituted by chlorine, methyl- , methoxy, trifluoromethyl, carbomethoxy or nitro in a molar ratio of 1: 2 'with aromatic amines of the general formula II, wherein R is aryl, optionally substituted with one to three groups such as chlorine, bromine, methyl, methoxy, ethoxy phenoxy-, trifluoromethyl-, nitro-, carbomethoxy-, cyano-, acylamino, ηο-, arylamino-, alkylcarbamoyl-, or arylcarbamoyl groups in an inert solvent at 60 to 180 ° C, characterized in that the condensation is carried out with the addition of a catalyst selected from optionally chlorinated acetic acid, acetic acid, thioacetic acid, oxalic acid, chlorpropionic acid, cinnamon, cyanuric, fumaric, violet and nitrobenzene, dimethylformamide, dibenzamide, phthalimide, benzanilide and piperldone, in a molar ratio of 0.1 to 10: 1 based on the amine of formula II, when they are liquid up to 1: 1 by weight with the solvent used as the reaction medium.

The quality of the resulting azo condensation pigments is not adversely affected by the addition of the acid catalyst; on the contrary, it is possible to work under milder reaction conditions, i.e. either with a shorter reaction time or at a lower temperature. of pigment quality, since the undesirable side reactions are suppressed. Unlike pyridine condensation, there is also no risk of hydrolysis of the dichloride used, which is catalysed by pyridine in the presence of water.

In general, compounds of formula IV can be used as acid catalysts

O

OF

Ri-C \

XH

Rž

(IV), wherein X is an oxygen, sulfur or nitrogen atom, R 1 is alkyl, aryl, aralkyl, alkenyl, arylalkonyl, wherein the aryl radical is optionally further substituted by chlorine, nitro or carboxyl and alkyl and the alkenyl radical is optionally further substituted by a carboxyl group or one or more chloro, R2 is hydrogen when X is oxygen or sulfur; in the case where X is nitrogen, R 2 is alkyl, aryl or acyl.

The compounds of formula IV are:

- saturated and unsaturated aliphatic carboxylic acids such as formic, acetic, propionic, butyric or aryl acids, -a- and β-halogen acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, α-chloropropionic acid or β-chloropropionic acid, - aromatic carboxylic acids such as benzoic, 1- or 2-naphthoic, phenylacetic, cinnamon, 2-chlorobenzoic, 4-chlorobenzoic, 3-nitrobenzoic or

3,5-dinitrobenzoic acid, - aliphatic and aromatic thioacids such as acetic acid or thiobenzoic acid, - aliphatic and aromatic dicarboxylic acids, saturated and unsaturated, such as oxalic, malonic, succinic, glutaric, maleic, fumaric, phthalic, isophthalic or terephthalic acid, alkyl amides, arylamides or diacylamides of carboxylic acids such as N-methylbenzamide, benzanilide, acetanilide, diacetamide or dibenzamide.

In the case of carboxylic acids, their salts can also be used instead of the free acids. In addition to the compounds of formula IV, heterocyclic compounds containing a carboxamido group —CO — NH— can also be used as catalysts of the condensation reaction between compounds of formulas I and II. They are:

- dicarboxylic acid or sulfonated carboxylic acid imides, such as succinimide, phthalimide, tetrachlorophthalimide, glutarimide or saccharin, - aliphatic γ- and d-aminocarboxylic acid lactams, such as pyrrolidone- (2) or piperidone- J 2), - other heterocyclic compounds with a suitable grouping of amide groups such as phthalic hydrazide, cyanuric acid or isatin.

The above catalysts are generally used in a molar ratio of 0.1-10: 1 based on the condensing aromatic amine, but larger amounts of catalyst can also be used, especially if they are liquid at the reaction temperature, such as acetic acid. In this case, it replaces part of the reaction medium.

