DE1186966B - Process for the production of anthraquinone dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C09b

German class: 22 b-3/03

Number: 1186 966

File number: C 20212 IV c / 22 b

Filing date: November 20, 1959

Opening day: February 11, 1965

It has been found that valuable vat dyes are obtained if 2MoI of an anthraquinone-2-carboxylic acid alkyl, cycloalkyl or aralkyl ester, which is an amino group in the 1-position and in at least one further «position has an amino group with 1 mol of a dicarboxylic acid halide or a heterocyclic compound which has at least twice the grouping

halogen

contains in the ring, and any exchangeable halogen atoms present in the reaction products obtained replaced by alkyl or arylamine radicals.

Of particular interest as starting materials are the 1 ^ -Diaminoanthraquinone ^ -carboxylic acid esters of formula

O NH ₂

-COOR

Process for the preparation of anthraquinone vat dyes

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and

Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man,

Patent Attorneys, Munich 9, Schweigerstr. 2

Named as inventor:

Dr. Walter Kern, Sissach;

Dr. Jacob Koch, Basel (Switzerland)

Claimed priority:
Switzerland of November 21, 1958,
dated October 16, 1959

(D

NH,

wherein R is an alkyl, aralkyl or cycloalkyl group. In addition to the above, others can be used Substituents, for example halogen atoms, alkyl, alkylsulf onyl, arylsulf onyl, alkylsulfamide or cyano groups, be present in the anthraquinone molecule. The carboxylic ester group is preferably derived from a lower aliphatic or cycloaliphatic or araliphatic alcohol, for example Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl or cyclohexyl alcohol, benzyl alcohol, Phenylethyl alcohol, «-Furylmethyl alcohol. Those to be used as acylating agents according to the process Dicarboxylic acid halides are preferably derived from aryldicarboxylic acids, for example of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, Azobenzene-4,4'-dicarboxylic acid, azodiphenyl-4,4 "-dicarboxylic acid, fluoranthene-4,12-dicarboxylic acid, Benzanthrone-2,6-dicarboxylic acid, anthraquinone-2,6-dicarboxylic acid, and also dicarboxylic acids of the type

HOOC

COOH

wherein each X is O, S, SO or SO ₂ , e.g. B.

the diphenylenedioxide or especially the thianthrene dicarboxylic acids. Further examples of heterocyclic carboxylic acids are the diphenylene oxide and diphenyl sulfide dicarboxylic acids, the 2,5-diphenyloxdiazole dicarboxylic acids called.

From the series of heterocyclic compounds suitable as acylating agents, containing at least twice the grouping

.N -

halogen

in the ring, especially the 1,3,5-triazines formula

N "'
Cl-C-

C-Cl

called, where X is a halogen atom, preferably a chlorine atom, a hydrogen atom, an alkyl radical, preferably a ^ lower alkyl, for example a methyl or ethyl radical, an aryl, in particular Benzene radical, for example the phenyl, 3- or

509 508/270

4-methylphenyl-, 2,4-dimethylphenyl-, 2- or 3-methoxyphenyl-, 4-chlorophenyl or 3,4-dichlorophenyl radical, denotes an alkylamine, arylamine or a phenoxy radical. In addition to the triazines are also Diazines called such. B. 2,4-dichloropyrimidine, 2,4-dibromopyrimidine, 2,4-dichloro-6-methylpyrimidine, 2,4-dichloro-6-phenylpyrimidine, 2,5-dichloropyrazine, 2,4-dichloroquinazoline, 2,4-dichloro-6,7-benzquinazoline, 2,4-dichloro-6,7-phthaloylquinazoline, 2-phenyl-4-chloro-6,7-phthaloylquinazoline, 2- (Anthraquinonyl-2 ') 4-chloroquinazoline, 1,3-di- (4'-chloro-6', 7'-phthaloylquinazolyl-2 ') benzene, 1,4-dichlorophthalazine, 4,4'-dichloro-6,6'-diphenyl-l , 1 '-3,3'-bis-diazine.

