GB1559724A - Preparation of fibre reactive dyestuffs - Google Patents

Abstract

New water-soluble fibre-reactive green phthalocyanineazo dyes of the formula I are obtained by diazotising an amine of the corresponding phthalocyanine series of the formula <IMAGE> where the amino group is attached to an aromatic carbon atom of the radical ar, and coupling in an aqueous medium at a pH of 3-8 with a succinic acid derivative of the formula <IMAGE> cyclising the resulting hydrazone by the action of alkalis to form a parazolone and coupling the latter with the diazonium compound of an amine of the formula <IMAGE> or with the diazonium compound of an amine of the formula H2N-B-E. The symbols A, B, Pc, ar, R1 to R4 , R7, k, l and m are each defined in Claim 1, the sum k + l + m being 3 or 4. When R7 in the formula I is hydrogen, E is nitro which is converted into amino or is <IMAGE>acyl), in which case the coupling dye is hydrolysed. In either case the dye obtained is reacted with a compound of the formula X-A, where X is a group that is detachable by nucleophilic attack from an amino group. The dyes of the formula I are highly suitable for dyeing and printing cellulose and natural and synthetic polyamide materials, show a high yield of fixation and produce yellowish to bluish green dyeings and prints of high brilliance and colour strength combined with very good fastness properties. <IMAGE>

Description

ERRATA SPECIFICATION No. 1,559,724 Page 2, line 14, delete existing formula insert (54) PREPARATI (71) We, CASSELL Farbwerke Mainkur Aktiengese of SZ6 Hanauer Landstrasse, i declare the invention, for whict method by which it is to be F following statement :- The present invention rela soluble fibre-reactive phthalocya

wherein A=a fibre-reactive radi, nuclear or dinuclear aromatic or is bonded to the group, Pc=the radical of a m radical of an optionally substin hydrocarbon, the alkylene chain (

Page 36, line 29, delete existing formula insert

TTIE PATENT OFFICE 7 r.-I pril, 1980

group, R1 = hydrogen, optionally substituted alkyl with 1-6 C atoms, phenalkyl or naphthalkyl with 1-3 C atoms in the aliphatic chain, phenyl or naphthyl, it being possible for the aromatic nuclei optionally to carry further substituents, R2=hydrogen, optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-20 C atoms, R, =hydrogen or optionally substituted alkyl with 1-6 C atoms, R, =hydrogen or optionallv substituted alkvl with 1-6 C atoms or unsubstituted alkvl with 7-18 (54) PREPARATION OF FIBRE-REACTIVE DYESTUFFS (71) We, CASSELLA ARTIENGESELLSCHAFT, formerly Cassella Farbwerke Mainkur Aktiengesellschaft, a body corporate under the laws of Germany, of 526 Hanauer Landstrasse, 6 Frankfurt (Main)-Fechenheim, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement :- The present invention relates to a process for the manufacture of valuable watersoluble fibre-reactive phthalocyanine azo dyestuffs of the formula I

wherein A=a fibre-reactive radical, B=the radical of an optionally substituted mononuclear or dinuclear aromatic or araliphatic hydrocarbon, the alkylene chain of which is bonded to the

group, Pc=the radical of a metal-containing or metal-free phthalocyanine, ar=the radical of an optionally substituted mononuclear or dinuclear aromatic or araliphatic hydrocarbon, the alkylene chain of which is bonded to the

group, Rl=hydrogen, optionally substituted alkyl with 1-6 C atoms, phenalkyl or naphthalkyl with 1-3 C atoms in the aliphatic chain, phenyl or naphthyl, it being possible for the aromatic nuclei optionally to carry further substituents, R, =hydrogen, optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-20 C atoms, R., =hydrogen or optionally substituted alkyl with 1-6 C atoms, R, =hydrogen or optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-18 C atoms, R, =hydrogen or optionally substituted alkyl with 14 C atoms and k 4 and the sum of k, 1 and m is 3 or 4, and their alkali metal, ammonium or alkaline earth metal salts, in which process an amine of the phthalocyanine series of the general formula II, the amino group being bonded to an aromatic C atom of the radical ar

and wherein Pc, ar, Rl R2X RJX k, l and m have the meanings given above, is diazotised and coupled with a succinic acid derivative of the formula III

wherein R,'denotes optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-18 C atoms, RS denotes optionally substituted alkyl with 1-6 C atoms or unsubstituted alkyl with 7-18 C atoms and Z denotes hydrogen, an optionally substituted alkyl radical with 1-10 C atoms, an optionally substituted phenyl radical or alkoxycarbony ! with 2-6 C atoms, in an aqueous medium at a pH value between 3 and 8 and the resulting hydrazones of the formula IV

wherein Pc, ar, Rl, R,, R,, R,, R,, k, 1 and m have the meanings given above, are converted into pyrazolones of the general formula V

wherein Pc, ar, Ri, R2, R,, k, I and m have the meanings given above, by the action of alkalis, and these are coupled with the diazonium compound of an amine of the general formula VI HzN-B-W VI wherein B has the meaning given above, and W is a group of the formula-N (R,) A, wherein R, and A have the meanings given above, or a precursor of the said group -N (R,) A, the group W, when it is a precursor of that group, being submitted to one or more reactions effective to convert it into the said group of the formula

