FR2522672A1 - REACTIVE DYES AND THEIR TINCTORIAL APPLICATIONS - Google Patents

Abstract

THE INVENTION RELATES TO THE FIELD OF TINCTORIAL CHEMISTRY. IT CONCERNS NEW REACTIVE COLORANTS OF FORMULA: (CF DRAWING IN BOPI) IN WHICH IS THE REMAINDER OF AN ORGANIC COLOR, Y IS A DIRECT BOND OR A BRIDGE CHAIN RELATING TO AN AROMATIC-CARBOCYCLIC OR AROMATIC-HETEROCHYCLIC ATOM R AND R REPRESENTING H OR AN ALKYL GROUP, R IS A -CHCH-X GROUP, X IS A -SSOH, DIALKYLAMINO OR QUATERNARY AMMONIUM GROUP, AND N IS EQUAL TO 1 OR 2, CORE B MAY BE A SUBSTITUTE. THE COLORANTS OF THE INVENTION ARE EXCEPTIONALLY SUITABLE FOR DYING AND PRINTING TEXTILES, NATURAL OR REGENERATED CELLULOSE OR NATURAL OR SYNTHETIC POLYPEPTIDES. HIGH YIELDS ARE OBTAINED DYES WITH GREAT STABILITY.

Description

The present invention relates to reactive dyes of the formula:

/ SO 2 R 21

  Wherein Y is the residue of an organic dye, Y is a direct bond or a bridge link

  bound to an aromatic carbon-carbon atom

  clique or aromatic-heterocyclic chromo-

  phore, R and R 1 represent hydrogen or an alkyl group, R 2 is vinyl, S-halogenovinyl or -CH 2 CH 2 -X, where X is a leaving group, and n is 1 or 2 , core B can carry

other substituents.

  Preferred alkyl radicals R 1 and R 1 are, for example, alkyl radicals having 1 to 4 carbon atoms,

  which may possibly carry other substituents.

  Preferred linkages are, for example, the N-alkylene-, R-chain

R - (HN-N-CO

(R 3) 0-2 (R 3) 0-2

and R

(R) 0-2 (R 3) 0-2

  the phenyl radicals being preferably bonded to the para or meta position, the alkylene group having 1 to 4 carbon atoms and R 3 being a 503 H, COOH or C 1 -C 4 alkyl group;

or C 1 -C 4 alkoxy.

  Preferred leaving groups X are for example -O 503 H, OH, -S 503 H, dialkylamino and quaternary ammonium groups. Dyes carrying reactive groups

  -502 R 2 are described in large numbers in the literature.

  A summary is given by E Siegel in "The Chemistry of Synthetic Dyes", Volume VI, "Reactive Dyes", K. Venkataraman, Academic Press, New York and London 1972, pp. 1 et seq.

  are in particular azo dyes, anthraquinone

  phthalocyanine type, formazane type, in particular

water-soluble dyes.

  Preferred dyes are, in a quite general manner, those wherein N is 1, those wherein Y is a direct bond, those wherein R and R 1 are hydrogen and those in which R 2 is

  a vinyl or β-sulfatoethyl group.

  Dyes of the following formulas are preferred: ool E. X

-NOT _; COOH II

  R 4 is a hydrogen atom, an alkyl or aryl group, especially an optionally substituted phenyl group; J X o A, _ A, oz N TO R

R 5 III

  R 5 is a hydrogen atom or an alkyl, alkoxy or acylamino group;

R IV

R N-A 03 Go O E V

EC S- ú 03 HQ 2

  The metal complexes of dyes of formula: ## STR1 ## are also preferred.

R 6 S O 03

  in which R 6 is a hydrogen or halogen atom or a

-NO 2 or alkyl group.

  Copper atoms are preferred as metal atoms

  (1: 1 complexes) or chromium and cobalt (1: 2 complexes).

  Chromium or cobalt complexes may contain

  once or twice the azo compound of formula VI, ie

  to say that they may have a symmetrical structure or an asymmetrical structure presenting as ligands any other group. Further preferred are the dyes of the formula wherein R 7 is -N-A. The fused rings shown in dotted lines represent alternative naphthalenic systems. Preferred anthraquinone dyes correspond to the general formula VIII 0 2

SO 3 VIII

  wherein R 8 is a hydrogen atom or an alkyl group

C 1 -C 4 or C 1 -C 4 alkoxy.

  Preferred dyes of the phthalocyanine type have the general formula IX: I O "Pc tones

\ 5 2 -SX

  Wherein R 9 and R 11 represent hydrogen or C 1 -C 4 alkyl or together form a C 4 or C 5 alkylene group optionally interrupted by nitrogen or oxygen , Pc is the balance of a copper or nickel phthalocyanine and the total number of substituents is

less than or equal to 4.

  In formulas II to IX, A represents residues of formula:

502 -R 2

  N R 1 F X preferably radicals in which R and R 1 represent hydrogen, R 2 is a group-OSO 3 H or -CH = CH 2 and the nucleus

B is not further substituted.

  The alkyl, aryl and alkoxy radicals of the formulas

  I to IX may optionally carry other substituents.

  In general, unsubstituted radicals are preferred, as well as, in the case of alkyl or alkoxy residues, those which have

1 to 4 carbon atoms.

