CS216451B1 - Process for the preparation of azocondensation pigments of bright shades - Google Patents

Abstract

Preparation of azocondensation pigments of the formula ^och3 coch3 R-NHCO-B-N=N-CHCONH-A-NHCOCH-N=N-B-CONH-R where R is aryl and A and B are arylene, optionally further substituted by groups having no solubilizing character, by condensation of dicarboxylic acid dichlorides with aromatic amines. The condensation is carried out in an environment free from added basic substances.

Description

The present invention relates to a process for the preparation of azo-condensation pigments of hues by condensation of dicarboxylic acid dichlorides containing and preferably two azo-moieties in the molecule, and aromatic amines not containing salt groups. Azocondensation pigments

The tint shades produced by the process of the invention have the general formula I

COCH ₃ ClOCH ₃

R-NHCO-B-N = N-CHCONH-A-NHCO-N = N-B-CONH-R (i).

where it means

R < 5 > is optionally substituted with One eS three groups selected from chloro or bromo, methyl, msthoxy, ethoxy, phenoxy, trifluoromethyl, nitro, carbomethoxy, cyano, acylamino, arylcarbamino, alkylcarbamino, alkylcarbamino, alkylcarbamino, arylamino;

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

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

A conventional process for preparing these pigments is to heat the dicarboxylic acid dichlorides of formula (I).

COCH, COCH,

I I

C1OC-BN = N-CHCONH-A-NHCOCH-N = N-BCOCl (II) and aromatic amines of formula 11 / r-nh ₂ (ΙΠ) (with the meaning of A, B and R above), * in the environment boiling organic solvents. To accelerate condensation It is recommended to work with the addition of basic substances that bind the hydrogen chloride produced by the reaction.

Conventionally, pyridine is used in an amount of 65 to 170 mol% (based on dicarboxylic acid dicarboxylic acid). Under these conditions and at a reaction temperature of 135-145 [deg.] C., the condensation takes 12 hours;

It has now been found that condensation can be carried out in a base-free environment. The reaction time ae thus significantly reduces and, moreover, eliminates the complications associated with the removal of the catalyst (e.g. pyridine) in the recovery of waste solvents. The quality of the resulting azocondensation pigments is not adversely affected by the absence of basic substances, on the contrary, condensation without the addition of pyridine makes it possible to work at milder

216,451 reaction conditions, i.e. either with a shorter reaction time or at a lower temperature, which in addition to saving anargatically water for better utilization of the process equipment and, in some cases, 1 to improve pigment quality because it suppresses unwanted side reactions. Unlike pyridine condensation, there is also no risk of hydrolysis of the dichloride used, which is catalysed by pyridine in the presence of water.

As reaction medium, anhydrous and inert organic solvents such as xylene, chlorobenzene, o-p-chlorotoluene, o-di-chlorobenzene, nitrobenzene or even mixtures of such solvents, optionally paraffinic or cycloparaffinic hydrocarbons or organic cell inorganic esters or ethers - such as tributylphosphate.

The dihloro dicarboxylic acid of formula (I) is obtained by a chloro-dye intermediate which contains two carboxyl groups in its molecule and two azo groups. For the preparation of such intercolours, the aminocarboxylic acid to be used as an active component can be used as active components.

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- Chlorobenzoic acid, 3-amino-4-carbomethoxybenzoic acid, 3-amino-4,6-dimethylbenzoic acid, 2-amino-4-chlorobenzoic acid, 2-amino-5-chlorobenzoic acid, 4-aminobenzoic acid and 4-amino- 3-nitro-benzo.

Among the passive components for the preparation of the intercolours, the bisacetoacetyl 1,4-dlaminobenzenes seem to be the most suitable as:

1,4- dlaminobenzene,

1,4-diamino-2-chlorobenzene,

1,4-dlamino-2-methylbenzene,

1,4-dlamino-2-methoxybenzene,

1,4-diamino-2-cyanobenzene,

1,4-dlamino-2-trifluoromethylbenzene,

1,4-diamino-2,5-dihlorobenzene,

1,4-diamino-2,5-dinylbenzene,

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

1,4-dlamino-2-methoxy-5-methylbenzene,

216 451 or 1,3-dlaminobenzene, where appropriate,

1,3-dlamino-4-chlorobenzene,

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

1,5-Diaminonaphthalene a

2.6- diamlnonaftalen.