In the amines of the phthalocyanine series of the general formula II to be employed according to the invention, Pc denotes, in particular, the radical of a metalcontaining phthalocyanine, ar denotes, in particular, the radical of a mononuclear or dinuclear aromatic or araliphatic hydrocarbon which is optionally substituted by a -SO, H group and which can be substituted in each nucleus by one substituent of the group alkoxy with 1-4 C atoms orSO2R6 or by an additional-SOH group, by one or two identical or different substituents of the groups halogen,

or-COOH or denotes a phenylene radical which is optionally substituted by a -SO, H group and which can be additionally substituted by one to three identical or different alkyl radicals with 1-4 C atoms, R, and Rl'independently of one another denote, in particular, hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical with 2-6 C atoms which is optionally substituted by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, preferably acetylamino, benzoylamino, alkanoyloxy with 1-6 C atoms, preferably acetyloxy,-COOH or-SOjH, a phenalkyl or naphthalkyl radical with 1-3 C atoms in the aliphatic chain, phenyl or naphthyl, it being possible for the aromatic nuclei to be substituted or further substituted by Cl, Br, OH, alkyl and/or alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms,-COOH or-SO, H, R, and R,'independently of one another denote, in particular, hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical with 2-6 C atoms which is optionally substituted by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C atoms,-COOH or-SO, H or an unsubstituted alkyl radical with 7-20 C atoms, R, denotes, in particular, hydrogen, methyl, carboxymethyl, sulphomethyl or an alkyl radical with 2-6 C atoms which is optionally substituted by CI, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C atoms,-COOH or-SO, H and Re denotes, in particular, methyl, carboxymethyl, alkyl with 2 or 3 C atoms, benzyl or phenyl, it being possible for the aromatic nuclei to be mono-substituted or disubstituted by-COOH or-SO, H.

The symbof k represents the numbers 0,1,2 or 3,1 represents 0,1 or 2 and m represents 1, 2,3 or 4 and the sum of k, I and m is 3 or 4.

Amines of the general formula II which are to be employed according to the invention and in which Pc denotes the radical of a metal-containing phthalocyanine, for example, of cobalt or copper phthalocyanine, but in particular the radical of nickel phthalocyanine, are preferred.

Araliphatic radicals represented by ar are always bonded to the-NHz group with an aromatic nucleus. Mononuclear aromatic or araliphatic radicals which can be represented by ar are the optionally substituted radicals phenylene and mono-or poly methylenephenylene of the general formula

in which n denotes an integer from 1 to 10.

Dinuclear aromatic or araliphatic radicals which can be represented bv ar are the optionally substituted radicals naphthylene, mono-or poly-methyienenap. rhylene of the general formula

in which n denotes an integer from 1 to 3. and the ootionaliv substinued radicals of

Examples of mononuclear or dinuclear aromatic or araliphatic hydrocarbon radicals which can be represented by ar in the amines of the formula II are: 1,4phenylene, 1,3-phenylene, 2-sulpho-1, 4-phenylene, 3-sulpho-1, 4-phenylene, 4-or 5sulpho-1, 3-phenylene, 2-carboxy-1, 4-phenylene, 3-carboxy-1, 4-phenylene, 4-, 5-or 6carboxy-1,3-phenylene, 2-carboxy-5-sulpho-1, 4-phenylene, 2-carboxy-6-sulpho-1, 4phenylene, 3-carboxy-6-sulpho-l, 4-phenylene, 6-carboxy-4-sulpho-l, 3-phenylene, 5carboxy-2-sulpho-1, 3-phenylene, 2,5-dicarboxy-1,4-phenylene, 4,6-dicarboxy-1,3phenylene, 2-chloro-5-sulpho-1, 4-phenylene, 2-chloro-6-sulpho-1, 4-phenylene, 3 chloro-6-sulpho-1, 4-phenylene, 6-chloro-4-sulpho-1, 3-phenylene, 2-chloro-5-carboxy- 1,4-phenylene, 2,6-disulpho-1, 4-phenylene, 2,5-disulpho-1, 4-phenylene, 4,6-disulpho1,3-phenylene, 3-chloro-6-carboxy-1,4-phenylene, 6-chloro-4-carboxy-1,3-phenylene, 4-chloro-5-carboxy-1, 3-phenylene, 2-methyl-5-carboxy-1, 4-phenylene, 2-ethyl-6carboxy-1,4-phenylene, 3-ethyl-6-sulpho-1,4-phenylene, 6-ethyl-4-carboxy-1, 3-phenylene, 6-propyl-4-sulpho-1, 3-phenylene, 5-isopropyl-4-sulpho-1, 3-phenylene, 5-iso- propyl-6-carboxy-1, 3-phenylene, 4-n-butyl-6-sulpha-1, 3-phenylene, 3-n-butyl-6- sulpho-1, 4-phenylene, 4-tert.-butyl-6-sulpho-1, 3-phenylene, 3-isobutyl-6-sulpho-1, 4phenylene, 2,5-diisopropyl-6-sulpho-1,4-phenylene, 2,4-diethyl-5-carboxy-1,3phenylene, 2,4,6-trimethyl-5-sulpho-1, 3-phenylene, 2-cyano-1,4-phenylene, 4-cyan- 1, 3-phenylene, 2-cyano-5-sulpho-1, 4-phenylene, 2-trifluoromethyl-1, 4-phenylene, 2 methylsulphonyl-1, 4-phenylene, 2-ethylsulphonyl-1, 4-phenylene, 4-sulpho-1, 5naphthylene, 8-sulpho-1, 5-naphthylene, 4-sulpho-2,6-naphthylene, 2-carboxy-1,4naphthylene, 2-carboxy-1, 5-naphthylene, 5-carboxy-1, 4-naphthylene, 3-carboxy-1, 8naphthylene, 3-carboxy-1, 5-naphthylene, 4-carboxy-2,6-naphthylene, 4-carboxy-2, 7naphthylene, 1-sulpho-2, 6-naphthylene, 8-sulpho-1, 3-naphthylene, 4,8-disulpho-2,6naphthylene, 3,7-disulpho-1, 5-naphthylene, 1-sulpho-4-chloro-2, 6-naphthylene, 1chloro-5-sulpho-2, 6-naphthylene, 1-chloro-7-sulpho-2, 6-naphthylene, 2-chloro-6sulpho-1, 4-naphthylene, 1-methyl-4-sulpho-2, 6-naphthylene and 2-methyl-7-sulpho1, 4-naphthylene. In each case, the hydrazone group is in the 1-position of the phenyl nucleus or in the 1-position or 2-position of the naphthalene nucleus. In the list which follows, examples of compounds from which further divalent radicals which are represented by ar are derived are indicated. The positions of the two bonds with which the divalent radicals are bonded on the one hand to the amino group (first position given) and on the other hand to the group-NR,- (second position given) cf the dyestuffs which can be manufactured according to the invention are indicated in the second column of the table.