  Of the very numerous dyes illustrated by formulas I to IX, the following groups are particularly preferred:

T-0 1 -

  Seen AIX has TM ,, TMIZ 1 Ir I x "Z LE -os iix ix

E O O D

1 v 1 D I? D ue e TAXIV 'H = a xix

* bone F '-os -

  111 AX Ir R m 1; s eoz IIAX 0 -1 Ir -0 IAX

9 H 9 DODHN-

  IE HDOD-HN IUOUIU Uq OR 'OUTMUIADU' D IDe to Exojlr Jú HD 'H = SUM E l S os Cc 1 1, Oz> l, - "; ii Y, 1"': a ,: XO,.: Ir Izo s L AX zz 9 zzsz

</ SHI XX

O 4;

HO 4 2 O CH -N-A

R

(505 E) 1-5

Ii / Cu-PC (3 (S Coi 2 o "to Y 2 X

NH XXI

CODEQ

  A having the definitions given above.

  The dyes of these formulas are remarkably suitable for the printing and dyeing of natural and regenerated cellulose textile bodies as well as natural or synthetic polypeptides. Dyes obtained in high yields

  these dyes are characterized by high stability

  fiber-dye bonding, as well as remarkable stability to oxidizing agents such as peroxidic or chlorinated detergents. Possibility of eliminating the hydrolysis products formed during

  dyeing or printing are excellent.

  The formulas indicated correspond in each case to the free acids. During the synthesis, in general, the salts, in particular the metal salts, are obtained.

  alkaline, which is also used for dyeing.

  The new dyes of general formula I can be obtained by the processes of conventional use in the synthesis of reactive dyes. For example, the corresponding dyes of formula

L / I Y-N XXII

t R /

Y / 1-2

  which are known in large numbers in the literature, with 1 or 2 moles of a difluorotriazine of formula:

SO 02 R 2

F if NeN SR XXIII R 1

N -N R 1

  Preferred compounds are, for example, XXIII

  2 '2' -3 'or 4' - (3-sulfatoethylsulfonyl) phenylaminol

  4,6-difluoro-3,5-triazine. Compound XXIII can also be reacted first with a dye precursor, for example a diazotizable component or a coupler, and then prepare the

dye by copulation.

  The reaction with the triazinic derivative XXIII

  is conducted at a pH ranging from slightly acidic to slightly

  alkaline and low temperature (0 ° C.) The hydrofluoric acid released during the condensation is neutralized by the addition of a dilute solution of hydroxide,

  carbonate or alkali metal bicarbonate.

  The production of the dyes of the general formula I can be modified in a general manner. Thus, dyes, an intermediate progenitor or an intermediate dye carrying amino groups can be reacted, first with 2,4,6-trifluoro- 1,3,5-triazine and then condensing the product with compounds of the formula: xxi 2 v R

HN O S 2-R 2 XXIV

p.1

  Other reactions of transformation of

  In addition, these or their progenitors, such as metallation reactions, sulfonations or the introduction of acylamino groups, can generally be carried out at any degree of dye synthesis. The synthesis of dyes of formula I carrying two reactive residues A can be carried out in a manner

  completely analogous, for example in the case of

  azo compounds, the presence of a reactive residue A is possible.

  ble in the diazonium component and in the coupler.

EXAMPLE 1

  81 parts of 4-aminophenyl are suspended

  e-sulfatoethylsulfone in 400 parts of water of p H equal to 4, is cooled between -2 and OC with about 400 parts of ice and, with vigorous stirring, is added 27 parts by volume of 2,4,6-trifluoro, 3.5-triazine The pH is maintained at 3.5 by addition of 105 parts by volume of saturated sodium bicarbonate solution.

  after 3 minutes, you can no longer detect amine.

  The condensation product (in the form of the free acid) forming a milky suspension and having the formula: ## STR2 ## in this form is suitable for reaction with dyes, progenitors dyes or intermediate dyes

carriers of amino groups.

EXAMPLE 2

  19 parts of 1,3-diaminobenzene acid are

  6-sulfonic acid in 250 parts of water and this acid is dissolved with 40 parts by volume of 20% solution of sodium carbonate This solution is slowly poured into 40 parts of the condensation product described in Example 1, in the form of The temperature is increased to 10-15 ° C. The pH is maintained at 6-7 with a 20% solution of sodium carbonate. The reaction product thus obtained (in the form of free) of formula:

SO 3 E

EH 50 S -; c 2 - y

  is diazotized directly with 28 parts of hydrochloric acid

  after addition of ice and 7 parts of nitrite

sodium.

  This compound is added to this suspension

  diazonium 30 parts by weight of 1-1 2 '-methyl-4' -

  sulfophenyl-3-carboxypyrazolone- (5) and the coupling is completed by adding about 80 parts by volume of a 20% solution of sodium carbonate. When the coupling is complete, the precipitation of the dye is completed by the addition 200 parts of potassium chloride or sodium chloride, then the precipitate is isolated by filtration and dried at 50 ° C. A yellow powder is obtained which dyes or prints the cotton

  in yellow shades tugging on the green.

  The resulting dyeing prints have outstanding wet fastness.

  in this example the coupler, that is to say the 1 (2 '-methyl-

  4'-sulfophenyl) -3-carboxypyrazolone- (5), by equimolar amounts of the pyrazoles shown in the following table,

  yellow reactive dyes are also obtained.

