CH624426A5 - Process for preparing reactive azo dyes - Google Patents

Description

The present invention relates to the production of new azo reactive dyes which, in the acid form of the formula ro ——- n = n-a

/ \ (I)

h2? s ° 3H

¥

sr ^ -nz, where R = optionally substituted alkyl, Ri = hydrogen or optionally substituted alkyl, W = a direct bond or a bridge member, A = the rest of a coupling component and Z = the rest of a heterocyclic reactive component of the formula -CO -Het, -SCh-Het or

-o means, where Het stands for a heterocycle bonded directly or via a bridge member and the mono- or polynuclear heterocycles Het and h0c 2 |

¥

r1-n-h correspond to 3h, where R, Ri and W have the meaning given, in particular those of the formula

30th

rq - ^ - nh2

(IV)

H2?

r1 -n-h so3h

40 wherein R and Ri have the meaning given.

The alkyl radicals can have substituents customary in dyes. The alkyl radicals preferably contain 1-6 carbon atoms. Suitable substituents R are, for example, CH3, C2H5, C3H7 and GtHs. Suitable substituents Ri are CH3, C2H5, 45 (CH2) 3COOH, (CH2> 4COOH and (CH2) 5COOH.

W preferably stands for a direct bond or else for a bridge member, for example

50

-O

-N-C-CH0-

I »2

K °

or

-N-C—

exhibit tuenten, especially those of the formula

I — K V-N = N-i at least one substituent reactive with cellulose or polyamide, where R: has the meaning given above.

Suitable radicals A are, for example, those of coupling components of the hydroxybenzene, aminobenzene, ami-nonaphthalene, hydroxynaphthalene, amino-hydroxynaphtha-lin, pyrazolone, aminopyrazole, acetoacetic acid arylamide, pyri-60 don and aminopyridine series.

The radicals A can contain customary substituents for azo dyes, for example sulfonic acid, carboxylic acid, optionally substituted sulfonamide, sulfone, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, hydroxy, 65 alkoxy -, Azo groups, halogen atoms such as fluorine, chlorine and bromine and the like.

Heterocyclic reactive groups Z are understood to mean those which have one or more reactive groups or

RO-N = N-A

(II)

h2c s03h

where R, Ri, Z and A have the meaning given.

As preliminary products of the manufacturing defined below

624426

have removable substituents on a heterocycle which, when the dyes are applied to cellulose materials in the presence of acid-binding agents and, if appropriate, under the action of heat with the hydroxyl groups of the cellulose or when applied to superpolyamide fibers, such as wool, with the NH groups of these fibers with the formation of covalent ones Bonds are able to react. A large number of such fiber-reactive groups are known from the literature.

Particularly suitable reactive groups which contain at least one removable substituent bonded to a heterocyclic radical include those which contain at least one reactive substituent bonded to a 5- or 6-membered heterocyclic ring, such as a monazine, diazine, Triazine, e.g. B. pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to such a ring system which has one or more fused aromatic rings, such as a quinoline, phthalazine, cinnoline , Quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system; the 5- or 6-membered heterocyclic rings, which have at least one reactive substituent, are therefore preferably those which contain one or more nitrogen atoms and may contain 5 or preferably 6-membered carbocyclic rings fused. The reactive substituents on the heterocycle include, for example, halogen (Cl, Br or F), ammonium, including hydrazinium, sulfonium, sulfonyl, azido (N3), rhodanido, thio, thioether, oxyether, sulfinic acid and sulfonic acid. In particular, mono- or dihalo-symmetrical triazinyl radicals, for. B. 2,4-dichlorotriazinyl-6-, 2-amino4-chlorotriazonyl-6-, 2-alkylamino4-chlorotriazinyl-6-, such as 2-methylamino4-chlorotriazinyl I-6-, 2-ethylamino or 2-propylamino4- chlorotriazinyl-6-, 2-ß-oxäthylamino4-chlorotriazinyI-6-, 2-di-ß-oxäthylamino4-chlorotriazinyl-6- and the corresponding sulfuric acid semiesters, 2-diethylamino-4-chlorotriazinyl-6-, 2- Morphoiino or 2-piperidino-4-chlorotriazinyl-6-, 2-cyclohexylamino4-chlorotriazinyl-6-, 2-arylamino and substituted arylamino4-chlorotriazinyl-6-, such as 2-phenylamino4-chlorotriazinyl-6-, 2- (o -, m- or p-Carboxy- or sulfophenyl) -amino4-chlorotriazinyl-6-, 2-alkoxy4-chlorotriazinyl-6-, such as 2-methoxy- or ethoxy4-chlorotriazinyl-6-, 2- (phenylsulfonylmethoxy) 4-chlorotriazinyl -6-, 2-aryloxy- and substituted aryloxy-4-chlorotriazinyl-6-, such as 2-phenoxy4-chlorotriazinyl-6-, 2- (p-sulfophenyl) -oxy-4-chlorotri-azinyl-6-, 2- (o-, m- or p-methyl- or methoxyphenyl) -oxy-4-ehlorotriazinyl-6-, 2-alkylmercapto- or 2-arylmercapto- or 2- (substituted aryl) merc apto4-chlorotriazinyl-6, such as 2-ß-hydroxyethyl-mercapto-4-chlorotriazinyl-6-, 2-phenylmercapto4-chlorotriazinyl-6-, 2- (4'-methylphenyl) -mercapto4-chlorotriazinyl-6- , 2- (2 ', 4'-dinitro) -phenylmercapto4-chlorotriazinyl-6-, 2-methyl4-chlorotriazinyl-6-, 2-phenyl4-chlorotriazinyl-6-, mono-, di- or trihalopyrimidinyl residues, such as 2,4-dichloropy-rimidinyl-6-, 2,4,5-trichloropyrimidinyl-6-, 2,4-dichloro-5-nitro- or -5-methyl- or -5-carboxymethyl- or -5-carboxy - or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-di- or -trichloromethyl- or -5-carboalkoxy-pyrimidinyl-6-, 2,6-dichloropyrimidine4- carbonyl-, 2,4-dichloropyrimidine-5-carbonyl-, 2-chloro-4-methylpyrimidine-5-carbonyl-, 2-methyl] 4-chloropyrimi-din-5-carbonyl-, 2-methylthio4-fluoropyrimidine-5- carbonyl-, 6-methyl-2,4-dichloropyrimidine-5-carbonyK2,4,6-trichlorpyrimi-din-5-carbonyl-, 2,4-dichloropyrimidine-5-sulfonyl-, 2-chloroquinoxaline-3-carbonyl -, 2- or 3-mono-chloroquinoxaline-6-carbonyl, 2- or 3-mono-chloroquinoxaline-6-sulfonyl-, 2,3-dichloro inoxaline-6-carbonyl-, 2,3-dichloroquinoxaline-6-sulfonyl-, 1,4-dichlorophthalazin-6-sulfonyl- or -6-carbonyl-, 2,4-dichloroquinazoline-7- or -6-sulfonyl - or-carbonyl-, 2- or 3- or 4- (4 ', 5'-dichloropyri-dazon-6'-yl-1'> phenylsulfonyl or carbonyl-, ß- (4 ', 5'-dichloropyridazone -6'-yl-l '> ethylcarbonyl-, N-methyl-N- (2,4-dichlorotria-