Position of the bonds Compound from which-ar-is derived of-ar- Dipheny I 4, 4 2,2'-dimethyl-diphenyt 4, 4 3,3'-dimethoxy-diphenyl 4, 4 3,3'-dichloro-diphenyl 4,4' 3,3'-dimethyl-diphenyl 4,4' 2,2'-disulpho-diphenyl 4,4' diphenyl-ethane 4,4' diphenyt ether 4, 4' 2,2'-di sulpho-diph enyl-methane 4, 4' 2,2'-disulpho-diphenyl-ethane 4,4' 3,3'-disulpho-diphenyl-ethane 4,4' 2,2'-disulpho-diphenyl ether 4, 4' 2-sulphamido-diphenyl-ethane 4, 4' 2,2'-di sulphamido-diphenyl-ethane 4, 4' 2, 2'-di- -hydroxyethylsulphamido-diphenyl-ethane 4,4' stilbene-2, 2'-disulphonic acid 4, 4' methyl-phenyl 4, 1-methyl-phenyl-3-sulphonic acid 4, 1-ethyl-phenyl-2-sulphonic acid 4,# 1-propyl-phenyl-3-sulphonic acid 4,# 5-methyl-naphthalene-l-sulphonic acid 2,# diphenylamine 4, 4' 6-methoxy-diphenylamine-2'-sulphonic acid 3,4' 4-methyl-diphenylamine-2'-sulphonic acid 3,4' diphenylketone-5, 5'-disulphonic acid 3,3' diphenylketone-3'-sulphonic acid 3,4' diphenylsulphone 4, 4' 4, 4'-dichloro-diphenylsulphone 3, 3' 4,4'-disulpho-diphenylsulphone 3,3' @ @@@@@@@ @ @@@@@@ @@@@@@@@@@@@@@@@ @ @' In the amines of the formula II to be employed according to the invention, the optionally substituted radicals phenylene, naphthylene,

are preferred for ar.

The optionally substituted mononuclear or dinuclear aromatic or araliphatic hydrocarbon radical represented by ar in the amines of the formula II to be employed according to the invention appropriately contains at least one sulpho group or carboxyl group, but valuable dyestuffs according to the invention can also be obtained with radicals of the general definition of ar which contain no acid group conferring solubility in water. In addition, each nucleus of ar can be substituted by one substituent of the group-OH, alkoxy with 1-4 C atoms,-CN,-CF, or-SOR, or by an additional-SO, H group or by one or two identical or different substituents of the groups halogen,

or-COOH. If ar is derived from a phenylene radical, in addition to aSO3H group which may be present, it can be substituted by one to three identical or different alkyl radicals with 1-4 C atoms.

Amines of the formula II in which ar is phenylene or phenylene which is substituted by one or two carboxyl groups or by one or two sulpho groups, or a naphthylene radical which is substituted by one or two sulpho groups or a stilbenylene radical which is substituted by one or two sulpho groups, and in particular those in which ar is a radical of the formula

the position shown here corresponding to the position in the general formula I, are particularly preferably employed.

Amongst amines of the formula II which contain a

group in ar, those in which R, and R,'independently of one another denote hydrogen, an alkyl radical with 2 or 3 C atoms which @s oprionally substituted by OH, alkoxy with 1-3 C atoms, -COOH or -SO3H, methyl, carboxymethyl or sulphomethyl and also those in which R2 and R/independendy of one another denote an alkyl radical with 2 or 3 C atoms which is optionally st : bsiituted by OH, alkoxy with 1-3 C atoms,-COOH or-SO :, H or an unsubstir-red aHcyt radical with 1-20 C atoms, but in particular hydrogen, methyl, carboxyrHi or n alkyl radical with 2 or 3 C atoms which is optionally substituted by OH, are preferred.

Particularly preferred meanings of R, and R:arehydrogen,methylorj8-hydroxy- ethyl. Similarly, hydrogen, methyl and @-@@@@@@@@@@@@ are particularly prefo@@ed Amines of the formula II which, except for carboxylic acid and sulphonic acid radicals, carry no further substituents in the divalent radical ar, are particularly preferred.

Further preferred groups of amines of the general formula II to be employed according to the invention are characterised in that R, denotes hydrogen, methyl, carboxymethyl, sulphomethyl or an ethyl radical which is optionally substituted by Cl, OH, alkoxy with 1 or 2 C atoms,-COOH or-SO., H, in particular hydrogen or methyl.

Amongst the amines of the formula II which contain a-SOz-Rw group in ar, those in which Rb is methyl, ethyl, phenyl or carboxymethyl are preferred.

Those amines of the general formula II to be employed according to the invention in which I is 0, k is 2 or 3 and m is 1 or 2 and the sum of k+m is 4, are particularly preferred.

The substituents indicated in formula II can be in the 3-positions and/or 4-posi- tions of the phthalocyanine. The 3-position of the substituents indicated is preferred.

In the phthalocyanine, 3-positions are the 3-position, 3'-position, 3"-position and 3"'-position and 4-positions are the 4-position, 4'-position, 4"-position and 4"'position.

In the case where 1 represents 0, the amines of the general formula II required for the manufacture according to the invention of the dyestuffs of the formula I are obtained by reacting phthalocyanine 3-di-sulphochlorides, 3-trisulphochlorides, 4-di- sulphochlorides, 4-uri-sulphochlorides or, preferably, 3-tetra-sulphochlorides or 4 tetra-sulphochlorides with amines of the general formula X

wherein R3 and ar have the meanings indicated above. Monoacylated amines, for example acylated amines of the formula Xa

can also be employed instead of amines of the formula X. In this case, the condensation product formed is subsequently saponified with phthalocyanine sulphochloride.