  N of ex Acylated Diamine Copolymer 3 1,3-diaminobenzene acid 3methylpyrazolone- (5) 6-sulfonic acid

4 "1,3-dimethylpyrazo

  lone- (5) N of ex Acylated Diamine Copolymer Copolymer 1,3-diamino-carboxymethyl-3-methyl-benzene-6-sulfonic acid pyrazolone- (5) 6 "1- (4'-sulfophenyl) -3-carboxypyrazolone- ( 5)

1- (2 ', 5'-disulfophenyl) -

3-methylpyrazolone- (5)

8 "1- (2'-chloro-5'-sulpho)

phenyl) -3-méthylpyrazolone-

(5)

  9 "1- (3'-sulfophenyl) -3-methyl-

-aminopyrazole

EXAMPLE 10

  A solution of 21 parts of 1,3-diamino-2-methylbenzene-5-sulphonic acid in the form of the sodium salt in 300 parts of water is added slowly to 40 parts of the condensation product described in Example 1 under The hydrochloric acid released is then neutralized by the dropwise addition of a 20% solution of sodium carbonate. When the condensation is complete, the reaction product is directly diazotized at 5 ° C. 10 C by addition of ice, 7 parts of sodium nitrite and 28 parts of hydrochloric acid, then it is copulated by addition of 30 parts

  by weight of 1- (2'-methyl-4'-sulfophenyl) -3-carboxypyrazo

  lone- (5) and about 80 parts-of a 20% solution of sodium carbonate, by the azo dye of formula:

H O X COOH

  H 0350-H 4 Cr -025 _> Su 03 r The precipitation of the dye is completed by salting out with 150 parts of sodium chloride.

  the dye by filtration and dried at 50-100.

  A yellow powder is obtained which is remarkably suitable for printing and dyeing cotton. If, in this example, the coupler is replaced by the pyrazole derivatives indicated in Examples 3 to 9, yellow reactive dyes are also obtained.

  having very good dyeing properties.

EXAMPLE 11

  19 parts of 1,4-diaminobenzene acid are

  2-sulphonic acid in the form of the sodium salt in 250 parts of water and this acid is selectively condensed with 40 parts of the product described in Example 1, in aqueous suspension by addition of 30 parts of a 20% solution.

  of sodium carbonate, the pH is then maintained at 5.8%.

  When the condensation is complete, the suspension is directly diazotized by addition of ice, 7 parts

  of sodium nitrite and 28 parts of hydrochloric acid.

  The suspension of the diazonium compound is added with a solution of the salt

  of 29 parts of 1- (4'-sulfophenyl) -3-carboxylic acid

  pyrazolone- (5) in 150 parts of water and the coupling is completed by addition of 50 parts of 20% solution of sodium carbonate. The salting out is then carried out with portions of potassium chloride, the precipitate is isolated and dried. A yellow powder is thus obtained, which dyes the cotton in shades of a golden yellow. The dye corresponds to the formula: HO p 80 -SHC-2 HO 3 so-E, C 2 -0 7 St H Obtains shades similar when

  replace in this example the 1- (4 '-sulfophenyl) -3-carboxy-

  pyrazolone- (5) by equimolar amounts of the pyrazoles

indicated in Examples 3 to 9.

EXAMPLE 12

  A solution of 0.1 mol of the aminoazo dye prepared by conventional methods, of the formula: 503% S Os HN in 600 parts of water, is slowly added to 40 parts of the product described in Example 1, and then in the range of 6 to 8 by the addition of dilute sodium hydroxide solution or sodium carbonate solution. When condensation is complete, the dye is recovered, isolated and dried. The resulting dye in the form of a yellow powder of the formula: S Oz

1103502-2-050:

  dyes the cotton in solid yellow shades to light

and chlorine.

  If in this example the 2-amino acid is replaced

  4,6,8-trisulphonic naphthalene with 2-amino-naphthalic acid

  lene-4,8-disulphonic acid, 2-amino-naphthalene-6,8-

  disulfonic acid, 2-amino-naphthalene-3,6,8-trisulfonic acid

  whereas, aminobenzene-2,4-disulphonic acid or 2,5-aminobenzene-2,5-disulphonic acid also gives yellow reactive dyes having remarkable light and wet fastness. By a similar process, reactive dyes can be obtained. of this type when replacing in this example the aniline used as coupler

  with 3-methylaniline, 2-methoxyaniline, 3-acetyl-

  aminoaniline, 3-ureidoaniline or 2-methoxy-5-

methylaniline.

EXAMPLE 13

  0.1 mol of the condensation product obtained according to Example 2 was added from 19 parts of 1,3-diaminobenzenesulfonic acid and 40 parts of the product described in Example 1 to a solution of the diazonium obtained by conventional methods from 0.1 mole of 2-aminonaphthalene-4,6,8-trisulfonic acid and the coupling is terminated by neutralization with a dilute solution of sodium carbonate. After release, filtration and drying, the following is obtained: the dye of formula: -NB Sis C NEt-0503 EC% S

  in the form of a yellow powder, It is remarkable-

  dyeing and printing of cotton, in

shades of a golden yellow.

EXAMPLE 14

  The solution of 24 parts by weight of 2-amino-5-hydroxynaphthalene-7-sulfonic acid in the form of the sodium salt in 200 parts of water is added to 40 parts of the product described in Example 1. condensation can be completed with vigorous stirring in one hour at 1520 with simultaneous neutralization with sodium hydroxide solution

  diluted or a 20% solution of sodium carbonate.

  The suspension of the condensation product is combined with the suspension, produced by conventional methods, of a diazonium compound obtained from 2-naphthylamino-1,5-disulphonic acid and the coupling is

  completed by addition of 10 parts of lithium carbonate.

  The reactive dye of orange color, of formula:

03 S H O E

SOUND 503 H

  is salted out, isolated and dried.

  orange, which is remarkably suitable for dyeing and

  cotton pressure by conventional methods for

reactive dyes.