Anhydrous and inert organic solvents such as xylene, chlorobenzene, o- or p-chlorotoluene, o-dichlorobenzene, trichlorobenzene, nitrobenzene or even mixtures of such solvents, optionally paraffinic or cycloparaffinic hydrocarbons or organic or inorganic esters or ethers or ethers or ethers are used as reaction medium. - such as tributy] phosphate.

The dicarboxylic acid dichloride of formula (I) is obtained by chtoridation of an intermediate dye which contains two carboxyl groups and two azo groups in its molecule. Diazotized aminocarboxylic acids can be used as active components for the preparation of such dyes. With regard to the application properties of pigments, these are in particular aminobenzoic acids, such as:

3-aminobenzoic acid, 3-amino-4-chlorobenzoic acid, 3-amino-4-methylbenzoic acid, 3-amino-4-methoxybenzoic acid, 3-amino-6-chlorobenzoic acid, 3-amino-4, 6-dichlorobenzoic acid, 3-amino-4-carbomethoxybenzoic acid, 3-amino-4,6-dimethylbenzoic acid, 2-amino-4-chlorobenzoic acid, 12-amino-5-chlorobenzoic acid, 4-aminobenzoic acid and 4- amino-3-nitrobenzoic acid.

Among the passive components for the preparation of dyes, bisacetoacetyl 1,4-diaminobenzenes are most suitable as:

1,4- diaminobenzene,

1,4-diamino-2-chlorobenzene,

1,4-diamino-2-methylbenzene,

1,4-diamino-2-methoxybenzene,

1,4-diamino-2-cyanobenzene,

1,4-diamino-2-trifluoromethylbenzene,

1,4-diamino-2,5-dichlorobenzene,

1,4-diamino-2,5-dimethylbenzene,

1,4-diamino-2-chloro-5-methylbenzene

1,4-diamino-2-methoxy-5-methylbenzene, optionally also

1,3-diaminobenzene,

1,3-diamino-4-chlorobenzene,

1,3-diamino-4,6-dichlorobenzene,

1,5-Diaminonaphthalene a

2.6- diaminonaftalen.

Among the aromatic amines of the general formula II suitable for the utility properties of azocondensation pigments, the aniline derivatives of the general formula V are particularly suitable for condensation

wherein Z 1, Z 2, Z 5 are a halogen, alkyl, alkoxy, phenoxy, trifluoromethyl, nitro, carbalkoxy, cyano, acylamino, arylamino, alkylcarbamoyl or arylcarbamoyl group.

Examples include 2-, 3- or 4-chloroaniline; 2,5- or 2,4-dichloroaniline; 3, 4, 5 or

2.4.5- trlchloraniline; 4-bromoaniline; nitroanilines such as 2-, 3- or 4-nitroaniline and 2,4-dinitroaniline; alkylanilines such as toluidines, xylidines, haloalkylanilines such as 3-trifluoromethylaniline, arylanilines such as 4-aminodiphenyl, alkoxy or aryloxyanilines such as 2-ethoxyaniline, 2- or 4-methoxyaniline, 2,5-dimethoxyaniline; 4-aminophenyl ether and 2-aminodiphenyl ether, cyananilines such as 3-cyananiline and aniline substituted with arylcarbamoyl, arylamino, acylamino or carbomethoxy such as methyl 2-, 3- or methyl ester

4-aminobenzoic acid, dimethyl ester of aminoterephthalic acid or 4-aminobenzoic acid;

3-acetamidoaniline, 4-amidodiphenylamine.