If I in formula I and IV represents the number 1, phthalocyanine 3-sulphochloride or 4-sulphochloride is reacted, in any desired sequence, with an amine of the general formula XI

in which Ri and R2 have the meanings indicated above, and with an amine of the formula X in order to obtain amines of the formula II.

In addition, however, there is also the possibility of using from the beginning a mixture of amines of the formulae X and XI. The reaction of phthalocyanine sulphochloride with the amines mentioned is carried out in a manner which is in itself known by adding the amines, either consecutively or as a mixture, to a concentrated aqueous suspension of the sulpho-chlorides in water or in a mixture of water and organic solvents which are miscible with water. However, it can also be carrvd out in organic solvents alone. The temperature of the reaction mixture is kept at 0 o 35'C and the pH value, which during the reaction continually shifts to the acid range, is kept between 4 and 10, preferably between 6 and 8, by the gradual addition of alkali.

Possible alkalis are the customary substances which have an alkaline action, such as sodium hydroxide solution, sodium carbonate, potassium carbonate and trisodium phosphate. Sodium hydroxide solution is preferred. A tertiary amine, such as, for example, pyndine, is advantageously added in catalytic amounts to accelerate the reaction. It is possible to further process the amines of the formula II directly in the a-; uenlls cOlu : n in which they are obtained, but normally it is advantageous to isolate them in order to free them from any fraction of unreacted amine of the formula X and/or XI which may still be present.

The following may be mentioned as amines of the formula XI which can be used for the manufacture of amines of the formula II: ammonia, methylamine, dimethyl- amine, ethylamine, diethylamine, -hydroxyethylamine, -methoxyethylamine, bis-B- hydroxyethylamine, aminoacetic acid, taurine, N-methyltaurine, butylamine, capryl amine, laurylamine, aniline, toluidine, chloroaniline, aniline-o-, aniline-m-or aniline p-sulphonic acid, aniline-o-, aniline-m-or aniline-p-carboxylic acid, N-methylaniline, N-ethylaniline-o-, N-ethylaniline-m-or N-ethylaniline-p-sulphonic acid, aniline-#- methane-sulphonic acid, benzylamine, N--hydroxyeihyi-benzylamine, benzytamine- sulphonic acid and -acetylaminoethylamine.

The following may be mentioned as examples of amines of the formula X which can also be employed in the form of the monoacyl compound: p-phenylenediamine, N-methyl-p-phenylenediamine, N-carboxymethyl-p-phenylenediamine, m-phenylene diamine, N--hydroxyethyl-m-phenylenediamine, l, 4-phenylenediamine-2-sulphonic acid, l-amino-4-N-sulphomethylamino-phenylene-2-sulphonic acid, 1,4-phenylenedi amine-2, 5- or -2,6-disulphonic acid, 1-amino-4-N-methylamino-phenylene-2, 6-di sulphonic acid, 1, 3-phenylenediamine-4-sulphonic acid, 1, 3-phenylenediamine-4, 6 disulphonic acid, 2,4-diamino-toluene-6- or-6-sulphonic acid, 2,6-diamino-toluene-4 sulphonic acid, 2,5-diamino-1,3, 5-trimethylbenzene-4-sulphonic acid, 2,6-diamino-l, 3 diethylbenzene-4-sulphonic acid, 2, 4-diamino-l-chlorobenzene-6-sulphonic acid, 2,4 diamino-l-tert.-butyl-benzene-6-sulphonic acid, 2, 4-diaminotoluene-5- or -6-sulph amide, 2,6-diamino-toluene-4-ethanol or-diethanolsulphamide, 1,4-diaminophenylene 2-dimethylsulphamide, 1, 3-diaminophenylene-4-sulphanilide, 1,3-diaminophenylene 4- -hydroxyethylsulphone, N-ethyl-p-phenylenediamine, N-propyl-p-phenylenedi amine, N-butyl-p-phenylenediamine, N-pentyl-p-phenylenediamine, N-hexyl-p phenylenediamine, N- -hydroxy-propyl-p-phenylenediamine, N- -carboxy-propyl-p- phenylenediamine, N-y-chloro-butyl-p-phenylenediamine, N4-methoxy-butyl-p- phenylenediamine, N4-propoxy-butyl-p-phenylenediamine, N- -acetylamino-ethyl-p- phenylenediamine, N-, 8-butyrylamino-ethyl-p-phenylenediamine, N-benzoylamino ethyl-p-phenylenediamine, 1-N-methyl-3-amino-benzene-4-sulphonic acid, 1-N-butyl- 4-amino-benzene-3-sulphonic acid, 2,4-diamino-phenol-6-sulphonic acid, 2,4-diamino l-methoxybenzene-5-sulphonic acid, 1, 5-diaminonaphthalene, 1,5-diaminonaphthalene 3-sulphonic acid, 1, 5-diaminonaphthalene-4-sulphonic acid, 1, 5-diaminonaphthalene-2- sulphonic acid, 1, 6-diaminonaphthalene-4-sulphonic acid, 1, 4-diaminonaphthalene-2 sulphonic acid, 1, 4-diaminonaphthalene-5-sulphonic acid, 1, 4-diaminonaphthalene-7 sulphonic acid, 1, 8-diaminonaphthalene-4-sulphonic acid, 2,6-diaminonaphthalene-8 sulphonic acid, 2,6-diaminonaphthalene-4, 8-disulphonic acid, 1,5-diaminonaphthalene 3,7-disulphonic acid, 1, 4-diaminonaphthalene-5-carboxylic acid, 1,4-diaminonaphthal ene-2-carboxylic acid, 1, 8-diaminonaphthalene-3-carboxylic acid, 4,4'-diaminodi phenyl, 2,2'-dimethyl-4,4'-diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodiphenyl, 4,4' diaminodiphenyi-2, 2'-disulphonic acid, 3,3'-dimethoxy-4,4'-diaminodiphenyl, 1-amino 4-aminomethyl-benzene, 1-amino-4-aminomethyl-benzene-3-sulphonic acid, 1-amino 4-,-aminoethyl-benzene-2-sulphonic acid, I-anaino-4--/-aminopropylbenzene-3-suI- phonic acid, 2-amino-5-aminomethyl-naphthalene-l-sulphonic acid, 4,4'-diamino-di phenylmethane-2, 2'-disulphonic acid, 4,4'-diamino-diphenylethane-2, 2'-disulphonic acid, 4,4'-diamino-diphenylethane-mono-sulphonamide, 4,4'-diamino-diphenylethane disulphamide, 4,4'-diaminostilbene-2,2'-disulphonic acid, 4,4'-diamino-diphenyl- methane, 4, 4'-diamino-diphenylethane-di- -hydroxyethylsulphamide, 4,4'-diamino diphenylamine-3-sulphonic acid, 3, 4'-diamino-6-methoxy-diphenylamine-2'-suplphonic acid, 3,4'-diamino-4-methyl-diphenylamine-2'-sulphonic acid, 3,3'-diaminobenzo phenone-5, 5'-disulphonic acid, 3, 4'-diaminobenzophenone-3'-sulphonic acid, 4,4' diaminodiphenylsulphone, 4,4'-dichloro-3, 3'-diamino-diphenylsulphone, 3,3'-diamino 4-methyl-diphenylsulphone-5-sulphonic acid and 3,3'-diamino-diphenylsulphone-4,4' disulphonic acid.