  If the condensation product, described in this example, is copulated from the product of

  Example 1 and 2-amino-5-hydroxynaphthalene-7-

  by the known methods with the diazonium compounds obtained from the amines indicated below, remarkable reactive dyes are also obtained.

giving the specified shades.

  Acid from which the diazonium compound is derived: Nuance 2-aminonaphthalene-1,5,7-trisulphonic acid Orange-2-anilino-2-sulfonic acid Orange 1-amino-3-acetylaminobenzene-6-sulfonic acid Orange

  1-amino-3-triazinylaminobenzene-6- acid

  sulfonic acid Orange 1-amino-4-methoxybenzene-2-sulfonic acid 1-amino-4-methoxybenzene-2,5-disulfonic acid scarlet 2-amino-naphthalene-3,6,8-triisulfonic acid scarlet 1-amino-4-acylaminobenzene-1 sulfonic acid scarlet 1-amino-4-acylaminobenzene-2,5-disulfonic acid scarlet

EXAMPLE 15

  A solution of 32 is added dropwise

  parts by weight of 1-amino-8-hydroxynaphthalene-3,6-

  disulfonic acid in the form of the sodium salt in 200 parts

  of water, with vigorous stirring, at 40 parts of

  product prepared in accordance with Example 1, and

  then read the acid released by addition of dilute sodium hydroxide or sodium carbonate After one hour

  approximately, condensation under these conditions is complete.

  The condensation product thus obtained is then combined with the diazonium compound, obtained by

  conventional processes, from 0.1 mole of aniline

  2-sulfonic acid, and the coupling is completed at pH 7 After release, isolation and drying, a dark powder of the dye of formula is obtained: Hf-EN 502-C 2 H 4 O 503 E SO QHF / 0 EEO s which dissolves in water giving a red hue and which dyes or prints the cotton in shiny red shades. If, in this example, the diazonium compound obtained from anilino-2-sulphonic acid is replaced by the equimolar amounts of the diazonium compounds obtained from the amines below, brilliant red reactive dyes are also obtained: Aniline Aniline-2,5-disulfonic acid 4-methylaniline-2-sulphonic acid 4-methoxyaniline-2-sulphonic acid 4-methoxyaniline-2,5-disulfonic acid 3-pyrimidinylamino-aniline-6-sulphonic acid 4-triazinylaminoaniline-2-sulphonic acid 2-amino-naphthalene acid -sulfonic acid 2-Aminonaphthalene-1,5-disulfonic acid 2-Aminonaphthalene-1,5,7-trisulfonic acid

EXAMPLE 16

  If 15.0.1 mol of the product described in the example is condensed under the conditions indicated in the example.

  1 and 0, 1 mole of 1-amino-8-hydroxynaphthalene-4,6-

  disulfonic acid and if the coupling of the condensation product is carried out by analogous methods with the diazonium compound derived from aniline-2-sulphonic acid, the dye of the following formula is obtained after salting, isolation and drying: -C 2 E 4-05 o 3 H

S% H HO

SOLE H

  in the form of a dark powder that dissolves in water, giving a red hue that turns yellow and is remarkably suitable for printing and dyeing

  cotton in shiny red shades.

  If, in this example, the diazonium compound derived from aniline-2-sulphonic acid is replaced by equimolar amounts of the diazonium compound of the amines indicated following Example 15, the same is obtained.

  bright red reactive dyes.

EXAMPLE 17

  A solution of the sodium salt of 32 parts by weight of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid in 200 parts of water is added as described in Example 15 to 40 parts of the product described in US Pat. Example 1 and condensed at 15-20 The solution of the condensation product is then combined with the

  diazonium obtained from 0.1 mole of 2-amino acid

  naphthalene-4,6,8-trisulfonic acid in 200 parts of water and the coupling is carried out at pH 7 by the addition of an alkaline base. When the coupling is complete, the red dye solution is treated with 35 parts by weight of Copper sulfate and a mixture of 50 parts of a 30% solution of hydrogen peroxide and 130 parts of a 20% solution of sodium acetate are added dropwise at 15 and at pH 4.6. The temperature is then maintained in the range of 10 to 150 by addition of about 200 g of ice. When the copper incorporation by oxidation is complete, the copper complex dye of formula at S 2 -C-CU 4 OSO 5 s% to oO P-_g B

HO 5 HO 5 SO: E

SO 5 H

  is released, isolated and dried A dark colored powder is obtained which dissolves in water giving a blue hue and which is suitable for printing and dyeing cotton in navy blue shades with good durability

in the light.

  The diazonium compound obtained from 2-naphthylamine-4,6,8-trisulfonic acid can be replaced in this example by the diazonium compounds of the amines shown in the following table.

  oxidation takes place in a similar manner.

  Diazonium compound Nuance Aniline 4-sulfonic acid violet Violet aniline 3,5-disulfonic acid Purple-red aniline Blue 2-aminonaphthalene-4,8-disulphonic acid Blue 2-amino-naphthalene-6,8-disulfonic acid 2-Aminonaphthalene-1,5,7-acid -trisulfonic blue

EXAMPLE 18

  A suspension of the diazo-

  nium obtained from 0.1 mole of 2-aminonaphthalene

  4,6,8-trisulfonic acid in 250 parts by volume of water to a solution obtained by the method described in Example 14 for the preparation of the condensation product from 2-amino-5-hydroxynaphthalene-7sulfonic acid and of the product of Example 1 and the coupling is completed by addition of 20 parts of sodium bicarbonate. The solution thus obtained after copulation is treated with 250 parts of a 20% solution of sodium acetate and

  500 parts of a 3% solution of hydrogen peroxide.