Among the aromatic amines of the formula II suitable for the properties of the azo condensation pigments used, the aniline derivatives of the formula V are particularly suitable for condensation.

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

They are, for example, 2-, 3- or 4-chloroaniline; 2,5- or 2,4-dlchloraniline; 3,4,5- or 2,4,5-trichlaraniline; 4-bromoaniline; nitroanilines such as 2-, 3- or 4-nitroaniline;

2,4-dlthroaniline; alkylanines such as toluidines, xylidines, haloalkylanilines such as 3-trifluoromethylaniline, arylanines such as 4-aminodiphenyl, alkoxy or aryloxyanilines such as 2-ethoxyaniline, 2- or 4-methoxyaniline, 2,5-dimethoxyaniline; 4-aminodiphenyl ether and 2-aminodifeethyl ether, cyananines such as 3-cyananiline and aniline substituted with arylcarbamoyl, arylamino, acylamino or carbomethoxy groups such as 2-, 3- or 4-amino-benzoic acid methyl ester, aminoterephthalic acid, aminobutyl amine or aminolsophthalic acid methyl ester , 4- or 3-acetamidoaniline, 4-aminodiphenylamine. Also suitable are aniline derivatives substituted with several different substituents at the same time

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-chloro-5-methylaniline,

2-chloro-4-methylaniline,

3-chloro-4-methylaniline,

4-chloro-2-trifluoromethylaniline,

2-chloro-5-trifluoromethyleniline,

4-chloro-2-methoxyaniline,

2-chloro-4-methoxyaniline,

5-chloro-2-methoxyaniline,

216 451

4-chloro-2,5-dimethoxyaniline,

5-chloro-2,4-dimethoxy aniline

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

2-methoxy-5-methylaniline;

5-Methoxy-2-methylaniline

2-methoxy-5-trifluoromethylaniline,

4-Aeetamido-3-methoxyaniline

4-ae thyl-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-Aethoxy-5-ethyl-4-nitroaniline,

2-cyano-4-nitroaniline,

2-phenoxy-5-trifluoromethylaniline,

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

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

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

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

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

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

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

4- (4-chlorophenoxy) aniline,

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

2.5-3-amino-4-chlorobenzoic acid chloranilide,

3-Amino-4-carbomethoxybenzoic acid 5-chloro-2-methylanilide,

3-amino-4-methoxybenzoic acid, 3-chloro-2-methylanilide,

2.5-Dichloro-3-amino-4-methylbenzoic acid dichloride,

4-chloro-2-methoxyanilide of 3-amino-4-chlorobenzoic acid,

3-Amino-4-chlorobenzoic acid 4-chloro-2-methoxy-5-methylanilide a

3-Amino-4-chlorobenzoic acid 2-chloro-4-methylenilide.

The dichloro dicarboxylic acids of the formula I can also be condensed with other amines such as 1-aminonaphthalene, 1-aminoantraquinone, 1-amino-5-chloroanthraquinone or 1-amino-5-benzoylaminoantraquinone.

The pigments prepared by the process according to the invention have a wide range of applications because they are thermostable, light-stable, in organic solvents and in migration. They can be used for dyeing polypropylene, polyvinyl chloride, polyethylene, polyacrylonitrile, olyethylene, polyester, polyamide, polyurethane, rubbers, in the medical industry from below.

The process of the invention is illustrated in more detail in the following examples.

EXAMPLE 1 / Disazo dye prepared by coupling 2, 1-bis-3-amino-4-carbomethoxybenzoic acid, 1,4-bisecetoacetylemino-2-fluoro-5-methylbenzene with a chlorine reagent such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride or phosgene the corresponding dicarboxylic acid dichloride. 38.7 g of isolated and washed carbon tetrachloride are stirred in 700 g of o-dichlorobenzene and heated to 110 ° C. 14.9 g of 3- * chloro-2-methylaniline as a 20% dichlorobenzene solution are then added successively and the suspension is heated to 110 ° C for 4.5 hours while stirring well. After this time, the condensation is complete, the product is isolated by filtration and washed with hot o-dichlorobenzene with ethanol and water. After drying and e, 46.7 g of a yellow pigment are obtained.

Condensation with addition of pyridine takes about 15 hours under otherwise identical conditions.