In the manufacture according to the invention of the dyestuffs of the general formula I, an amine of the phthalocyanine series of the general formula II, the free amino group being bonded to an aromatic C atom of the radical ar

and wherein Pc, ar, Rl, R2, R"k, l and m have the meanings indicated above, is initially diazotised and coupled with a succinic acid derivative of the formula III

wherein R,'and Rs have the meanings indicated above and Z denotes hydrogen, an alkyl radical with 1-10 C atoms which is optionally substituted by alkoxy with 1-4 C atoms or alkoxycarbonyl with 2-6 C atoms, a phenyl radical which is optionally substituted by Cl, Br, alkyl or alkoxy with 1-4 C atoms or alkoxycarbonyl with 2-6 C atoms, in an aqueous medium at a pH value between 3 and 8.

Preferred succinic acid derivatives of the formula III are those in which R,' denotes an alkyl radical with 2-6, preferably 2, C atoms which is substituted by Cl, OH or alkoxy with 1-4, preferably 1-2, C atoms or an unsubstituted alkyl radical with 1-18, preferably 1-6, C atoms, R, denotes an ethyl radical which is substituted by Cl, OH or alkoxy with 1-2 C atoms or an unsubstituted alkyl radical with 1-18 C atoms and Z denotes hydrogen, alkyl with 1-3 C atoms, phenyl, methylphenyl or alkoxycarbonyl with 2 or 3 C atoms.

Succinic acid derivatives of the formula III in which R, and R. are identical and denote methyl or ethyl and Z represents a methyl group, are particularly preferred.

The diazotisation of amines of the general formula II is carried out in a manner which is in itself known in an aqueous acid medium by reacting them with nitrous acid or an agent which releases nitrous acid. A salt of nitrous acid, in particular an alkali metal salt, such as sodium or potassium nitrite, is generally employed, in a mineral acid medium, as an agent which releases nitrous acid. In a preferred embodiment a solution of sodium nitrite is added in the molar ratio 1 : m to the neutral aqueous solution of 1 mol of an amine of the formula II and this mixture is then allowed to run into at least 2.5 mols, preferably 3 mols, of dilute approximately 5-15% strength hydrochloric acid per mol of amino group present at temperatures between 5 and +25 C., preferably 2 to +S C., whilst stirring. The diazo suspension thus obtained is then reacted with a succinic acid derivative of the general formula III at a pH value between 3 and 8, preferably between 4.5 and 5. 5, by, for example, adding the succinic acid derivative to the acid suspension of the diazonium compounds and then adjusting the pH value to the desired value by adding alkali, for example sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate, potassium carbonate or sodium phosphate. After stirring for 1-3 hours, the diazotised amine can no longer be detected and the formation of the hydrazone is complete. It can be separated out from the solution by salting-out, that is to say by adding a neutral water-soluble salt, for example, sodium or potassium chloride. However, separating out is in no way necessary for the further processing of the hydrazones; on the contrary, it is appropriate and advantageous to employ the reaction solutions obtained during the coupling direct for the further processing.

The aqueous medium in which the coupling reaction of diazotised amines of the formula II with succinic acid derivatives of the formula III is carried out can also contain organic water-miscible solvents, in particular lower aliphatic alcools, for example, methanol, ethanol or isopropanol. Similarly, known coupling accelerators, for example, urea or pyridine, can be present during the coupling reaction.

The second reaction step of the manufacturing processes according to the invention, that is to say the cyclisation of the hydrazone IV to the pyrazolone V, is carried out extremely easily by the alkaline treatment of the aqueous solution of hydrazones of the formula IV at temperatures between 0 and 100 C., preferably 15 to 30 C., at a pH value between 8 and 14 with splitting off of the alcohol of the formula R, OH.

The cyclisation can be coupled with a saponification of the group-COOR, of the 1 1 1. 1 ~ T~ 1.'.'. 1 out the reaction near the upper limit of the pH value range indicated, for example at pH values of 10 to 14. The cyclisation is appropriately carried out direct in the reaction solution, obtained during coupling, of hydrazones of the formula IV by increasing its pH value to 10 to 14, room temperature generally being sufficient. A diazo solution of an amine of the formula VI

rs appropriately added to the solution, thus obtained, of the pyrazolone V without isolating the pyrazolone and after cooling to temperatures between-5 and +35 C, preferably +3 10 +20 C, and the mixture is subsequently stirred, if necessary with cocjing, at temperatures between -5 and +25 C, preferably + 5 to + 15 C, until the zig reaction has ended. During the course of the coupling reaction, which has generally ended after only a few minutes, the pH value is kept at values from 3 to 8, table 5 to 6, by the successive addition of a buffer substance or an alkali.