  The incorporation of copper by oxidation is then obtained by dropwise addition of 250 parts of a

  20% solution of copper sulphate When incorporating

  Once the copper is complete, the dye of formula: ## STR1 ## is salted out with a mixture of 400 parts of sodium chloride and 100 parts of potassium chloride. then it is isolated and dried A dark powder is obtained which dissolves in water giving a violet hue and which

  dyes the cotton in light purple-blue shades.

  If we replace in this example the compound

  of diazonium obtained from 2-aminonaphthalene

  4,6,8-trisulfonic acid by diazonium compounds of the following aromatic amines, violet reactive dyes are also obtained: Aniline 4-sulfonic acid Aniline 3-sulfonic acid Aniline 3,5-disulfonic acid 2-Aminonaphthalene-4,8-disulfonic acid 2-Aminonaphthalene-6,8-disulfonic acid 1-Aminonaphthalene-4,6-disulfonic acid 1-Aminonaphthalene-4,7-disulfonic acid 2-Aminonaphthalene-3,6,8-trisulfonic acid

EXAMPLE 19

  1.5 mol 0.1 ml of the aminoazoic compound of the following formula is dissolved in 1500 parts by volume of water:

  that can be obtained by coupling 1-aminonaphthalic acid

  lene-4,6-disulfonic acid with 2-acetylamino-5-hydroxy-acid

  naphthalene-4,8-disulfonic then incorporation of copper by oxidation and saponification of the acetylamino group, and the solution obtained is added dropwise to 40 parts of the condensation product described in Example 1, neutralizing the acid liberated with a solution of sodium carbonate so that the pH is maintained at 6.5 during the condensation period of about two hours. When the reaction is complete, the dye of formula:

H, 50HMI 502-C 2H-0505

  R 03 is isolated and dried under vacuum at about 50 dark powder is obtained which dissolves in water giving a blue tint and dyes the cotton in shades of a blue pulling red The same dye can be obtained by copulation of the 1-aminonaphthalene-4,6-disulfonic acid diazonium compound with the product

* condensation obtained from 2-amino-5-hydroxy-acid

  Naphthalene-4,8-disulfonic acid and the product of Example 1, followed by the incorporation of copper by oxidation Dyes which dye the cotton in similar shades of a reddish-blue can be obtained when In this example, the acid diazonium compound is replaced by

  1-aminonaphthalene-4,6-disulfonic acid by that of the amines

  1-Aminonaphthalene-4,7-disulfonic acid 1-Aminonaphthalene-4-sulfonic acid 2-Aminonaphthalene-6,8-disulfonic acid 2-Aminonaphthalene-4,6,8-trisulfonic acid 2-Aminonaphthalene-3,6-disulfonic acid

  1-amino-8-hydroxynaphthalene-4,6-disulfonic acid.

EXAMPLE 20

  0.1 mol of 1: 2 chromium complex of the following formula is dissolved in 1000 parts of water at a pH of:

EC O EXS O

02 N N your

02 N 4?

0 O 03 E

  Cr that can be obtained by copulation of 5-nitro-2-aminophenol

  diazotized with 1-amino-8-hydroxynaphthalene-3,6-disul-

  and conversion to the chromium complex 1: 2 and condensed with 80 parts of the difluorinated product of Example 1 The neutralization of the acid released is then carried out by dropwise addition of a dilute solution of sodium carbonate. sodium When the condensation is complete, the dye is relabelled, isolated and dried. It is in the form of a dark powder which dyes or prints the cotton in shades of a gray pulling green. In this example, the pure chromium complex is replaced by a 1: 1 mixture of the chromium complex and the corresponding cobalt complex, a mixture of dyes which dyes or prints the cotton is obtained.

  neutral black and gray shades, solid in the light.

EXAMPLE 21

  0.1 mol of the cobalt complex of formula

02 X E

AN-N

H 03 S '1 / "O

  Co in 800 parts by volume of water at pH 6 and condensed with 80 parts of the product of Example 1 with vigorous stirring The acid liberated is neutralized by addition

  dropwise solution of 20% sodium carbonate.

  When the condensation is complete, the reactive dye obtained is salted out, isolated and dried. It is in the form of a dark powder which dissolves in water with a brown tint and dyes the cotton in layers. shading

solid browns in the light.

EXAMPLE 22

  0.1 mol of the chromium complex is added to 1: 1

  dye obtained from 6-nitro-1-diazo-2- acid

  hydroxynaphthalene-4-sulphonic acid and 2-hydroxynaphthalene at 0.1 mol of the dye obtained by alkaline coupling of 4-chloro-2-amino-1-hydroxybenzene-6-sulphonic acid diazotized with 1-amino-8-hydroxynaphthalene-3,6-acid disulfonic

  in 300 parts of water at 70-80 C and at a pH of 8-9.

  A dark blue solution is rapidly formed. The resulting mixed chromium 1: 2 complex is acylated in about 2 hours at a pH of 6.5-7.5 with 45 parts of the condensation product of Example 1. is then kept constant by dropwise addition of a solution of% sodium carbonate. The reactive dye is

  salted out with 20% sodium chloride, isolated and dried.

The dye of formula:

EOA SR "1

E 03 SO 3 HE

  C- dyes the cotton in solid blue-gray shades in the light.