Aniline derivatives substituted simultaneously by several different substituents are also suitable, such as

4-chloro-2-nitroaniline,

2-chloro-4-nitroaniline,

3-chloro-2-methylaniline,

5-chloro-2-methylaniline,

4-chloro-2-methylaniline

6-chloro-2-methylaniline,

2-Chloir-5-methylaniline

2i-chloro-4-methylaniline

3-chloro-4-methylaniline,

4-Chloro-2-trifluoromethylaniline

2-chloro-5-trifluoromethylaniline,

2-chloro-2-methoxyaniline,

2-chloro-4-methoxyaniline,

5-chloro-2-methoxyaniline

4-chloro-2,5-dimethoxyaniline,

5-chloro-2,4-dimethoxyaniline

4-chloro-2-methoxy-5-methylaniline,

2-methoxy-5-methylaniline,

5-methoxy-2-methylaniline

2-methoxy-5-trifluoromethylaniline;

4-acetamido-3-methoxyaniline,

4-methyl-2-nitroaniline,

2-methyl-5-nitroaniline,

4-methyl-3-nitroaniline,

2-methyl-4-nitroaniline,

2-methoxy-4-nitroaniline,

4-methoxy-2-nitroaniline,

2-methoxy-5-nitroaniline,

2,5-dimethoxy-4-nitroaniline,

2-methoxy-5-methyl-4-nitroaniline,

2-cyano-4-nitroaniline,

2-Phenoxy-5-trifluoromethylaniline

1 N 5 N 13

2- (4-chlorophenoxy) -4-chloro-5-trifluoromethylaniline,

2- (4-Methylphenoxy) -4-chloro-5-trifluoromethylaniline

2- (2,4-dichlorophenoxy) -4-chloro-5-trifluoromethylaniline,

2- (4-methoxyphenoxy) -3-trifluoromethylaniline,

2- (4-terhutylphenoxy) -5-trifluoromethylaniline,

2- (4-isopropylphenoxy) -5-trifluoromethylaniline,

2- (3-chloro-4-isopropylphenoxy) -5-trifluoromethylaniline,

4-, (4-chlorophenoxy) aniline,

5-chloro-2- (4-chlorophenoxy) aniline

3-Amino-4-chloro-benzoic acid 2,5-dichloroanilide,

5-chloro-2-methylaniline of 3-amino-4-carbomethoxyhenzoic acid,

3-chloro-2-methylanilipd acid

3-amino-4-methoxybenzoic acid,

3-chloro-2-methylanilide acid

3-amino-4-methoxyhenzoic acid,

3-Amino-4-methylbenzoic acid 2,5-dichloroanilide,

4-chloro-2-methoxyanilide acid

3-amino-4-chlorobenzoic acid,

4-chloro-2-methoxy-5-methylanilide

3-amino-4-chloro-benzoic acid and 2-chloro-4-methylanilide

3-amino-4-chlorobenzoic acid.

The dicarboxylic acid dichlorides of the formula I can also be condensed with other amines, such as 1-aminonaphthalene, 1-aminoanthraquinone, 1-amino-5-chloroanthraquinone or 1-amino-5-benzoylaminoanthraquinone.

The pigments prepared by the process according to the invention are widely used because they are thermostable, stable in light, in organic solvents and in migration. It can be used for dyeing polypropylene, polyvinyl chloride, polyethylene, polyacrylonitrile, polystyrene, polyester, polyamide, polyurethane, rubbers, in the paint industry and the like.

The process according to the invention is illustrated by the following examples.

Example 1

Disazo dye prepared by coupling of diazotized 3-amino-4-carbomethoxybenzoic acid with 1,4-bisacetoacetylamino-2-chloro-5-methylbenzene in a molar ratio of 2: 1 by treatment with chlorinating agents such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride or phosgene, is converted to the corresponding dicarboxylic acid dichloride. 38.7 g of the isolated and washed dichloride are stirred in 700 g of o-dichlorobenzene, 0.6 g of acetic acid are added and the suspension is heated to 100 ° C. Then, 14.9 g of 3-chloro-2-methylaniline as a 20% dichlorobenzene solution is added successively and the suspension is heated to 135-140 ° C with good stirring for

0.5 hours. After this time the condensation is complete, the product is isolated by filtration and washed with hot o-dichlorobenzene, ethanol and water. After drying, 46.7 g of a yellow pigment are obtained.