zinyl-6 -) -carbamyl-, N-methyl-N- (2-methvlamino4-chlorotriazonyl-6> carbamyl-, N-methyl-N- (2-dimethyJamino-4-chlorotriazonyl-6) -carbamyl -, N-Methyl- or N-ethyl-N- (2,4-dichlorortriazi-nyI-6) -aminoacetyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacetyl- , N-methyl-N- (2,3-dichloroquinoxaline-6-carbo-nyl) aminoacetyl, and the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic radicals, including, for example, 2-fluoro-4-pyrimidinyl -, 2,6-difluoro-4-pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluor-5,6-dichloro-4-pyrimidinyl-, 2,6-difluoro-5-methyl4-pyrimidinyl- , 2,5-difluoro-6-methyl-4-pyrimidinyl-, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl-, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl-, 5-bromo- 2-fluor4-pyrimidinyl, 2-fluor-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluor4-pyrimidinyl, 5-chloro-6-chloromethyl -2-fluoro4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimidinyl, 2-fluoro-5-bromo-6-methyl4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl 4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-nitro4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro 6-methyl4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromethyl-2-fluoro-4- pyrimidinyl, 2-fluoro-5-nitro4-pyrimidinyl, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or -5-methylsulfonyl4-pyrimidinyl, 2-fluoro-5-carbonamido-4- pyrimidinyl, 2-fluoro-5-carbomethoxy4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl4-pyrimidinyl, 2-fluoro-6-carbonamido4-pyrimidinyl, 2-fluoro-6-carbomethoxy4-pyrimidinyl, 2-fluoro 6-phenyl4-pyrimidinyl, 2-fluor-6-cyan-4-pyrimidinyI, 2,6-difluoro-5-methylsulfonyl4-pyrimidinyl, 2-fluoro-5-sulfonamido4-pyrimidinyl, 2-fluoro-5-chloro-6- carbomethoxy4-pyrimidinyl, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl; triazine residues containing sulfonyl groups, such as 2,4-bis (phenylsulfonyl) triazinyl-6-, 2- (3'-carboxyphenyl) sulfonyl4-chlorotriazinyl-6-, 2- (3'-sulfophenyl> sulfonyl4-chlorotriazonyl) -6-, 2,4-bis- (3'-carboxy-phenylsulfonyl-> triazinyl-6-; sulfonyl group-containing pyrimidine rings, such as 2-carboxymethylsulfonyl-pyrimidinyM-, 2-methylsulfonyl-6-methyl-pyrimidinyl4-, 2-Me- thylsulfonyI-6-ethyl-pyrimidinyl-4-, 2-phenylsulfonyl-5-chloro-6-methylpyrimidinyl4-, 2,6-bis-methylsulfonyl-pyrimidinyl4-, 2,6-bis-methylsulfonyl-5-chloro-pyrimidinyl-4 -, 2,4-bis-methylsulfonyl-pyrimidine-5-sulfonyl, 2-methylsulfonyl-pyrimidinyl4-, 2-phenyl-sulfonyl-pyrimidinyl4-, 2-trichloromethylsulfonyl-6-methyl-pyrimidinyl4-, 2-methylsulfonyl-5 -chloro-6-methyl-pyrimidinyl4-, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidinyl4-, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidinyl-4-, 2-methylsulfonyl- 5-chloro-6-chloromethyl-pyrimidinyl4-, 2-methylsulfonyl4-chloro-6-methylpyrimidine-5-sulfonyl-, 2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl4-, 2,5,6-tris-ethylsul fonyl-pyrimidinyl4-, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl4-, 2-methylsulfonyl-6-chloro-pyrimidinyl-4-, 2, 6-bis-methylsulfonyl-5-chloro-pyrimidinyl4-, 2-methylsulfonyl-6-carboxypyrimidinyl4-, 2-methylsulfonyl-5-sulfo-pyrimidinyl4-, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl4-, 2-methylsulfonyl-5-carboxypyrimidinyl4-, 2-methylsulfonyl-5-cyano-6-methoxypyrimidinyl4-, 2-methylsulfonyl-5-chloropyrimidinyl-4-, 2-sulfoethylsulfonyl-6-methyl-pyrimidinyl- 4-, 2-methyl-sulfonyl-5-bromo-pyrimidinyl4-, 2-phenylsulfonyl-5-chloro-pyrimidinyl4-, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidynyl-4-, 2- Methylsulfonyl-6-chloropyrimidine4- and -5-carbonyl-2,6-bis (methylsulfonyl) pyrimidine4- or -5-carbonyl-, 2-ethyl-sulfonyl-6-chloropyrimidine-5-carbonyl-2,4-bis - (methylsulfonyl) pyrimidine-5-sulfonyl-, 2-methylisulfonyl4-chloro-6-methylpyrimi-din-5-sulfonyl- or carbonyl-; tri-azine rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino- or 4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2- (l, l-dimethyl-hydrazinium) -4-phenylamino- or - 4- (o-, m- or p-sulfophenyl> aminotriazinyl-6-, 2- (2-isopropylidene-l, l-dimethyl) hydrazione 4-phenylamino- or 4 <o-, m- or p -sulfophenyl> amino-triazinyl-6-, 2-N-aminopyrrolidinium- or 2-N-aminopiperidi-

4th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

624426

nium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6-, furthermore 4-phenylamino- or 4- (sulfophenylamino) -triazinyl-6-residues, which in 2 Division via a nitrogen bond containing the 1,4-bis-azabicyclo- [2,2,2] octane or the 1,2-bis-aza-bicyclo- [0,3,3] octane bonded in a quaternary manner, 2- Pyridmium4-phe-nylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6- and corresponding 2-oniumtriazinyl-6 radicals, which are in 4-position by alkylamino, such as Methylamino, ethylamino or ß-hydroxyethylamino, or alkoxy, such as methoxy or aroxy, such as phenoxy or sulfophenoxy groups are substituted; 2-chlorobenzthiazole-5- or 6-carbonyl- or -5- or -6-sulfonyl-, 2-arylsulfonyl- or -alkylsulfonylbenzthiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl- , such as 2-methylsulfonyl- or 2-ethylsulfonylbenzthiazole-5- or -6-sulfonyl- or -carbonyl-, 2-phenylsulfonyl-benzothiazole-5- or -6-sulfonyl- or carbonyl- and the corresponding 2-containing sulfo groups in the condensed benzene ring -Sulfonylbenzthiazol-5- or -6-carbonyl- or -sulfonyl-derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl- or -sulfonyl-, 2-chlorobenzimidazole-5- or -6-car-bonyl- or sulfonyl -, 2-Chloro-l-methylbenzimidazole-5- or -6-carbonyl- or sulfonyl-, 2-chloro-4-methylthiazole- (l, 3) -5-car-bonyl- or 4- or -5-sulfonyl -, N-Oxide of 4-chloro or 4-nitroquinoline-5-carbonyI.

Preferred compounds in the context of the new dyes correspond to the following formulas:

R-0 - N = N 0H

h «c

I.

-N-Z

so3h

Dò "(s03H) n

Are hydrogen or a sulfonic acid group, acyl for an acyl group, e.g. B. is an alkylcarbonyl, alkylsulfonyl, arylcarbonyl or arylsulfonyl group. Preferred alkyl groups are those with 1-4 C atoms, preferred aryl 5 groups optionally substituted phenyl groups, for example phenyl groups optionally substituted by Cl, Ci-Ct-alkyl, Ci-Ct-alkoxy.

Further preferred dyes are those of the formula

10th

.5 r-0 — f \ -n-n

(V)

wherein R, Ri and Z have the meaning given and n is 1, 2 or 3;

/ —A OH NH acyl r-o — f y — N = N

h2c

R ^ -N-Z

M

h, c

I.

-N-Z

so3h ch,

I 3 c = o

I.

ch

C-N — fv \

II h v = /

wherein R, Ri and Z have the meaning given and the «radical D may also contain further substituents.

Suitable substituents in D are, for example, halogen such as Cl, Br, F, Ci-Ct-alkyl, Ci-Ct-alkoxy, sulfo.