The proportions are advantageously chosen so that 1 mol of a dicarboxylic acid chloride or a heterocyclic compound of the type mentioned above with 2 moles of the diaminoanthraquinone-2-carboxylic acid ester is implemented. The halogen atoms in the diazines or triazines can also be replaced in stages. The first halogen atom can for example by a residue of a diamino-2-carboxylic acid ester and the second halogen atom by the residue of the same or different from the first Diamino-2-carboxylic acid ester are replaced. In the cyanuric chloride there are three interchangeable Chlorine atoms available, two of which are replaced by diaminoanthraquinone-2-carboxylic acid ester residues will. Under vigorous conditions, the third halogen atom can also be used, for example by heating with primary or secondary aliphatic or aromatic amines, for example aniline, N-methylaniline, N-Äthylanih'n, methylamine, ethylamine, Dimethylamine, di (oxyethyl) amine, can be replaced by amino groups.

The same dyes can be obtained even more advantageously if cyanuric chloride is used instead a dichlorotriazine in which one chlorine atom has already been replaced by one of the amine radicals mentioned, with Reacts 2 moles of the diaminoanthraquinone carboxylic acid ester.

The condensation can advantageously be carried out in such a way that the diaminoanthraquinone carboxylic acid esters and the acylating agents in solvents or suspending agents, such as nitrobenzene, trichlorobenzene, chlorobenzene, naphthalene, toluene or glacial acetic acid, are allowed to act on one another for a sufficient time, the temperature im is generally between 90 and 210 ^° C., if necessary with the addition of condensing agents, for example copper (I) chloride, possibly also others, e.g. B. hydrogen halide binding agents. The solvent can also be omitted by removing the compo-

ao nents, if necessary with the necessary additives, simply melts together. Under the mentioned conditions only the amino group in the 4-, 5- or 8-position is acylated, while the amino group remains free in the 1-position because of the hindering influence of the carboxylic acid ester group.

The products obtained according to the process are suitable for dyeing and printing the most diverse Materials, in particular for dyeing and printing fibers made from natural and regenerated cellulose. The dyeings obtained are distinguished by good fastness properties, in particular chlorine fastness. The dyes obtained can also be used as pigments. Are of particular interest the dyes of the formula

NH,

-COOR

NH

H ₉ N

ROOC

A-

HN

where R is an organic radical, A is the radical of a dicarboxylic acid, a diazine or triazine radical. These dye the cellulose fibers in blue to violet shades of excellent light, chlorine and soda cooking fastness. It is extraordinarily surprising that the carboxylic ester groups under Do not saponify the strongly alkaline conditions of the vatting and the soda boiling test.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

60

2.26 parts of 4-phenyl-2,6-dichlorotriazine- (1,3,5) with 6.2 parts!, ^ diaminoanthraquinone ^ -carboxylic acid ethyl ester and 168 parts of trichlorobenzene for 3 hours at 170 to 173 °. After cooling down is suctioned off, washed with methyl alcohol and dried. 6.9 parts of a blue one are obtained Dye that dyes cotton from a reddish brown vat in pure reddish blue, very real tones.

Example 2

2.26 parts of 4-phenyl-2,6-dichlorotriazine- (l, 3.5) are with 6.76 parts of l ^ -diaminoanthraquinone ^ -carboxylic acid isobutyl ester and 168 parts of trichlorobenzene for 3 hours at 170 to 173 °. After cooling down is suctioned off, washed with methyl alcohol and dried. You get 6 parts of one blue dye, the cotton from the reddish brown vat in pure reddish blue, very real tones colors.

Example 3

2.26 parts of 4-phenyl-2,6-dichlorotriazine- (1,3.5) with 7.26 parts of 1,4-diaminoanthraquinone-2-carboxylic acid cyclohexyl ester and 168 parts of trichlorobenzene Stirred for 3 hours at 170 to 173 °. After cooling, it is suctioned off and washed out with methyl alcohol and dried. 6.4 parts of a blue dye are obtained, the cotton from red-brown Küpe colors in pure reddish blue, very real tones.