In amines of the formula VI to be employed according to the invention as diazo -jpooents, A denotes a fibre-reactive radical. Fibre-reactive radicals A are to be as those which contain a radical which can be split off as an anion or as @ @@@@@ral radical or contain a double bond which is capable of addition reactions, and @@@@@ are thus capable of reacting with the hydroxyl groups of cellulose when the are applied to cellulose materials in the presence of acid-binding agents and/ the the action of heat, or, when applied to high-molecular weight polyamide 3G such as wool, with the nucleophilic centres of these fibres with the formation of ==K bonds Radicals which can be split off by nucleophilic attack are those which, @@ @@@@ of their position in the periodic system and/or because, of a positive charge - sre strongly electron-attracting. Activated double bonds are, for example, those BdL are conjugated with a polar double bond, for example a carbonyl group. A @@@ @@@ber of fibre-reactive groupings of this type are known from the literature.

- T3 Triples of known hbre-reactive radicals A, there may be mentioned: radicals acids, such as the radicals of acrylic acid, a-chloroacrylic acid, said acid and propiolic acid, also the radicals of acids which either contain @ @@@@@@@@@@@t which can be easily replaced nucleophilically, for example, a halogen atom, diwols of a,-unsaturated acids when a neutral or anionic group is split

@@ which contains a vinylsulphone or-halogenoalkyl or ss-sulphatoalkylsulphone @@@ @ as the radicals of chloroacetic acid, ss-chloropropionic acid, ss-phenyl- @@@@@@@@@@@@@pienic acid, ss-pyridiniumpropionic acid, ss-sulphatopropionic acid ss- @@@@@@@@@@@@@@@@@@phenic acid, #-(ss-chloroethylsulphonyl)-butyric acid or 4-ss-chloro- acid. carboxylic or sulphonic acids which carry a substituent @@@@@ @ @@@@@ replaced during the course of the application by the radical of cellulose @@ @@ @ @@@@@ophilic group of the wool or the polyamide, for example, the radicals of @@@@@@@@@@@@@@@@@@@line-5- or -6-sulphonic acid, 2,3-dichloroquinoxaline-5- or-6- @@@@ @@@@, 2,4-dichloroquinoazoline-6- or -7-sulphonic acid, 2,4-dichloroquinazo @@@@@@@@@@@@@ acid, 1,4-dichlorophthalazine-6-carboxylic acid and the corresponding -...2-.-trdceno-monomethyl-sulphonyl or monohalogeno-mono-ethylsulphonyl acid or 2,4-dichloro-, 2,4-dibromo- or or-6--carboxylic acid or the corresponding monohalogeno @@@@@@@@@@@@benyl or monohalogeno-monoethylsulphonyl derivatives, and 2-chloro @@@@@@@@@@@@@@@@@@ acid or 2-chlorobenzthiazole-sulphonic acid.

@@@@@@ @@ @@@-membered heterocyclic compounds containing 2 or 3 N atoms, such --'-*- pyrimidin-2-yl or s-triazin-4-yl and pyrimidin-4-yl radicals, which 1 theremaining2-positions, 4-positions or 6-positions, at least -t-t which can be nucleophilically replaced. Substituents on the hetero j----c*:'?hinbenucleophilically replaced which may be mentioned are, , Br or F, tertiary and quaternary amino, including hydrazin las C,-C,-alkylsWphonyl and option @@ @@@@@@@@@@@@@ phemysulphonyl, thiocyano, sulphinic acid and sulphonic acid. In cases @@@@@@ @@@ @@@@@@@@@ ring or triazine ring only carries one such labile substituent, this "-----''''bUebtuentonthe remaining carbon atom or more non @@@@ @@@@@@@@@@@@ an @@@@@@@@ @@@@@@ atoms. A non-labilesubstituent is to be under- by a covalent bond, this covalent bond not being broken open under the conditions used in applying the reactive dyestuff.

Examples of these non-labile substituents which may be mentioned are the amino group and mono-substituted or di-substituted amino groups and etherified hydroxyl and mercapto groups.

Substituted amino groups which can be non-labile substituents of the heterocyclic compounds are, in particular, monoalkylamino and dialkylamino groups with 1-4 C atoms in the optionally substituted alkyl radicals and phenylamino and naphthylamino groups which are unsubstituted or contain one or two groups, preferably sulphonic acid groups, but can also contain other known substituents customary in dyestuff chemistry.

Amines which can be used as non-labile substituents are, for example: ammonia, methylamine, dimethylamine, ethylamine, pentylamine, hexylamine, diethylamine, npropylamine, i-propylamine, di-i-propylamine,"B-hydroxyetl1ylamine, y-aminopropanolss 8-eihoxyethylamine, -propoxyethylamine, jS-methoxyethyIamine, bis-jS-methoxyethyI- amine, bis-ss-hydroxyethylamine, ethylethanolamine, cyclohexylamine, N-methylcyclohexylamine, aminoacetic acid, ss-sulphato-propylamine, taurine, N-methyltaurine, nbutylamine, i-butylamine, dimethylaminopropylamine, piperidine, morpholine, aniline, o-, m-or p-toluidine, o-, m-or p-chloroaniline, aniline-o-, aniline-m-or aniline-psulphonic acid, aniline-2,4- or aniline-2,5-disulphonic acid, aniline-o-, aniline-m-or aniline-p-carboxylic acid, 4-aminotoluene-2-or 4-aminotoluene-3-sulphonic acid, N methylaniline, N-ethylaniline-o-, N-ethylaniline-m-or N-ethylaniiine-p-sulphonic acid, aniline-w-methane-sulphonic acid, benzylamine, N--hydroxyedtyt-benzylamine, benzyi- aminesulphonic acid and ss-acetylaminoethylamine.