30th

(VIII)

R1-N-Z

wherein R, Ri and Z have the meaning given, E for a Ci-Gt-45 alkyl, phenyl or naphthyl group substituted by at least one water-solubilizing group, in particular a sulfonic acid group, M for a methyl, carboxy or carbonamide group and G represents an OH or NH2 group in which R, Ri and Z have the meaning given, u and v stands for, and those of the formula

(VI)

O-Cu-O

(IX)

(S ° 3H) n

■ in which R, Ri, Z and n have the meaning given, R2 stands for a substituent and p stands for the numbers 0 to 2.

Suitable substituents R2 are in particular Ci-Ct-alkyl, Ci-Ct-alkoxy, sulfo.

In the dyes I to IX, R preferably stands for CH3, Ri preferably for H, W preferably for a direct bond, 65 R2 for Ci-Ct-alkyl, C1-C4 alkoxy, sulfo.

According to the invention, the dyes of the formula I are prepared by azo dyes of the formula

624426

R-0

N = N-A

(XI)

R ^ N-H

condensed with a reactive component X-Z, where X is a removable substituent.

Preferably in dyes of the formula

(XJ)

Hoe SO, H

I 3

R1 -N-H

wherein R, Ri, W and A have the meaning given, the groups -N-Ri-H by condensation with a reactive component of the general formula

X-Z

(XII)

where Z has the meaning given and X represents a removable substituent, is converted into a group -N-Ri-Z.

Suitable reactive components of the formula (XII) are, for example, those on which the aforementioned reactive groups Z are based, that is to say in general the halides, in particular the chlorides, of the acyl components Z mentioned. Extracts from the large number of available compounds are mentioned here : Trihalogen-symmetrical-triazines, such as cyanuric chloride and cyanuric bromide, dihalogen-monoamino and mono-substituted-amino-symmetrical triazines, such as 2,6-dichloro-4-amino-triazine, 2,6-dichloro-4 -methylaminotriazine, 2,6-dichloro-4-ethylaminotriazine, 2,6-di-chloro-4-oxyethylaminotriazine, 2,6-dichloro-4-phenylaminotriazine, 2,6-dichloro4- {o-, m- or p- sulfophenyl) aminotriazine, 2,6-di-chloro-4- (2 ') 3' -, - 2 ', 4' -, - 3 ', 4'-or-3', 5'-disulfophenyl) amino -triazine, dihalogenalkoxy- and aryloxy-sym.-triazines, such as 2,6-di-chloro-4-methoxytriazine, 2,6-dichloro-4-ethoxytriazine, 2,6-dichloro-4-phenoxy-triazine, 2, 6-dichloro-4- (o-, m- or p-sulfophenyl-oxy) -triazine, dihalo-alkyl mercapto - and -arylmercapto-sym.-triazine, such as 2,6-dichloro-4-ethylmercapto-triazine, 2,6-dichloro-4-phe-nylmercaptotriazine, 2,6-dichloro4- (p-methylphenyl) mercapto -triazine; Tetrahalopyrimidines, such as tetrachloro-, tetrabromo- or tetrafluoropyrimidine, 2,4,6-trihalopyrimidines, such as 2,4,6-trichloro-, tribromo- or trifluoropyrimidine, dihalopyrimidines, such as 2,4-dichloro- Dibromo or difluoropyrimidine; 2,4,6-trichloro-5-nitro- or -5-methyl- or -5-carbomethoxy- or -5-carboethoxy- or -5-carboxymethyl- or -5-mono-, -di- or trichloromethyl- or -5-carboxy- or -5-sulfo- or -5-cyano- or -5-vinyl-pyrimidine, 2,4-difluoro-6-methylpyrimidine, 2,6-difluoro4-methyl-5-chloropyrimidine, 2,4 -Difluoropyrimidine-5-ethylsulfone, 2,6-difluor4-chloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 2,6-difluor4-methyl-5-bromopyrimidine, 2,4-difluoro-5 , 6-dichloro- or -dibromopyrimidine, 4,6-difluoro-2,5-dichloro- or -dibromopyrimidine, 2,6-difluoro4-bromopyrimidine, 2,4,6-trifluoro-5-bromopyrimidine, 2,4,6 Trifluoro-5-chloromethylpyrimidine, 2,4,6-tri-fluoro-5-nitropyrimidine, 2,4,6-trifluoro-5-cyanopyrimidine, 2,4,6-tri-fluoropyrimidine-5-carboxylic acid alkyl ester or -5- carboxylic acid

amides, 2,6-difluoro-5-methyl4-chloropyrimidii., 2,6-difluoro-5-chloropyrimidine, 2,4,6-trifluoro-5-methylpyrimidine, 2,4,5-trifluoro-6- methyl-pyrimidine, 2,4-difluoro-5-nitro-6-chloropyrimidine, 2,4-difluoro-5-cyanopyrimidine, 2,4-difluoro-5-methylpyrimidine, 6-trifluoromethyl-5 5-chloro-2 , 4-difluoropyrimidine, 6-phenyl-2,4-difluoropyrimidine, 6-trifluoromethyl-2,4-difluoropyrimidine, 5-trifluoromethyl-2,4,6-trifluoropyrimidine, 2,4-difluoro-5-nitro -pyrimidine, 2,4-difluoro-5-trifluoromethyl-pyrimidine, 2,4-difluoro-5-methylsulfonyl-pyrimidine, 2,4-difluoro-5-phenyl-pyrimidine, 2,4-difluoro-5-carbonamido -pyri-io midin, 2,4-difluoro-5-carbomethoxy-pyrimidine, 2,4-difluoro-6-tri-fluoromethyl-pyrimidine, 2,4-difluoro-5-bromo-6-trifluoromethyl-pyrimidine, 2,4-difluoro-6-carbonamido-pyrimidine, 2,4-difluoro-6-car-bomethoxy-pyrimidine, 2,4-difluoro-6-phenyl-pyrimidine,

2,4-difluoro-6-cyanopyrimidine, 2,4,6-trifluoro-5-methylsulfonyl-15 pyrimidine, 2,4-difluoro-5-sulfonamido-pyrimidine, 2,4-difluoro-5-

chloro-6-carbomethoxypyrimidine, 5-trifluoromethyl-2,4-difluoropyrimidine, 2,4-dichloropyrimidine-5-carboxylic acid chloride, 2,4,6-trichloropyrimidine-5-carboxylic acid chloride, 2-methyl4-chloropyrimidine 5-carboxylic acid chloride, 2-chloro-4-methylpyrimidine-5-car-20 acid chloride, 2,6-dichloropyrimidine-4-carboxylic acid chloride; Pyrimidine reactive components with removable sulfonyl groups, such as 2-carboxymethylsulfonyl4-chloropyrimidine, 2-methylsulfonyl-4-chloro-6-methylpyrimidine, 2,4-bis-methylsulfonyl-6-methylpyrimidine, 2,4-bisphenylsulfonyl 5-chloro-6-methylpyrimi-25 din, 2,4,6-trismethylsulfonylpyrimidine, 2,6-bis-methylsulfonyl-

4,5-dichloropyrimidine, 2,4-bis-methylsulfonylpyrimidine-5-sulfonic acid chloride, 2-methyisulfonyl4-chloropyrimidine, 2-phenylsulfonyl4-chloropyrimidine, 2,4-bis-trichloromethylsulfonyl-6-methylpyrimidine, 2,4- Bis-methylsulfonyl-5-chloro-6-methylpyrimidine,