Example 4

3.4 parts of 1 ^ -diaminoanthraquinone ^ -carboxylic acid isobutyl ester are heated in 30 parts of nitrobenzene. At 130 °, 1.06 parts of isophthalic acid dichloride are added and then stirred for a further 2 hours at 170 to 180 °. After cooling, it becomes the condensation product suctioned off, washed with alcohol and dried. 3.7 parts of a violet dye are obtained, which Cotton from a red vat dyes pure, very real purple tones.

If the cyclohexyl ester of 1,4-diaminoanthraquinone-2-carboxylic acid is used instead of the isobutyl ester, then a dye with similar properties is obtained.

If the dichlorides of other dicarboxylic acids are used instead of the dichloride of isophthalic acid, analogous dyes are then obtained, their vat colors and hues of the cotton dyeings can be seen in the table below.

Dicarboxylic acid used as dichloride

Ester used colour the 1,4-diamino the vat anthraquinone 2-carboxylic acid Red-brown Isobutyl Red-brown Cyclohexyl Red-brown Isobutyl Red-brown Isobutyl Red Isobutyl Red Cyclohexyl Brown Isobutyl Yellow-brown Cyclohexyl Brown Isobutyl

hue

the coloring

on cotton

1 terephthalic acid

2 terephthalic acid

3 azobenzene-4,4'-dicarboxylic acid

4 Azodiphenyl-p ^ '- dicarboxylic acid

5 thianthrene dicarboxylic acid

6 thianthrene dicarboxylic acid

7 fluoranthene-4.11-dicarboxylic acid

Fluoranthene-4,11-dicarboxylic acid

Fumaric acid

Example 5

1 part of 2,4-dichloro-quinazoline, 4 parts of 1,4-diaminoanthraquinone-2-carboxylic acid isobutyl ester and 40 parts of nitrobenzene are heated to boiling for 8 hours. After cooling, it becomes the condensation product suctioned off, washed with alcohol and dried. It dyes cotton from red-brown vat in real ones greenish blue tones.

Example 6

3.4 parts!, S-diaminoanthraquinone - ^ - carboxylic acid isobutyl ester are heated in 30 parts of nitrobenzene. 1.06 parts of terephthalic acid dichloride are added at 130 ° and then stirred for a further 2 hours at 170 to 180 °. After cooling, it becomes the condensation product suctioned off, washed with alcohol and dried. 3.2 parts of a red-brown dye are obtained, which dyes cotton from the red-brown vat in real copper-red tones.

If isophthalic acid dichloride is used instead of terephthalic acid dichloride, one obtains one Navy blue

Navy blue

Gray

Gray

Navy blue

Navy blue

Gray

Corinth

Navy blue

Dye of similar properties, while that of fluoranthene-4,11-dicarboxylic acid dichloride and 1,5 - diaminoanthraquinone - 2 - carboxylic acid isobutyl ester resulting condensation product cotton colors in reddish orange tones.

Example 7

2.26 parts of 4-phenyl-2,6-dichlorotriazine- (1,3.5) are mixed with 6.48 parts of M-diaminoanthraquinone ^ -carboxylic acid n-propyl ester and 168 parts of trichlorobenzene for 3 hours at 170 to 173 °. After cooling down is suctioned off, washed with methyl alcohol and dried. 6.6 parts are obtained of a blue dye, the cotton from the red-brown vat in very real, pure red-tinged blue Tones colors. Despite the ester group, the dye is still washable and soda-proof.

The table below shows other dyes with analogous dyeing properties, with variations in the ester Properties listed. They can be produced according to the information in paragraph 1.