EXAMPLE 23

  Diazotize as described in the example

  2 0.1 mol of the 1,3-acid condensation product

  diaminobenzene-6-sulfonic acid and the product of Example 1 and the suspension is copulated at a pH of 2-3 with 0.1 mole

  of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid.

  When the copulation is complete, the solution of dark red dye is added with the suspension

  diazotization product obtained from aniline

  To carry out the second coupling, the pH of the reaction mixture is adjusted to 7-8 by the dropwise addition of a 20% solution of sodium carbonate. When the coupling is complete, the dye of formula: 0 HEN o OEH 03

6 N N N N N

  It is isolated and dried. It is in the form of a dark powder which dissolves in water in the following manner: giving a blue hue and dyeing cotton in shades

ranging from dark blue to black.

EXAMPLE 24

  The coupling, carried out in a slightly acidic pH range, of 0.1 mol of the diazonium compound obtained from aniline-2,5-diisulfonic acid with

  0.1 mole of 1-amino-8-hydroxynaphthalene-3,6-

  disulfonic, gives a dark red solution of the monoazo dye which can be copulated to a dark blue dye at a pH of 6-7 with 0.1 mole of the diazonium compound

  obtained from the 1,3-acid condensation product

  diaminobenzene-6-sulfonic acid and the product of Example 1.

  After release, isolation and drying, the dye of formula is obtained: n / a 3 Ho HNH H: 3 z

N / A X 3 H N N 'N

SOISE 03 SE NE - {/ N

  F in the form of a dark powder that dissolves in water with a blue color and dyes the cotton in

  shades ranging from dark blue to black.

EXAMPLE 25

  12.6 g of 4-aminophenyl-8-sulfatoethylsulfone are dissolved in 250 ml of water. After cooling the solution to 0.degree. C., the pH is adjusted to 4.5. 4.2 ml of cyanuric fluoride are added in the course of 15 minutes and the pH is maintained at 4.0-4.5 by addition of 2 N sodium carbonate solution. The resulting reactive component is added dropwise to the suspension. minutes, a neutralized solution

  19.0 g of 1-amino-4- (3'-amino-2'-methylphenyl)

  amino) -anthraquinone-2,5'-disulphonic in 350 ml of water.

  The temperature of the reaction solution is then maintained at 0.degree.-50.degree. C. and the pH is adjusted to

  6.0-6.5 by addition of sodium carbonate solution.

  After two hours, the temperature is gradually raised to 100 in 15 hours. When the condensation is complete, the dye of the formula ## STR5 ## is liberated in the solution with 10% sodium chloride, filtered off with suction, washed with a solution of

  % sodium chloride and dried under vacuum at 45 ° C.

  The dye gives on cotton and fibranne blue impressions of bright color, having excellent solidities.

EXAMPLE 26

  12.6 g of 4-aminophenyl-8-sulfatoethylsulfone are condensed as described in Example 25 with 4.2 ml of cyanuric fluoride at a pH of 4.1 to 4.5.

  and at a temperature of from 0 to 5, in 4- (2'-4'-difluoro-6 '-

  triazinylamino) -phenyl-S-sulfatoethylsulfone. A 20.0 g neutralized solution is added dropwise to this reactive component over 20 minutes.

  of 1-amino-4- (4'-methylamino-phenylamino) anthra

  2,2'-diisopropyl quinone in 300 ml of water so that the temperature of the mixture is adjusted to 0-5. The pH is maintained at 6.0-6.5 with a 2N sodium carbonate solution. the reaction is complete, the temperature is raised to 20. The resulting dye of formula: -Ch -he -080 is salted out with 5% sodium chloride, filtered off with suction, the residue of the filter is washed with a solution of 5% sodium chloride and then dried at 45 ° C

under vacuum.

  It gives in prolonged bath to 40, dyes

very solid blue on cotton.

EXAMPLE 27

  If, in place of 4-aminophenyl-esulfatoethylsulfone, 12.6 g of 3-amino-e-sulphatoethyl sulphate is used in Example 25, and if it is otherwise carried out as described in this example, For example, there is obtained a dye of formula: which also gives cellulosic fabrics blue prints with very good fastness properties. Other similar dyes are obtained by reacting the anthraquinone components and the

  reactive components shown in the following table.

BOARD

  Ex. -Anthraquinone component reactive component

NOT '

2,192%, 503 E

O 'SE "

btileriaint on the blue green

blue -

  pulling blue blue green pulling blue green

CEZCH 20803 X

  7-1 S NE-c-SO, c E CE, OSO, it c X 04, OSO, 1 \ 502 cul caz O Sc E

H 03 S

1 503 E

E 'S H 3

03 J

  -lu, Nl 4 H 03 S 503 a-d E E 3 NS NA a a%

EXAMPLE 34

  14.7 g of 1-amino-4- (3'-amino)

  phenylamino) -anthraquinone-2,4'-disulphonic acid in 250 ml of water at pH 5 and at 0-5 2.8 ml of cyanuric fluoride are added dropwise in the course of 5 to 10 minutes to the solution of the dye component and the pH is maintained at 4.2 4.7 by addition of carbonate solution of

  sodium 2 N After a short period of agitation, the condensation

  difluorotriazinyl dye is complete.

  9.4 g of 4-aminophenyl-e-

  sulfatoethylsulfone to a solution of the reactive component and the pH is then maintained at 5.0-5.6 It is then maintained at 6.0-6.5 and allowed to rise gradually.

  temperature to 20 in 15 hours, then complete the condensation

  The dye that has developed is then

  salted out in two hours with 8% potassium chloride.