30 2,4-bis-methylsulfonyl-5-bromo-6-methyl-pyrimidine, 2-methylsulfonyl4,5-dichloro-6-methylpyrimidine, 2-methylsulfonyl4,5-di-chloro-6-chloromethylpyrimidine, 2-methylsulfonyl -4-chloro-6-methylpyrimidine-5-sulfonic acid chloride, 2-methylsulfonyl4-chloro-5-nitro-6-methylpyrimidine, 2,4,5,6-tetramethylsulfonylpyrimidine, 35 2-methylsulfonyl4-chloro-5, 6-dimethylpyrimidine, 2-ethylsulfonyl4,5-dichloro-6-methylpyrimidine, 2-methylsulfonyl4,6-dichloropyrimidine, 2,4,6-tris-methylsulfonyl-5-chloropyrimidine, 2-methylsulfonyl4-chloro 6-carboxypyrimidine, 2-methylsulfonyl4-chloropyrimidine-5-sulfonic acid, 2-methylsulfonyl4-chloro-6-carbome-40 thoxyprimidine, 2-methylsulfonyl4-chloropyrimidine-5-carboxylic acid, 2-methylsulfonyl4-chloro-5-cyan -6-methoxypyrimidine, 2-methylsulfonyl4,5-dichloropyrimidine, 4,6-bis-methylsulfonyl-pyrimidine, 4-methylsulfonyl-6-chloropyrimidine, 2-sulfoethylsulfonyl4-chloro-6-methylpyrimidine, 2-methylsulfonyl4-chloro-5 -bromo-45 pyrimidine, 2-methylsulfonyl4-chloro-5-bromo-6-methylpyrimidine, 2,4-bis-methylsulfonyl-5- chlorpyrimidine, 2-phenylsulfonyl4,5-dichloropyrimidine, 2-phenylsulfonyl4,5-dichloro-6-methylpyrimidine, 2-carboxymethylsulfonyI4,5-dichloro-6-methylpyrimidine, 2- (2'- or 3'- or 4 '-Carboxyphenylsulfonyl) 4,5-dichloro-6-50 methylpyrimidine, 2,4-bis- (2'- or 3'- or 4'-carboxyphenylsulfonyl> 5-chloro-6-methylpyrimidine, 2-methylsulfonyl-6 -chloropyri-midin4- or -5-carboxylic acid chloride, 2-ethylsulfonyl-6-chloropy-rimidin4- or -5-carboxylic acid chloride, 2,6-bis (methylsulfonyl) pyrimidine4-carboxylic acid chloride, 2-methylsulfonyl-6-methyl4-55 chloro- or 4-bromopyrimidine-5-carboxylic acid chloride or bromide, 2,6-bis (methylsulfonyl) -4-chloropyrimidine-5-carboxylic acid chloride; further reactive components of the heterocyclic series with reactive sulfonyl substituents are, for example

3,6-bis-phenylsulfonyl-pyridazine, 3-methylsulfonyl-6-chloropyri-60 dazine, 3,6-bis-trichloromethylsulfonyl-pyridazine, 3,6-bis-methyl-

sulfonyl4-methylpyridazine, 2,5,6-tris-methylsulfonylpyrazine, 2,4-bis-methylsulfonyl-l, 3,5-triazine, 2,4-bis-methylsulfonyl-6- (3 '-su! fophenylamino) -l , 3,5-triazine, 2,4-bis-methylsulfonyl-6-N-methylanilino-l, 3,5-triazine, 2,4-bis-methylsulfonyl-6-phenoxy-l, 3,5-65 triazine, 2,4-bis-methylsulfonyl-6-trichloroethoxy-l, 3,5-triazine, 2,4,6-tris-phenylsulfonyl-l, 3,5-triazine, 2,4-bis-methylsulfonylchi-nazoline, 2,4-bis-trichloromethylsulfonylquinoline, 2,4-bis-carboxymethylsulfonylquinoline, 2,6-bis (methylsulfonyl) pyridine4-car-

624426

bonic acid chloride and l- (4'-chlorocarbonylphenyl- or 2'-chlorocarbonylethyl) 4,5-bis -methylsulfonyI-pyridazone- (6); Further heterocyclic reactive components with movable halogen include 2- or 3-monochloroquinoxaline -6-carboxylic acid chloride or -6-sulfonic acid chloride, 2- or 3-mono-bromoquinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 2,3-dichloroquinoxaline -6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-dibromoquinoxaline-6-carboxylic acid bromide or -6-sulfonic acid bromide, 1,4-dichlorophthalazine-6-carboxylic acid chloride or -6-sulfonic acid chloride and the corresponding bromine compounds, 2, 4-dichloroquinazoline-6- or -7-carboxylic acid chloride or -7-sulfonic acid chloride and the corresponding bromine compounds, 2- or 3- or 4- (4 ', 5'-dichloropyridazon-6'-yl-1'> phenylsulfonic acid chloride or -carboxylic acid chloride and the corresponding bromine compounds, ß- (4 ', 5'-di-chloropyridazon-6' -yl-1 ') ethylcarboxylic acid chloride, 2-chloroquinoxaline-3-carboxylic acid chloride and the corresponding bromine compound, N-methyl-N- ( 2,4-dichlorotriazinyl-6> carbamic acid chloride, N-methyl-N- (2-chloro-4-methylamino- triazinyl-6> carbamic acid chloride, N-methyl-N- (2-chloro-4-dimethylamino-triazinyl-6) -carbamic acid chloride, N-methyl or N-ethyl-N- (2,4-dichlorotriazinyl-6) -aminoacetyl chloride , N-methyl, N-ethyl or N-hydroxyethyl-N- (2,3-dichloroquinoxaline -6-sulfonyl- or -6-carbonyl) -aminoacetyl chloride and the corresponding bromine derivatives, furthermore 2-chlorobenzothiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride and the corresponding bromine compounds, 2-arylsulfonyl- or 2-alkylsulfonyl-benzothiazole-5- or -6-carboxylic acid chloride or -5- or -6-sulfonic acid chloride, such as 2- Methylsulfonyl- or 2-ethylsulfonyl- or 2-phenylsulfonyl-benzothiazole-5- or -6-sulfonic acid chloride or -5- or -6-carboxylic acid chloride as well as the corresponding 2-sulfonylbenzothiazole derivatives containing sulfonic acid groups in the fused benzene ring, 3,5- Bismethylsulfonyl-isothiazole-4-carboxylic acid chloride, 2-chloro-benzoxazole-5- or -6-carboxylic acid chloride or -sulfonic acid chloride and the corresponding bromine derivatives, 2-chlorobenzimidazole-5- or -6-carboxylic acid chloride or sulfonic acid chloride and the corresponding bromine derivatives, 2-chloro-l-methylbenzimidazole-5- or -6-carboxylic acid chloride or sulfonic acid chloride as well as the corresponding bromine derivatives, 2- Chlor4-methyl-thiazole- (1,3> 5-carboxylic acid chloride or 4- or -5-sulfonic acid chloride, 2-chlorothiazole4- or -5-sulfonic acid chloride and the corresponding bromine derivatives.

These condensation reactions are generally carried out in an aqueous or organic medium and in an alkaline, neutral or weakly acidic range.

The dyes of the general formula (XI) used as starting material for this process can be prepared by diazotized amines of the formula (III) and in particular (IV) in mineral acid, acetic acid, neutral, bicarbonate-alkaline, soda-alkaline or sodium-alkaline medium with coupling components

AH

(XIII)

couples.