Etherified hydroxyl and mercapto groups are, in particular, alkoxy and alkylthio groups with up to 4 carbon atoms which are optionally substituted in the alkyl radical, phenoxy and phenylthio groups which can preferably carry in the phenyl radicals sulphonic acid substituents, but also other known substituents customary in dyestuff chemistry; also chlorine atoms and cyano, nitro and carboxyl groups in the 5-position of a pyrimidinyl radical fall within the category of non-labile substituents, as do one of the two chlorine atoms in the 2,3-dichloroquinoxaline, 2,4-dichloroquinazoline or 1,4 dichlorophthalazine radical.

Hydroxy or thio compounds which can be used to introduce non-reactive substituents are, for example: methanol, ethanol, propanol, it ; propanol, butanol, i-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, alkylphenyl with 1-9 C atoms in the alkyl chain, phenol-o-, phenol-m-or phenol-p-sulphonic acid, methylmercaptan, ethylmercaptan, thiophenol and 8-hydroxyethylmercaptan.

Amino groups which for their part additionally carry a reactive radical are an important group of non-labile, substituted amino groups. If this additional reactive radical is designated A', this group of non-labile substituents of the radical A has the general formula Het-BR-Het'-A' wherein Het and Het'independently of one another are an oxygen or sulphur atom, but preferably an optionally substituted-NH group, the bridge member BR is a divalent aliphatic, aromatic or araliphatic radical and A'is one of the radicals mentioned above for A, but which for its part contains no further reactive group in a non-labile group which may be present.

With regard to the preferred meaning of Het and Het'mentioned, the grouping -Het-bridge member-Het'is preferably derived from aliphatic or aromatic diamines.

Suitable aliphatic diamines contain alkyl chains with 2-6 C atoms or cycloalkyl chains with 5 or 6 C atoms, it being possible for two cycloalkyl chains also to be linked by the radical of a hydrocarbon with 1-3 C atoms. Although the aikyl and cycloalkyl radicals can be substituted, except for the two amino groups they generally contain no further substituents. Alkyl chains which are interrupted by a secondary or tertiary nitrogen atom and diamines in which one or both nitrogen atoms are sub- stituted by an additional alkyl group with 1-6 C atoms or by a cycloalkyl group with 5 or 6 C atoms, in addition to being substituted by the alkyl chain, are also suitable.

Ethylene-diamine is preferred. Further examples which may be mentioned are: 1,3diaminopropane, 1,2-propylenediamine, 3-methylamino-propylamine, bis- (3-amino- propyl)-methylamine, dipropylenetriamine, 2-aminomethylcyclopentylamine, 3-amino-l- propane, 2,2-bis- (4-aminocyclohexyl)-propane, 1,4-diaminobutane and 1,6-diaminohexane.

Suitable aromatic or araliphatic diamines contain as the hydrocarbon radical radicals of optionally substituted mononuclear or dinuclear aromatic compounds of the benzene, alkylbenzene, naphthalene, alkylnaphthalene, biphenyl or diphenyl series, for example, the radical of benzene, sulphobenzene, disulphobenzene, naphthalene, sulphonaphthalene, disulphonaphthalene, dimethylbiphenyl, disulphobiphenyl, diphenylmethane, diphenylethane, sulphodiphenylmethane, sulphodiphenylamine and sulphodiphenyl ether. The radical of benzene and its monosulphonic acid and disulphonic acids, for example, the 1,4-phenylene, 1,3-phenylene, 2-sulpho-1, 4-phenylene, 3-sulpho1,4-phenylene, 4-or 5-sulpho-l, 3-phenylene, 2,6-disulpho-1,4-phenylene, 2,5-disulpho1,4-phenylene and 4,6-disulpho-l, 3-phenylene radicals.

The following list contains further radicals of mononuclear or dinuclear aromatic compounds which may be used as bridge members: 2-carboxy-1, 4-phenylene, 3-carboxy1,4-phenylene, 4-, 5-or 6-carboxy-1, 3-phenylene, 2-carboxy-6-sulpho-1, 4-phenylene, 2,5-dicarboxy-1, 4-phenylene, 4-sulpho-l, 5-naphthylene, 4-sulpho-2, 6-naphthylene, 2carboxy-1, 5-naphthylene, 1-sulpho-Z, 6-naphthylene, 4,8-disulpho-2,6-naphthylene and 3,7-disulpho-1,5-naphthylene.

Further bridge members which may be used are derived from the following hydrocarbons, the positions indicated in brackets after the names designating the positions of the bonds to the radicals Het (first number) and Het' (second number): 2,2'dimethyl-diphenyl (4,4'), 3,3'-dimethoxy-diphenyl (4,4'), 2,2'-disulpho-biphenyl (4,4'), diphenyl-ethane (4,4'), diphenyl-methane (4,4'), 2,2'-disulpho-diphenylmethane (4,4'), 3,3'-disulpho-diphenyl-ethane (4,4'), 2,2'-disulpho-diphenyl ether (4,4'), stilbene-2, 2'-disulphonic acid (4,4'), methylphenyl (4, w), 1-methyl-phenyl-3- sulphonic acid (4, w), 5-methyl-naphthalene-l-sulphonic acid (2,) diphenylamine (4,4'), 2-sulphodiphenylamine (4,4') and 6-methoxy-diphenylamine-2-sulphonic acid (3, 4').

Preferred radicals A and A'are, in particular, radicals of six-membered heterocyclic compounds which are derived from s-triazine.