1,4-diaminoanthraquinone
2-carboxylic acid ester Vat color Hue of staining
on cotton 1 M-diaminoanthraquinone ^ -carboxylic acid isopropyl-
ester Red-brown pure, reddish blue 2 Benzyl M-diaminoanthraquinone ^ -carboxylate Red-brown pure, reddish blue 3 l ^ -Diaminoanthraquinone ^ -carboxylic acid n-butyl ester Red-brown pure, reddish blue 4th M-diaminoanthraquinone ^ -carboxylic acid-sec.-butyl-
ester Red-brown reddish blue 5 l ^ diaminoanthraquinone ^ -carboxylic acid-phenyl-
ethyl ester Red pure, reddish blue

Example ^{8 6} 5 acid methyl ester and 168 parts of trichlorobenzene

Stirred for 3 hours at 170 to 173 °. After he-

2.26 parts of 4-phenyl-2,6-dichlorotriazine- (l, 3.5) are cold, suctioned off, with methyl alcohol 5.92 parts of M-diaminoanthraquinone ^ -carbon- washed and dried. 6.1 parts are obtained

Claims (3)

of a blue powder, the cotton washed out from red-brown methyl alcohol and dried. Man Küpe in real, pure and reddish shades of blue is given a blue powder that dyes cotton from red, brown vat in strong reddish shades of blue. The result is similar, somewhat more neutral shades of blue. The product still contains chlorine.
one, if the 1 ^ diaminoanthraquinone - ^ - carbon- 5 A similar product is obtained if acid methyl ester with 1,4-diaminoanthraquinone instead of nitrobenzene trichlorobenzene 2-carboxylic acid amyl ester or 1,4-diaminoanthra and 16 Hours at 100 to 105 ° is stirred.
chmon-2-carboxylic acid cyclopentanyl ester is replaced. 2.45 parts of the Pro obtained in the first section Duktes with 15 parts of aniline for 10 hours Example 9 ¹⁰ stirred from 155 to 160 °, then left to cool, removed trated, washed out with methyl alcohol and 1.13 parts of 4-phenyl-2,6-dichlorotriazine- (1,3.5) are dried. Blue crystals are obtained, which consist of rotmit 3.22 parts l ^ diaminoanthraquinone ^ -carbon- brown vat cotton in very real and pure allyl acid ester and 84 parts of trichlorobenzene for 3 hours to color reddish blue shades. stirred at 170 to 173 °. After cooling, it is suctioned off with suction, with a little trichlorobenzene and then with borrowed dye, if the starting methyl alcohol is washed out and dried as the starting methyl alcohol. The dye of the second paragraph produces a blue crystalline powder that is used in cotton.
from red-brown vat in light and chlorine rights,
pure reddish blue tones. 20 B is ρ ie 1 13 Similar dyes are obtained if instead of 1. ^ diaminoanthraphinone ^ -carbon- 1.13 parts of 4-phenyl-2,6-dichlorotriazine- (1,3.5) allyl esters, the esters of 1,4-diaminoanthraquinone with 3.4 parts of 1,5-diaminoanthraquinone-2-carbon-2-carboxylic acid chloride and p-chloroethyl alcohol or isobutyl acid and 42 parts of trichlorobenzene Ethylene glycol or ethylene glycol monomethyl ether 25 stirred for 3 hours at 170 to 173 °. After being used will. cold is suctioned off, washed first with a little trichlorobenzene, then with methyl alcohol and Example 10 dried. 2.3 parts of a red-orange are obtained crystalline powder, the cotton made from orange 2.55 parts of 2-N-methylanilino-4,6-dichlorotri- 30 brown vat dyes in real red shades. From the azine (l, 3.5) and 7.1 parts 1,4-diaminoanthraquinone analysis (N found: 11.99%; N calculated: 11.82%) Isobutyl 2-carboxylates are used in 168 parts of tri it is found that it is the condensation product chlorobenzene for 3 hours at a temperature of 170 from 1 mole of 4-phenyl-2,6-dichlorotriazine- (l, 3.5) and stirred to 173 °. After cooling, 2 mol of 1,5-diaminoanthraquinone-2-carboxylic acid isomite are filtered off with suction Washed out methyl alcohol and dried. 