Suitable coupling components (XIII) are e.g. B. from the series of aminobenzenes, aminonaphthalenes, hydroxynaphthalenes, aminohydroxy-naphthalenes, acylamino-hydroxynaphthalenes, arylaminohydroxy-naphthalenes, pyrazolones, aminopyrazoles, acetoacetic acid amides, pyridones and aminopyridines. The following are some of the large numbers of azo components to be mentioned here: 2-acetoacetylamino-l, 4-dimethoxy-5-sulfo-benzene, 2-acetoacetylamino-l-methoxy4-methyl-5-sulfo-benzene, 2- Acetoacetylamino-l-β-hydroxyethoxy-5-sulfo-benzene, 2-acetoacetylamino-I, 4-disulfo-5-methoxy-benzene, 2-acetoacetylamino-l-methoxy4,6-disulfo-benzene,

2-acetoacetylamino- [l-methoxy4-sulfo-5- (5 ', 7' -disulfoM ', 2', 3 '-naphthotriazolyl-2'] benzene,

N-ethyl-2-hydroxy4-methyl-5-carbonamido-pyridone-6, N-ß-sulfoethyl-2-hydroxy4-methyl-5-carbonamido-pyridone-6, 5 N-carboxyimethyl-2-hydroxy-4-methyl -5-carbonamido-pyri-don-6,

N-carboxylmethyl-2-hydroxy4-methyl-5-nitro-pyridone-6, N-ß-sulfoethyl-2-hydroxy4-methyl-5-cyanopyridone-6, N-ethyl-2-hydroxy4-sulfomethyl-5- cyano-pyridone-6, io N-ethyl-2-hydroxy-4-methyl-5-sulfo-pyridone-6, N-ethyl-2-hydroxy4-methyl-5-sulfomethyl-pyridone-6,

2.4-diamino-5-cyan-6- (3'-sulfophenyl> amino-pyridine, l-amino-2-sulfo-5-acetylamino-benzene, 2-amino-5,6- or

7-suIfo-naphthalene, 2-amino-5,7-disulfonaphthalene, 2-amino-3,6-i5 disulfonaphthalene, l-amino-6- or 7-sulfonaphthalene,

1-amino-3-acetylamino-benzene, 1-amino-3-ureido-benzene, 1-amino-3-methyl-benzene, 1-amino-3-methyl-6-methoxy-benzene, 1-amino-2, 5-dimethoxy-benzene, 1-hydroxy-5-sulfonaphthalene, 1-hydroxy-3,6-disulfonaphthalene, 1-hydroxy-3,7-disulfonaphthalene, 20-thalin, l-hydroxy-3,8 -disulfonaphthalene, l-hydroxy4,6-disulfonaphthalene, l-hydroxy4,7-disulfonaphthalene, l-hydroxy4,8-disulfonaphthalene, 1 -hydroxy-3,5-disulfonaphthalene, l-hydroxy -8-benzoyl-amino-3,6-disulfonaphthalene, 1-hydroxy-

8-benzoylamino-3,5-disulfonaphthalene, l-hydroxy-8-ureido-3,6-25 disulfonaphthalene, l-hydroxy-8-ureido-3,5-disulfonaphthalene,

1-hydroxy-8-acetyIamino-3,5-disulfonaphthalene, 1 -hydroxy-8-acetylamino-3,6-disulfonaphthalene, l-hydroxy-7-amino-3-sulfonaphthalene, 1-hydroxy- 7-phenylamino-3-sulfo-naphthalene, l-hydroxy-8-amino-3,6-disulfonaphthalene, l-hydroxy-8-amino-3o 3,5-disulfonaphthalene, I-hydroxy-7-amino -3,6-disulfo-naphtha-lin, l-hydroxy-6-amino-3-sulfo-naphthalene, l-hydroxy-6-amino-

3,5-disulfo-naphthalene, 4-sulfo-benzokl azo 7> -8-amino-l-hydroxy-3,6-disulfo-naphthalene, 3-sulfo-benzokl azo 7> -8-amino-l-hydroxy-3, 5-disulfonaphthalene, 4-nitro-2-sulfobenzokl azo

35 7> -8-amino-l-hydroxy-3,6-disulfo-naphthalene,

1- (2 ', 3'- or 4'-sulfophenyl) -3-methyl-pyrazolone-5, 1- (2'-chloro4' or 5'-sulfophenyl) -3-methyl-pyrazolone-5 , l- (2'-Methyl4'-sulfo-phenyl) -3-methyl-pyrazolon-5, 1 - (2'-Methyl4'-sulfo-phenyl) -3-carboxy-pyrazolon-5, 40 I -ß- Carboxy-ethyl-3-carboxy-pyrazoIon-5.

1 - (4 ', 8' -disulfonaphthyl- (2)) - 3-methyl-pyrazolone-5,

1 - (5 ', 7' -disulfonaphthyl- (2)) - 3-methyl-pyrazolon-5, l- {2'-chloro-5'-sulfo-phenyl) -3-methyl-5-amino- pyrazole, H2'-chloro4'-sulfophenyl) -3-methyl-5-aminopyrazole, 45 H3 'or 4'-sulfophenyl) -3-methyl-5-aminopyrazole,

1-carboxy-methyl-3-methyl-pyr azolone-5,1-β-carboxyethyl-3-methyl-pyrazolone-5,1-β-carboxyethyl-3-methyl-5-amino-pyrazole, H4'- Sulfo-phenyl) -3-carboxy-pyrazolon-5.

If the monoazo dyes obtainable with the abovementioned coupling components 5o also contain diazotizable amino groups, they can also be diazotized by a customary process and reacted again with a suitable coupling component, resulting in disazo dyes.

55 For example, a compound from the series of coupling components (XIII) already mentioned can serve as the coupling component for the renewed reaction with the diazotized monoazo dye.

A further possibility of building up disazo dyes of the type fc0 mentioned is to prepare monoazo dyes which still contain sites capable of coupling and then to combine them with suitable diazo components in a second coupling step, the l-amino-2-2 to be used according to the invention can use sulfo-3-aminomethyl4-methoxy-benzene for the first or second coupling step. The coupling components used to build up such monoazo dyes are, in particular, those from the series of dihydroxy-benzenes, dihydroxynaphthalenes and ami-

624426

nohydroxynaphthalenes used. In addition to the components already mentioned, 1,3-dihydroxybenzene and 1,3-dihydroxynaphthalene-5,7-disulfonic acid may be mentioned as examples. The following can be used as the diazo component for the construction of such diazo dyes: l-amino-4-sulfo-benzene, l-amino-3-sulfo-benzene, l-amino-2-chloro-5-sulfo-benzene, 1-amino -2-sulfo-4-nitro-benzene, 1-amino-2,5-disulfobenzene, 1-amino-4-nitro-benzene, 1-amino-4-methyl-sulfonyl-benzene, 2-amino-4,8 -disulfonaphthalene, 2-amino-6,8-disulfonaphthalene.

According to Tscher-niak-Einhorn, the compounds of formula (IV) can be obtained by reacting l-amino-2-sulfo-4-alkoxy-benzenes such as l-amino-2-sulfo-4-methoxy-benzene with N-methyl Lolamides, N-methylolimides, alkyl ethers of N-methylolamides or N-methylolimides, N-halomethylamides, N-halogenomethylimides, N, N-methylene bisamides, N, N-alkylidene bisamides or mixtures of formaldehyde or formaldehyde - Produce derivatives and amides or nitriles in an acidic medium, preferably concentrated sulfuric acid and subsequent saponification of the resulting l-amino-2-sulfo-3-acylamino-methyl-4-methoxy-benzene. The saponification is expediently carried out at temperatures above 100 ° C. in an alkaline medium. Suitable reagents of the type mentioned above are, for example, N-methylolchloroacetamide, N-methylolbenzamide, N-methylolacetamide, N-methylolphthalimide, N-methyl-N-methylolacetamide, N-methylol-4-chlorobenzamide, N-methoxymethylbenzamide, N- Chloromethylbenzamide, N-chloromethyl phthalimide, N, N'-methylene-bischloroacetamide.