At a reaction temperature of 110 DEG C. with catalysis of 20 g of acetic acid, the condensation time of 38.7 g of the above dichloride with 17.0 g of 3-chloro-2-methylaniline is 2 hours, the condensation time of the uncatalyzed reaction is 4.5 hours, with pyridine added. reaction takes about 15 hours.

Example 2

35.3 g of disazo dye dichloride prepared by coupling diazotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetylamine O'-2,5-dimethylbenzene is stirred in 520 g of o-dichlorobenzene, 6.1 g of benzoic acid are added, reaction mixture was heated to .140 ^q C, then a solution of 11.6 g 2-toluidine in 50 g of o-dichlorobenzene. After heating at 135-140 ° C for 0.5 h, the reaction is complete, the suspension is neutralized by the addition of sodium bicarbonate, the pigment is isolated by filtration and washed as in Example 1. 40.5 g of pigment are obtained in the form of a reddish yellow powder soft texture. Without catalysis, the condensation takes 1.5 hours if the condensation is carried out according to USpat. No. 2,91316,300 with the addition of pyridine, the reaction time is 12 hours. When 15.6 g of 2-methyl-5-chloroaniline are used for condensation with said dichloride, the reaction time at 135-145 ° C with oxalic acid catalysis is 0.5, without catalysis 1.5 hours.

Example 3

Coupling of diazotized 3-amino-4-carbomethoxybenzoic acid with 1,4-bisacetoacetylamino-2,5-dichlorobenzene in a molar ratio of 2: 1 gives a disazo dye which is converted into dicarboxylic acid dichloride under phosgene treatment with anhydrous chlorobenzene under catalysis with dimethylformamide. After the chlorination is complete, a portion of chlorobenzene, along with excess phosgene and hydrogen chloride, is distilled off from the suspension containing 39.7 g of disazo dye dichloride, then 15 g of saccharin, 17.8 g of 2,5-dichloroaniline are added and the reaction mixture is heated to stirring. boil for 2 hours. The pigment was then filtered off and washed with solvents as described in Example 1. 47.5 g of a greenish-yellow pigment were obtained.

The following table gives further examples of the preparation of the azocondensation pigments according to the invention. The first column shows the aminocarboxylic acid used for diazotization to coupling the passive component in the second column. In the third column the aromatic amine is used for the condensation and in the fourth column the catalysts.

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Claims (1)

A process for the preparation of yellow-colored azo condensation pigments of general formula (I) COCH3 COCH3 R — NHCO — B — N = N — CHCONH — A — NHCOCH — N = N — B — CQNH — R (I) R aryl optionally substituted with one to three groups selected from chlorine or bromine, methyl, methoxy, ethoxy, phenoxy, trifluoromethyl, nitro, carbomethoxy, cyano, acylamino, arylamino, arylcarbamoyl, alkylcarbamoyl and alkylcarbamoyl A arylene optionally substituted by one or two of chloro, methyl, methoxy, ethoxy, trifluoromethyl and cyano; and B is a benzene group optionally substituted by a chlorine atom, methyl group, methoxy group, trifluoromethyl group, carbomethoxy group or nitro group, by condensation of dicarboxylic acid dichlorides of formula II COCH3 COCH3 I. AND C1CO-B-N = N-CHCONH-A-NHCOCH-N = N-B-COCl, where A and B are as defined above, in a molar ratio of 1: 2 with aromatic amines of formula III R - NH2 (III) wherein R is as defined above, in an inert solvent at 60 DEG to 180 DEG C., characterized in that the condensation is carried out with the addition of a catalyst selected from the group consisting of chlorinated acetic acid, acetic acid, thioacetic acid , oxalic, chlorpropionic, cinnamon, cyanuric, fumaric, phthalic and nitrobenzene, dimethylformamide, dibenzamide, phthalimide, benzanilide and piperidone, in a molar ratio of 0.1 to 10: 1, based on the amine of formula III and when the catalyst is a liquid up to 1: 1 by weight in the presence of a solvent used as the reaction medium.