  The precipitated dye of the formula: () is filtered and washed with a 10% solution of potassium chloride until the liquor flows through the precipitated dye of the formula: ## STR2 ## After drying under vacuum at 45, a product is obtained with which a cellulosic fabric can be printed.

  in bright blue shades endowed with excellent fastness.

EXAMPLE 35

  If we replace in example 34 the component

  anthraquinone indicated by 14.7 g of 1-amino-4- (4 '-

  aminophenylamino) -anthraquinone-2,3'-disulphonic acid and if the procedure indicated in this example is further followed, there is included a staining dye: ## STR2 ## or prints cellulosic fabrics into

  shades of a blue pulling green.

EXAMPLE 36

  13.0 g of 4-aminophenyl-e-sulfatoethyl are dissolved

  The solution is cooled to 0-5 and the pH is adjusted to 4.5. 4.4 ml of cyanuric fluoride is added dropwise in minutes and the pH is maintained at 4.0. 4.5 by addition of 2 N sodium carbonate solution to the reactive component obtained a neutralized solution, cooled to 0-5, of

  19.6 g of 1-amino-4- (6'-aminomethyl-4'-phenylamino) -

  2,2'-disulfonic anthraquinone and the pH of the mixture is maintained at 7.0 7.5 When the condensation is complete, the temperature is adjusted to 20 and the resulting dye of formula The crystals obtained from the dye are filtered off with suction, washed with a 15% solution of sodium chloride, and the resulting crystals are filtered off with suction.

dried at 45 under vacuum.

  With the dye thus formed, one can obtain on cotton and fibranne clear and bright impressions

  red-tinged blue, having excellent

TELL.

EXAMPLE 37

  If reacted in Example 36, instead of the anthraquinone component indicated in this example,

  for example, a neutralized solution of 20.4 g of 1-

  amino-4- (4'-methyl-aminomethyl-phenylamino) -anthraquinone-2,2'-disulfonic acid with the condensation product of 13.0 g of 4-aminophenyl esulfatoethylsulfone and 4.4 ml of cyanuric fluoride at 0 ° C. And at a pH of 6.5 to 7.0 and if the treatment is carried out as indicated in this example, a dye of the following formula is obtained: ## STR2 ## C, -CH% -o 8% H which gives on cotton in prolonged bath or by printing,

dyes of a bright blue.

  Other dyes are obtained when the anthraquinone components shown in the following table are reacted with reactive components as follows.

  the indications of examples 36 and 37.

Anthraquinone component

ICEH -NE

0 H 0 n H 503 a

CH 2 -NE,

0 NIB c 50, H -K Reactive component

CH 2 CH 2 OS <03 E

  Är'Nsoi SE 2 CH 2 CH 2 SW, blue shade reddish blue red blue red

blue pulling.

on the blue red N o "ex.

EXAMPLE 43

  6 g of a dye of formula: Cu-Pc- (3) (SH) are dissolved at a pH of 6-7 in 400 ml of water.

XSQ 2 -1 IHÉ

  obtained by reaction of equimolar amounts of 3,3 ', 3 ", 3 m copper phthalocyanine tetrasulfochloride and 3-aminoacetanilide, subsequent saponification of the unreacted sulfochloride groups, to a pH equal to and at a temperature of 50 C, then saponification of

  acetylamino group hot in 5% hydrochloric acid.

The solution is cooled to 0-5.

  It is added dropwise to the solution of

  dyeing a solution of 4- (2 ', 4'-difluoro-6'-triazinyl)

  aminophenyl) -e-sulfatoethylsulfone which was prepared according to the indications given in Example 25 from 6.5 g of 4-aminophenylS-sulfatoethylsulfone and

2, Q ml of cyanuric fluoride.

  The pH of the reaction mixture is maintained at 6.5-7.0, the temperature is allowed to rise gradually to 20 ° C. after 5 hours and the dye is again salted out with sodium chloride when the reaction is complete. formula: ## STR1 ## is filtered off with suction, washed with a chloride solution

  of sodium and dried under vacuum at 45.degree.

  The dye obtained gives on cotton prints

  bright turquoise blue, with very good solidity.

  If the following phthalocyanines are used in place of the phthalocyanine above, other dyes are obtained with which it is possible to print

  cotton in the shades indicated.

3 6 No of

example

  Phthalocyanine component component 1. Cu-Pc- (3) "(SO 3 11) 3 Cu-Pc- (3)" (SO 3 H) 3 SOZ-2 m-cgt-C Lz-% Cu-Pc- (3) - '(SO 311) 3

SO -IM 4

  COOII (% Ni-Pc- (3% C-lac NE 2 Ni-Po- (3) '' (n / a SO Cu-Pc- (3) -802 -M 4 SOZ -Im-CE 2 -Clt-N% ( SO II) a

\ 302 _NE_ (O NE 2

  blue turquoise blue turquoise blue turquoise blue pulling blue green pulling blue green turquoise blue turquoise blue turquoise

EXAMPLE 52

  21.2 g of a dye of formula: ## STR2 ##

SO 2 SO,

  After cooling to 0-5, 2.1 ml of cyanuric fluoride is added dropwise in the course of 5-10 minutes and the pH is maintained at 4.0-4.5. by addition

  2 N sodium carbonate solution.

  After completion of the addition, a neutralized solution of 6.7 g of 4-aminophenyl-8-sulfatoethylsulfone is added gradually to the dye solution and the pH is maintained at 5.5-6.0. After 4 hours slowly raise the temperature to 20 and when the reaction is complete, the dye is freed from sodium chloride which, in the form of the free acid, corresponds to the formula: (SO 2) 2 Cu-Pc- (3) ) -502 -H

E% S es

  The precipitated dye is filtered off with suction and the residue is washed.

  of the filter with a solution of sodium chloride and

  the product is dried at 40 ° C. under vacuum.