The reaction with the electrophilic reagents can be carried out in a known manner (see, for example, Organic Reaction, vol. 14, 1965, published by John Wiley & Sons, New York, London, Sidney, p. 124).

For example, in the reaction of l-amino-2-sulfo4-methoxy-benzene with N-methylolbenzamide in sulfuric acid at about 0-50 ° C and subsequent saponification in a yield of almost 90%, a uniform product is obtained, which according to NMR spectroscopy Examinations (in the form of free acid) correspond to the following formula:

nh,

h2n

The new dyes are suitable for dyeing and printing materials containing hydroxyl or amide groups, such as textile fibers, threads and fabrics made of wool, silk, synthetic polyamide and polyurethane fibers, and for washing and dyeing and printing native or regenerated cellulose, whereby the treatment of cellulose materials is carried out expediently in the presence of acid-binding agents and, if appropriate, by exposure to heat by the methods customary for reactive dyes.

The temperatures are degrees Celsius.

The formulas given in the description represent the dyes in the form of the free acids. In practice, their alkali metal salts, for example the Na, K or Li salts or their ammonium salts, are essentially used.

Example 1 a) Condensation

203 g of salt-free anisidic acid are introduced into 400 ml of monohydrate (100% pure sulfuric acid) at 10-15 °. Vz is allowed to stir for an hour and then 152 g of N-methylol

benzamide at 10-15 ° too. After standing for two days, 2050 g of ice / water are poured out. The mixture is then cooled to 5 ° and suction filtered.

The strong sulfuric acid paste is stirred in 500 ml of water and concentrated with 180 ml. Sodium hydroxide solution adjusted to pH 1. You suck off again.

The paste is struck again in 500 ml of water and concentrated with 58 ml. Sodium hydroxide solution adjusted to pH 7. The solution clarified via Celite measures 1.41 and contains 63 g of Ni.

b) saponification

The solution obtained above is concentrated with 180 ml. Sodium hydroxide solution added and heated in an autoclave at 140 ° for 4 hours. The result is a clear solution. Volume: 1570 ml = 62.0 Ni.

It is now concentrated with 360 ml. Hydrochloric acid to pH 1, whereby the benzoic acid is precipitated. It is suctioned off and the residue is washed with water.

Filtrate: 1970 ml = 62.0 g Ni.

Yield: 90%.

The solution can be used directly for diazotization.

If the solution is brought to pH 7 at 0-5 °, l-amino-2-sulfo-3-aminomethyl4-methoxy-benzene precipitates as an inner salt in the form of almost colorless crystals. The structure is proven by the 'H NMR spectrum (in DìO / NaOD): a 3.73 (s. OCHs), 4.06 (s, N-CH2), 6.78 (d, J = 9 Hz , 1 H) and 6.97 ppm (d, J = 9 Hz, 1 H).

The o-position of the nuclear protons is thus ensured by the size of the coupling constant (J = 9 Hz).

Example 2

a) condensation

102 g (0.503 mol) of salt-free anidisic acid are introduced into 250 ml of monohydrate (100% pure sulfuric acid) at temperatures up to 20 °, then 60 g of N-methylolpyrrolidone are added in small portions, the temperature being kept at 20 ° by cooling . Allow to stand at room temperature for two days and then apply to a mixture of ice and water. After standing for one day, the precipitate is suctioned off.

b) saponification

The sulfuric acid paste obtained is stirred in 500 ml of water and concentrated. Sodium hydroxide solution neutralized. Then again 90 ml of conc. Sodium hydroxide solution and heated in an autoclave at 140 ° for 8 hours. The solution can be used directly to prepare azo dyes. It contains the compound of the following structure (in the form of the free acid):

»—Nh,

h2c so ^ h h-n- (ch2) 3c00h

Example 3

33.6 g of l-amino-2-sulfo-3-aminomethyl-4-methoxy-benzene are stirred in 400 ml of ice water and concentrated with 40 ml. Hydrochloric acid added. 34 ml of 30% sodium nitrite solution are then added dropwise. After the excess nitrite has been removed with amidosulfonic acid, the resulting clear solution is added over a period of several hours to the solution of the coupling component, which was prepared as follows:

44.1 g of l-hydroxy-3,6-disulfonaphthalene are combined

8th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

mixed with 40 g of sodium hydrogen carbonate in 400 ml of water. The clutch goes slowly. The dye has partly failed. For the acylation, the temperature is lowered to 12-15 ° by throwing in ice. 24.5 g of 2,4,6-trifluoro-5-chloropyrimidine are added dropwise, maintaining a pH of 8-8.5 by simultaneously adding 2N NaOH. The dye goes into solution during acylation. The acylation is complete after the consumption of 140 ml of 2N NaOH. The dye is salted out with 20 vol .-% sodium chloride. After suction, drying and grinding, a powder which is readily soluble in water to with a clear red color is obtained. The dye obtained corresponds to the formula

Likewise valuable dyes with the shades listed in the last column are obtained if the procedure is analogous to that of Example 3, but instead of 2,4-trifluoro-5-chloropyrimidine an equivalent

624426

F

Amount of a reactive component mentioned in column 3 and, instead of l-hydroxy-3,6-disulfonaphthalene, an equivalent amount of one of the coupling components listed in column 2 is used.

E.g.

Coupling component

Reactive component

hue

4th

l-hydroxy-8-benzoyl-amino-

Cyanuric chloride

Bluish red

3,5-disuIfo-naphthalene

5

dito

2,4-dichloro-6-aminotriazine same

6

dito

2,4-dichloro-6- (4'-sulfophenylamino)

dito

-triazine

7

dito

4,5-dichloro-2-methylsulfonyl-6-

dito

l-hydroxy-8-benzoyl-amino-3,6-

methyl pyrimidine

8th

2,4,6-trifluoro-5-chloropyrimidine same

disulfonaphthalene

9

dito

Cyanuric chloride same as above

10th

1-hydroxy-8-acetylamino-3,5-

2,4,6-trifluoro-5-chloropyrimidine same

disulfonaphthalene

11

1-hydroxy-8-acetyl-amino-3,6-

ditto ditto

disulfonaphthalene

12th

l-Hydroxy-3,6-disulfonaphthalene ditto

Yellowish red

13

l-Hydroxy-4,6-disulfonaphthalene same as above

14

l-Hydroxy-4,7-disulfonaphthalene same as above

15

l-Hydroxy-3,5-disulfonaphthalene same as above

16

l-hydroxy-4,6-disulfonaphthalene

2,3-dichloroquinoxaline-6-carbon

dito

acid chloride

17th

dito

Cyanuric chloride same as above

18th

dito

Tetrachloropyrimidine ditto

19th

2-hydroxy-3,6-disulfonaphthalene

2,4,6-trifluoro-5-chloropyrimidine

red

20th

2-hydroxy-6-sulfonaphthalene same as above

Scarlet fever

21st

2-Hydroxy-7-sulfonaphthalene same as above

Example 22

33.6 g of l-amino-2-sulfo-3-aminomethyl-4-methoxy-benzene are diazotized directly as described in Example 3. The 55 clear solution obtained is added to a solution of 42 g of 1- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone-5 and 40 g of sodium hydrogen carbonate in 500 ml of water. After coupling is complete, the mixture is warmed to 40 °, 40 g of 2,3-dichloroquinoxa-lin-6-carboxylic acid chloride are sprinkled in and a pH of 7-8 is maintained by adding 10% sodium carbonate solution dropwise. The dye goes into solution during acylation. A paper chromatogram is used to convince yourself of the end of the acylation. After isolating, drying and grinding, a slightly water-soluble yellow powder is obtained. The color of the free acid corresponds to the following composition:

CH, 0- ^> N = N.