35 butyl ester. 6.7 parts of a blue, crystalline powder are obtained. The 1,5-diamino used in the first paragraph verse that is made from red-brown cotton vat in very isobutyl anthraquinone-2-carboxylate colors real and pure, somewhat reddish shades of blue. is made as follows: According to example 2 of the German patent specification Example 11 4 ° 360422 by exposure to fuming sulfur acid on the l, 5-dinitro-2-methylanthraquinone 1.93 parts of 2-dimethylamino-4,6-dichlorotriazine- (l, 3,5) tene S-nitroanthraquinone-l ^ -isoxazole is according to and 7.1 parts!, ^ - diaminoanthraquinone ^ -carbon- the details of German patent 464 863, acid isobutyl ester with 168 parts of trichloro Example 3, by heating with dilute sodium benzene 3 hours at a temperature of 170 to 45 hydroxide solution to 80 to 90 ° in the 1-amino-173 ° touched. After cooling, it is filtered off with suction, 5-nitroanthraquinone-2-carboxylic acid is cleaved and used Washed out methyl alcohol and dried. on the acid-man in nitrobenzene with thionyl chloride receives 6.4 parts of a blue crystalline powder, chloride produced (Cl found: 10.86%; Cl bedas melts at 295 to 297 ° and cotton calculates: 10.72%). This will be with excess red vat in very real and pure reddish 50 isobutyl alcohol by boiling for 2 hours in the Shades of blue color 1 - amino - 5 - nitroanthraquinone - 2 - carboxylic acid Is converted in place of 2-dimethylamino-4,6-dichlorotri-butyl ester (N found: 7.60%; N beazin- (l, 3.5) 2-diethylamino-4,6-dichlorotriazine- (1,3.5) calculated: 7.61%). The reduction of the nitro group used, one obtains a similar coloring is advantageously carried out by catalytic reduction in Dye. 55 dimethylformamide. Orange-red crystals are obtained, If you replace 2-dimethylamine-4,6'-dichloro- which melt at 150 to 152 ° and 8.25% nitrogen triazine- (l, 3,5) by 2-amino-4,6-dichlorotriazine (l, 3, 5), included (theory: 8.28%)
this also gives a dye that dyes cotton in blue tones. Patent claims: Example 12 1- Process for the preparation of Anthraquinone : vat dyes, dadur c h geken nzei ch- 6.76 parts!, ^ - diaminoanthraquinone ^ -carboxylic acid- net that 2 moles of an anthraquinone isobutyl ester and 1.84 parts of cyanuric chloride are 2-carboxylic acid alkyl, cycloalkyl or aralkyl stirred with 100 parts of nitrobenzene and in 5 minutes 65 esters, which is an amino group in the 1-position and heated to 90 °, then in a quarter of an hour in at least one other «position to 120 °. Now 5 hours at 120 to 125 ° amino group has, with 1 mole of a dicarbon touched. After cooling, it is filtered off, with acid halides or a heterocyclic mixture bond that implements the grouping at least twice C ^ "Halogen _g contains in the ring, and any replaceable in the reaction products obtained Halogen atoms replaced by alkyl or arylamine radicals. 2. The method according to claim 1, characterized ge ίο indicates that 2 moles of a 1,4-diaminoanthraquinone-2-carboxylic acid alkyl, cycloalkyl or aralkyl esters with 1 mol of an aromatic dicarboxylic acid halide or a di- or triazines containing at least two exchangeable halogen atoms. 3. The method according to claim 2, characterized in that a compound is used as the triazine the formula Cl-C. X-Cl used, in which X is a halogen atom, a hydrogen atom, denotes an alkyl, aryl, alkylamine, arylamine or phenoxy radical. Documents considered: German Patent No. 390 201; French Patent No. 1,167,798; British Patent No. 784,926; U.S. Patent No. 2,598,587. With the announcement of the registration there is a coloring table provided with explanations has been laid out.