  The dye gives on cotton prints and

  clear dyes of turquoise blue color.

  The dye indicated in Example 52 is obtained

  by condensation of equimolar amounts of 3-tetrasulphon

  copper phthalocyanine chloride and 2,4-diamino-

  benzenesulfonic acid in an aqueous medium, by controlling the pH 2, the equimolar quantity of ammonia and 1.5 equivalents of sodium hydroxide solution are added to the reaction product, and the sulfochloride groups are saponified.

  remaining at a pH equal to 10 and 40 C.

  Other reactive dyes which give onto cellulose are obtained by printing or dyeing the indicated shades, condensing the phthalocyanines shown in the table below with cyanuric fluoride and then with aminophenyl-8-sulphatoethyl sulphones.

  used as the second reactive component.

  No. 9, No. 2, Reactive Part II phthalocyanine, (SO H) z Cu-Pc- (3) -SO 2 NE 502 L 52 N 502 CE 2 CI 5050

1 _ (O

  ## STR2 ## in which C is 503H NR, -C-50, Cg, CI 0%

502 CE 2 CE 2 O% E

  NZ -b% 'Jorso 2 cz ZoeO 503 E turquoise blue turquoise blue turquoise blue turquoise green blue green blue O H 1 3 Cu-Pc- (3)' (SCE) 3

502 -NH NOSE

-SO 3 E

(SO Cu-Pc- (3) '\ Soz SCH

(SO 3 H) 2.

  Cu-Pc- (3) -S Oa-% 502 -N- <L1-N 42% E Ni-Pc- (3)

S 02 -NE NE 2

Ir I 503 E

(S% 11) 3

S CNEC "DNgz \ Sc, x 58

EXAMPLE 59

  14.7 g of 1-amino-4- (3'-aminophenylamino) -

  The 1,4'-anthraquinone-2,4-disulphonic acid is dissolved in 250 ml of water at a pH of 5 and at 0-5. 2.8 ml of cyanuric fluoride is added dropwise over 5-10 minutes to the solution of dye component and the pH is maintained at 4.2-4.7 by addition of 2N sodium carbonate solution After a brief stirring, the condensation by coloring

difluorotriazinyl is complete.

  9.4 g of 4-aminophenyl-vinylsulfone are added to the solution of the reactive dye and the pH is then maintained at 5.0-6.0. Then, the pH is maintained at 6.0-6.5 and allows the temperature to rise gradually

  hours to 20, then the condensation is completed.

  The dyestuff is then salted for 2 hours with 10% sodium chloride. The precipitated dye of formula

HOS 1

  and washed with a 1% solution of

  sodium until the resulting solution is clear.

  After drying under vacuum at 45, a product is obtained with which cellulosic fabrics can be printed in bright blue shades which are endowed with excellent fastness. The same dye is obtained by treating the dye of Example 34 for a few hours at a pH equal to 9 and 20, the elimination of the B-sulphate being possible.

be followed by chromatography.

  We can synthesize similar dyes

  using in Example 59, in place of the 4-amino

  phenyl-phenylsulfone 1 the following sulfonic component: 3-aminophenylvinylsulfone 2-aminophenylchlorethylsulfone 3-aminophenylchlorethylsulfone 4-aminophenyl-8-chlorethylsulfone 4-aminophenylbromethylsulfone

EXAMPLE 60

  13.0 g of 4-aminophenyl are suspended

  The suspension is cooled to 0-5 and the pH is adjusted to 4.5. 4.4 ml of cyanuric fluoride is added dropwise in the course of 10 minutes and the pH is maintained at 4 ° C., 0-4.5 by addition of 2N sodium carbonate solution is added at once to

  reactive component obtained a neutralized solution, cooled

  at 0-5, 19.6 g of 1-amino-4- (6'-aminomethyl)

  4 '-methylphenylamino) -anthraquinone-2,2'-disulphonic acid and the mixture is maintained at a pH of 7.0-7.5. When the condensation is complete, the temperature is adjusted to 20 and it is salted out with sodium chloride. the dye obtained of formula:

SOCS H X>

  The obtained dye crystals are filtered off with suction, washed with a 10% solution of sodium chloride and

dried under vacuum at 45.

  With this dye, one can obtain on cotton and fibranne bright, clear impressions, of a blue pulling

  on the red, endowed with excellent solidities.

Claims (2)

1 reactive dyes, characterized in that they correspond to the formula: 1 R WH R 1 SO   wherein: D is the residue of an organic dye, Y is a direct bond or a pontal linkage   bound to an aromatic carbon-carbon atom   clique or aromatic-heterocyclic chromo-   phore, R and R 1 represent hydrogen or an alkyl group R 2 is a group -CH 2 CH 2 -X, where X represents a group -SSO 3 H, dialkylamino or quaternary ammonium, and n is 1 or 2, the core B can carry other substituents.   2 dyes characterized in that they correspond to the formula: Soz 4 X X '"' N; COH / 1E 2 IT,} I L AT   R 4 in which R 4 is a hydrogen atom, an alkyl group or   an aryl group, in particular an optionally substituted phenyl group   killed and A is a group of formula: Ns // \ 2 i 2 N R 1   F with the substituent definitions given in the claim 1.