CH,

NH I

c = o ci Cl so3H HO

• CH,

/ 3rd

Cl

H03s

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According to one of the dyeing instructions described in Example 3, strong yellow dyeings with very good wet and light fastness properties are obtained on cotton.

If the procedure of this example is followed, but instead of 2,3-dichloroquinoxaline-6-carboxylic acid chloro

Example coupling component

10th

rid the reactive components mentioned in column 3 and instead of l- (2'-chloro-5'-sulfo-phenyl> 3-methyl-pyrazolone-5 the coupling components listed in column 2, you also get valuable dyes, whose color shades on cotton 5 are given in the last column.

hue

Reactive component

23

1 - {2 '-Sulfophenyl) -3-methyl

2,4,6-trifluoro-5-chloropyrimidine

yellow

-pyrazolone-5

24th

dito

Cyanuric chloride

yellow

25th

dito

Tetrachloropyrimidine

yellow

26

dito

2,3-dichloroquinoxaline-6-carbon

yellow

acid chloride

27th

1 - (2 ', 5' -disulfophenyl) -3-

dito

yellow

methyl-pyrazolone-5

28

dito

2,4,6-trifluoro-5-chloropyrimidine

yellow

29

dito

Cyanuric chloride

yellow

30th

H4 ', 8' -DisuIfo-naphthyl- (2) -

dito

yellow

3-methyl-pyrazolone-5

31

dito

T etrachloropyrimidine

yellow

32

dito

1,4-dichlorophthalazine-6-carbon

yellow

acid chloride

33

dito

Cyanuric chloride

yellow

34

1 - (5 ', 7' -disuIfo-naphthyl- (2) -

dito

yellow

3-methyl-pyrazolone-5

35

dito

3- (4 ', 5'-dichloropyridazon-6'-yl-l') -

yellow

phenylsulfonic acid chloride

36

dito

2-methylsulfonyl-benzothiazole-5-car

yellow

bonic acid chloride

37

1 - (4 ', 8' -DisuIfo-naphthyH2)>

2,4,6-trifluoro-5-chloropyrimidine

yellow

3-methyl-5-aminopyrazole

38

dito

Cyanuric chloride

yellow

39

l- (2'-methyl-4'-sulfo-phenyl) -3-

Cyanuric chloride

yellow

methyl-5-aminopyrazole

40

dito

2,4,6-trifluoro-5-chloro-pyri-

yellow

midin

41

dito

2-methylsulfonyl-4,5-dichloro-

yellow

6-methyl-pyrimidine

42

1- (2'-chloro-4'-sulfo-phenyl) -

dito

yellow

3-methyl-pyrazolone-5

43

dito

Cyanuric chloride

yellow

44

dito

2,4,6-trifluoro-5-chloropyrimidine

yellow

45

dito

2,3-dichloroquinoxaline-6-carbon

yellow

acid chloride

46

dito

2,3-dichloroquinoxaline-6-sulfone

yellow

acid chloride

47

H2 ', 5'-dichloro-4'-sulfo

2,4,6-trifluoro-5-chloropyrimidine

yellow

phenyl> 3-methyl-pyrazolon-5

48

1 - (2 '-M ethyl-4' -sulfo-6 '-chlor-

dito

yellow

phenyl) -3-methyl-pyrazolon-5

49

1 - (2 '-methyl-4' -sulfo-phenyl) -

2,4,6-trifluoro-5-chloropyrimidine

Reddish

3-carboxy-pyrazolone-5

yellow

50

dito

2,3-dichloroquinoxaline-6-

Reddish

carboxylic acid chloride

yellow

51

dito

Tetrachloropyrimidine ditto

52

1- (4'-sulfo-phenyl> 3-carboxy-

2,4,6-trifluoro-5-chloropyrimidine

Reddish

pyrazolone-5

yellow

53

dito

Tetrachloropyrimidine ditto

54

1-carboxy methyl-3-methyl-

2,3-dichloroquinoxaline-6-carbon

yellow

pyrazolone-5

acid chloride

55

1-carboxymethyl-3-methyl

Cyanuric chloride

yellow

pyrazolone-5

56

dito

2,4,6-trifluoro-5-chloropyrimidine

yellow

57

Hß-carboxyethyl) -3-methyl-

dito

yellow

pyrazoion-5

58

dito

Cyanuric chloride

yellow

59

dito

2-methylsulfonyl-4,5-dichloro-

yellow

6-methyl-pyrimidine

60

dito

2,4,6-trifluoro-5-chloropyrimidine

yellow

61

1 - {ß-Carboxyäthy I> 3-methyl-5-

dito

yellow

aminopyrazole

11

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For example, coupling component reactive component color

62

1 - <4 ', 8' -disulfonaphthyl- (2)) - 3-

2,4,6-trifluoro-5-chloropyrimidine

yellow

methyl-5-aminopyrazole

63

H5 ', 7'-disulfonaphthyl- (2)) - 3-

dito

yellow

methyl-5-aminopyrazole

Golden yellow

64

1 - (4 ', 8' -disulfonaphthyl- (2)) - 3-

dito

carboxy-pyrazolone-5

65

1 - (5 ', 7' -disulfo-naphthyl- (2)) - 3-

dito

Golden yellow

carboxy-pyrazolone-5

66

dito

2,4-dichloropyrimidine-5-carbon

Golden yellow

acid chloride

67

l-hydroxy-3-sulfo-7- (3'-carboxy-

dito

brown

phenylamino) naphthalene

68

dito

2,4,6-trifluoro-5-chloropyrimidine

brown

Example 69 20

33.6 g of l-amino-2-sulfo-3-aminomethyl-4-methoxy-benzene are diazotized as described in Example 3. A neutral solution of 32.3 g of 1-aminosulfonaphthalene in 300 ml of water is added dropwise to the acidic solution of the diazotization. The coupling is brought to an end by dulling to pH 4-5 with sodium carbonate solution. The monoazo dye obtained has the following constitution as free acid:

NH,

The partially precipitated dye is mixed with sodium hydroxide solution until solution has occurred (pH 8-9). After adding 34 ml of 30% sodium nitrite solution, the solution of the mono ■ azo dye is mixed to a mixture of 40 ml of conc. Hydrochloric acid and 200 ml of ice water. During the diazotization, a temperature of 10-15 ° is maintained by throwing in pieces of ice. The diazotization is colored yellow and partly failed. After removal of the excess sodium nitrite with amidosulfonic acid, it is added to a mixture of 44.1 g of 1-hydroxy-4,8-disulfonaphthalene and 40 g of sodium bicarbonate in 400 ml of water. The resulting disazo dye is separated by adding sodium chloride.

The water-moist paste is stirred in 1 liter of water, 40 g of CuSO-f 5H2O and 60 g of sodium acetate (NaAc • 3H2O) are added, and then enough of a 3% strength H2C> 2 solution is added at room temperature until complete oxidative coppering has occurred. The dye is deposited again by adding sodium chloride. The moist paste is mixed in water. At 12-15 ° and pH 8-8.5 is acylated with 20 g of 2,4,6-tri-fluoro-5-chloropyrimidine. About 110 ml of 2N NaOH are consumed. The dye is separated by adding sodium chloride. After drying and grinding, a black powder is obtained which dissolves in water with a blue color. After one of the printing or dyeing processes listed in Example 3, strong greenish-blue dyeings with very good lightfastness are obtained on cellulose-free material. In the form of the free acid, the dye corresponds to the following formula:

CH3 ° N = N

H0C S0, H

Cl

NH

% =>

0-Cu

N = N

F

If the procedure of Example 69 is followed, but using the middle and end components listed below, valuable dyes are also obtained, the color shades of which are listed in the last column.