Example 2

35.3 g of disazo-dye chloride prepared by coupling of palzotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetylamino-2,5-dimethylbenzene are stirred in 520 g of o-dichlorobenzene, the reaction mixture is heated to 140 DEG C. and then a solution is added. 11.6 g of 2-toluidine in 50 g of o-dichlorobenzene. After heating at 135-140 ° C for 1.5 hours, 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 as a reddish-yellow powder Soft texture. According to US Pat. 2,936,306 is the reaction time with addition of pyridine 12 hours.

and

When 15.6 g of 2-methyl-5-chloreniline are used to condense with said dichloride, the reaction takes 1.5 hours at 135-145 ° C.

Example 3

Coupling of palzotized 3-amino-4-carbomethoxybenzoic acid with 1,4-bisacetoacetyl-amino-2,5-dichlorobenzene in a 2: 1 molar ratio yields a disazo dye which is converted to dicarboxylic acid dichloride under phosgene treatment with anhydrous chlorobenzene under catalysis with dimethylformamide. After the chlorination is complete, a portion of chlorobenzene together with excess phosgene and hydrogen chloride is distilled off from the suspension containing 39.7 g of disazoic acid chloride, then 17.8 g of 2.5 dl chloroaniline are added and the reaction mixture is heated under gentle reflux for 7 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.

216 451

The following table gives further examples of the preparation of the azo condensation pigments of the invention.

Active component Passive component / bisaeetoacetylated diamine / Arylamine 3-Amino-4- acid -cblorbenzoová 1,4-diamino-2,5-dichlorobenzene 5-chloro-2-methylaniline 3-Amino-4- acid -chlorobenzoová 1,4-diamino-2-methylbenzene 2-chloroaniline 3-Amino-4- acid -ehlorbenz oová 1,4-Diamino-2-methoxy-5- -methylbenzene 2,4-dinitroaniline 3-Amino-4- acid -methoxybenzoic acid 1,3-diamino-4-chlorobenzene 4-acetamidoaniline 3-amino-4,6- -dichlorbenzo 1,4-diamino-2,5-dimethylbenzene; 2-chloro-5-trifluoro- -methylaniline 2-Amino-4- acid -chlorobenzoic 1,4-diamino-2,5-dimethylbenzene 5-chloro-2- (chlorophenoxy) aniline 4-amino-3- acid -nitrobenzoová 1,4-diamino-2,5-dimethylbenzene 2-Cyano-4-nitroaniline 3-Amino-4- acid -chlorobenzoová 1,4-diamino-2-chloro-5-methylbenzene 3-chloro-2-methylaniline 3-Amino-4- acid -chlorobenzoová 1,4-diamino-2-chloro-5-methylbenzene 3-chloro-2-methylaniline 3-Amino-4- acid -chlorobenzoová 1,4-diamino-2,5-dichlorobenzene 5-chloro-2-methylaniline 3-Amino-4- acid -carbme thoxybenzo 1,4-diamino-2-chlorobenzene 3-chloro-2-methylaniline 3-Amino-4- acid 1,4-diamino-2-cyanobenzene 4-methyl-2-nitroaniline

-carbmethoxybenio

216 451

3-Amino-4- acid -carbmethoxybenzoic 1,3-dlamino-4,6-dichlorobenzene 3-Amino-4-chloro-2,5-dichloroaniline zoové 3-Amino-4- acid -chlorobenzoic 1,5-Dlaminonaphthalene 2-methoxy-4-nitroaniline 3-amino-4- - chlorobenzoic 1,4-dlamino-2-methylbenzene 1-aminoantraquinone 3-Amino-4- acid -chlorobenzoic 1,4-dlamino-2-chloro-5-methylbenzene 5-chloro-2-methylanilide 3-amino-4- -carbmethoxybenzoic

Claims (1)

Process for preparing azocondensation pigments COCH, COCH, I I R-NHCO-B-N-N-CHCONH-A-NHCOCH-N = N-B-CONH-R (I) where 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 by COCH, COCH, I I C1CO-B-N = N-CHCONH-A-NHCOCH-N = N-B-COCl (II), wherein A and B are as defined above, in a molecular ratio of 1: 2 with aromatic amines of formula III R-NH ₂ (III), wherein R is as defined above, in an inert organic solvent at 60 to 180 ° C, characterized in that the condensation is carried out in an environment free of added basic substances.