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12

Example middle component

Final component

Reactive component

hue

70 l-amino-6-sulfonaphthalene

71 ditto

72 ditto

73 l-Amino-3-methyl-benzene

74 ditto

1-hydroxy-3,6-disulfonaphthalene

1-Hydroxy-4,6-disuIfo-naphthalene

2-hydroxy-3,6-disulfonaphthalene l-hydroxy-4,8-disulfonaphthalene l-hydroxy-3,6,8-trisulfonaphthalene

2,4-trifluoro-5-

chloro-pyrimidine ditto ditto ditto

blue

Greenish

blue

blue

blue

blue

Example 75

33.6 g of l-amino-2-sulfo-3-aminomethyl-4-methoxy-benzene are diazotized as described in Example 3. The resulting diazo solution is concentrated with a solution of 19.9 g of 20 l-amino-2-methoxy-5-methyl-benzene in 12 ml. Hydrochloric acid and 100 ml of water. Then you dull the coupling suspension with sodium acetate solution. After stirring for several hours, the precipitated coupling product is dissolved by adding sodium hydroxide solution (pH 12-12.5), mixed with 34 ml of 30% sodium nitrite solution and concentrated to a mixture of 60 ml. Add hydrochloric acid and 200 ml water at 15-20 ° C. The resulting diazo solution is added to a solution of 44.1 g of l-hydroxy-3,6-disulfonaphthalene and 60 g of sodium hydrogen carbonate in 500 ml of water. The precipitated disazo dye is filtered off, stirred in 500 ml of water and, after adding 100 ml of a 25% ammonia solution, 70 ml of di

ethanolamine and 70 g CuSC> 4-5H20 copper demmethylated by heating under reflux for two hours. The dye which has precipitated after cooling is suctioned off

The paste obtained is stirred in 500 ml of water at 45 ° and acylated with 40 g of 2,3-dichloroquinoxaline-6-carboxylic acid chloride. The pH is kept between 7 and 8 by the dropwise addition of a 10% sodium carbonate solution. After the acylation has ended, the solution is clarified and the dye is salted out of the filtrate by adding sodium chloride. After suction, drying and grinding, a black powder is obtained which dissolves in water with a blue color. According to one of the application methods customary for reactive dyes, a reddish-blue dyeing of very good light and wash fastness is obtained on cellulose fibers. The dye obtained corresponds in the form of the free acid to the following formula:

O-Cu

In this example, if the l-hydroxy-3,6-disulfonaphthalene is replaced by l-hydroxy-4,8-disulfonaphthalene, 1-hydroxy-4,7-disulfonaphthalene, 1-hydroxy-4,6-disulfonaphthalene naphthalene, 2-hydroxy-3,6-disulfonaphthalene, 2-hydroxy-5,7-disulfonaphthalene and otherwise operates according to the same procedure, valuable blue reactive dyes are also obtained. Likewise valuable blue reactive dyes are obtained if, instead of 2,3-dichloroquinoxaline-6-carboxylic acid chloride, the reactive components listed below are used and the acylation is carried out using the reaction conditions known from the literature: 2,4,6-trifluoro-5-chloro pyrimidine, 2,4,6-trichlorotriazine, 2,4,5,6-tetrachloropyrimidine, 1,4-dichlorophthalazin-6-carboxylic acid chloride.

b5

Example 76

33.6 g of l-amino-2-sulfo-3-aminomethyl-4-methoxy-benzene are diazotized as described in Example 3. The clear diazo solution obtained is added to a solution of 33.8 g of 2-aceto-acetylamino-1-methoxy-4-methyl-5-sulfo-benzene and 40 g of sodium bicarbonate in 400 ml of water. The coupling product fails for the most part. By throwing in ice, the temperature is lowered to 12-15 ° and then acylated with 24.5 g of 2,4,6-trifluoro-5-chloropyrimidine. After about 140 ml of 2N sodium hydroxide solution have been consumed, the acylation is complete. The dye is brought into solution by heating to 45 ° and salted out with 5% by volume sodium chloride. After suction, drying and grinding, a yellow powder is obtained which dissolves in water with a clear yellow color and, after one of the application processes listed in Example 3, gives a clear greenish-yellow color on cellulose fibers which are distinguished by good light and wet fastness and have remarkable stability to treatment with chlorine. In the form of the free acid, the dye has the following structure:

13 624426

CH,

i 3

c = o

However, if one proceeds according to the information in this example and reactive components, valuable reactive dyes are also obtained using the coupling 20 strongly greenish yellow listed below.

Ex.

Coupling component

Reactive component

hue

77

2-acetoacetylamino-l, 4-dime-

2,4,6-T richlorotriazine

Green tinted

thoxy-5-sulfo-benzene

yellow

78

dito

2,4-dichloro-6-amino

Greenish

triazine

yellow

79

dito

2,4-dichloro-6-methoxy

Greenish

triazine

yellow

80

dito

2,4-dichloro-6- (3'-sulfo

Greenish

phenyl) amino triazine

yellow

2,4-dichloro-6- (2 ', 5' -di

sulfo-phenyl> amino

triazine

81

2-acetoacetylamino-l-methoxy

2,4,6-trifluoro-5-chloro

Greenish

4,6-disulfobenzene pyrimidine

yellow

82

dito

2,4,6-trichlorotriazine

Greenish

yellow

Claims (7)

624426 PATENT CLAIMS 1. Process for the preparation of azo reactive dyes which are in the acid form of the formula ro —— n = n-a H2f S03H (I) V r1-n-z 3. The method according to claim 1 for the production of azo-reactive dyes in the acid form of the formula oh ro (V) 10th h2c s0, h H ' r1-n-z (so3h) correspond to n, where R = optionally substituted alkyl, Ri 15 = hydrogen or optionally substituted alkyl, W = a direct bond or a bridge member, A = the rest of a coupling component and Z = the rest of a heterocyclic reactive component of the formula -CO-Het, -SCh-Het or 20 means, where Het stands for a heterocycle bonded directly or via a bridge and the mono- or polynuclear heterocycles correspond to Het and, where n is 1 -3. 4. The method according to claim 1 for the preparation of azo-reactive dyes in the acid form of the formula (VI) ho3s u -Ö have at least one substituent reactive with cellulose or polyamide, characterized in that azo dyes of the formula ro n = n-a h ~ c ns0, h (xi) 2 | 3rd ¥ I. r1-n-h condensed with a reactive component X-Z, where Z has the meaning given and X is a removable substituent. correspond in which u and v are hydrogen or a sulfo group and acyl is an acyl radical, in particular acetylene or benzoyl. 5. The method according to claim 1 for the preparation of azo-reactive dyes in the acid form of the formula 35 40 (VIII) correspond to r1-n-z, in which E represents an alkyl, phenyl or naphthyl radical substituted by at least one water-solubilizing group, M represents a methyl, carboxy or carbonamid group and G represents an OH or NH2 group. 6. The method according to claim 1 for the preparation of azo-reactive dyes in the acid form of the formula 2. The method according to claim 1 for the production of azo Reactive dyes, which in the acid form of the formula n = n -i ro hpc ^ so, h 2 | 3rd correspond to r-j -n-z. (II) 55 60 65 ch, I 3 c = 0 ro -fa-n = n-ch h0c H r ^ j -n-z SO3H (VII) correspond, in which the ring D may contain further substituents. 624426 7. The method according to claim 1 for the preparation of azo reactive dyes in the acid form of the formula O-Cu-O, \ « correspond, in which n stands for 1,2 or 3, R2 represents a substituent, and p stands for the numbers 0,1 or 2. Processes can serve amines that are in the acid form of the formula , o-fV nh, 20 \ - / 2 (iii)