B is, in particular, a radical of a mononuclear or dinuclear aromatic or araliphatic hydrocarbon which is optionally substituted by one-SO3H group and which can be substituted, in each nucleus, by alkoxy with 1-4 C atoms,-SO, R,' or an additional -SO ; H group, by one or two identical or different substituents of the groups halogen,

or-COOH or by one to three identical or different alkyl radicals with 1-4 C atoms, R,"denoting hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical with Z-6 C atoms which is optionally substituted by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, preferably acetylamino, benzoylamino, alkanoyloxy with 1-6 C atoms, preferably acetyloxy,-COOH or-S03H, a phenalkyl or naphthalkyl radical with 1-3 C atoms in the aliphatic chain, phenyl or naphthyl, it being possible for the aromatic nuclei to be substituted by Cl, Br, OH, alkyl and/or alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms,-COOH or-SO3H, Rx"being hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical with 2-6 C atoms which is optionally substituted by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C atoms,-COOH or-SO, H or an unsubstituted alkyl radical with 7-20 C atoms and Re'denoting methyl, carboxyoxymethyl, alkyl with 2 or 3 C atoms, benzyl or phenyl, it being possible for the aromatic nuclei to be monosubstituted or disubstituted by-. COOH or-SO, H.

Araliphatic radicals represented by B are always bonded to the primary amino group with the aromatic nucleus and to the-NR, A group with the alkylene chain. Monouclear aromatic or araliphatic radicals which can be represented by B are the optionally substituted radicals phenylene and monomethylene-phenylene or poly methylene-phenylcne of the general formula

in which n denotes an integer from 1 to 10.

Dinuclear aromatic or araliphatic radicals which can be represented by B are the optionally substituted radicals naphthylene, monomethylene-naphthylene or polymethyl- ene-naphthylene of the general formula

in which n denotes an integer from 1 to 3, and the optionally substituted radicals of the formulae

Examples of mononuclear or dinuclear aromatic or araliphatic hydrocarbon radicals which can be represented by B in the dyestuffs which can be manufactured according to the invention are: 1,4-phenylene, 1,3-phenylene, 2-sulpho-1,4 phenylene, 3-sulpho-1,4-phenylene, 4-or 5-sulpho-1, 3-phenylene, 2 carboxy-1, 4-phenylene, 3-carboxy-1, 4-phenylene, 4-, 5-or 6-carboxy-1, 3 phenylene, 2-carboxy-5-sulpho-1, 4-phenylene, 2-carboxy-6-sulpho-1, 4 phenylene, 3-carboxy-6-sulpho-1,4-phenylene, 6-carboxy-4-sulpho-1, 3 phenylene, 5-carboxy-3-sulpho-1, 3-phenylene, 2,5-dicarboxy-1,4-phenylene, 4,6-dicarboxy-1,3-phenylene, 2-chloro-5-sulpho-1, 4-phenylene, 2-chloro 6-sulpho-1,4-phenylene, 3-chloro-6-sulpho-1, 4-phenylene, 6-chloro 4-sulpho-1, 3-phenylene, 2-chloro-5-carboxy-1, 4-phenylene, 2,6-disulpho 1,4-phenylene, 2,5-disulpho-1,4-phenylene, 4,6-disulpho-1,3-phenylene, 3-chloro-6-carboxy-1, 4-phenylene, 6-chloro-4-carboxy-1, 3-phenylene, 4-chloro-5-carboxy-1, 3-phenylene, 2-methyl-5-carboxy-1, 4-phenylene, 2-ethyl-6-carboxy-1, 4-phenylene, 3-ethyl-6-sulpho-1, 4-phenylene, 6-ethyl-4-carboxy-1, 3-phenylene, 6-propyl-4-sulpho-1, 3-phenylene, 5-isopropyl-4-sulpho-1, 3-phenylene, 5-isopropyl-6-carboxy-1, 3 phenylene, 4-n-butyl-6-sulpho-1, 3-phenylene, 3-n-butyl-6-sulpho- 1,4-phenylene, 4-tert.-butyl-6-sulpho-1, 3-phenylene, 3-isobutyl-6- sulpho-1, 4-phenylene, 2,5-diisopropyl-6-sulpho-1,4-phenylene, 2,4-diethyl 5-carboxy-1, 3-phenylene, 2,4,6-trimethyl-5-sulpho-1, 3-phenylene, 2 cyano-1,4-phenylene, 4-cyano-1,3-phenylene, 2-cyano-5-sulpho-1,4 phenylene, 2-trifluoromethyl-1, 4-phenylene, 2-methylsulphonyl-1, 4-phenylene, 2-ethylsulphonyl-1,4-phenylene, 4- -methoxy-ethylsulphonyl-1,3 phenylene, 4-sulpho-1,5-naphthylene, 8-sulpho-1,5-naphthylene, 4-sulpho 2,6-naphthylene, 2-carboxy-1,4-naphthylene, 2-carboxy-1,5-naphthylene, 5-carboxy-1, 4-naphthylene, 3-carboxy-1,8-naphthylene, 3-carboxy-1, 5 naphthylene, 4-carboxy-2,6-naphthylene, 4-carboxy-2, 7-naphthylene, 1- sulpho-2,6-naphthylene, 8-sulpho-1,3-naphthylene, 4,8-disulpho-2,6 naphthylene, 3,7-disulpho-1,5-naphthylene, 1-sulpho-4-chloro-2, 6 naphthylene, 1-chloro-5-sulpho-2, 6-naphthylene, 1-chloro-7-sulpho- 2, 6-naphthylene, 2-chloro-6-sulpho-1, 4-naphthylene, 1-methyl-4-sulpho- 2,6-naphthylene and 2-methyl-7-sulpho-1,4-naphthylene. In each of these radicals the azo group is in the 1-position of the phenyl nucleus or in the 1-position or 2-position of the naphthalene nucleus. In the list which follows, examples of compounds from which further divalent radicals which can be represented by B are derived are indicated. The positions of the two bonds with which the divalent radicals are bonded on the one hand to the azo group (first position given) and one the other hand to the group-NR, A (second position given) of the dyestuffs which can be manufactured according to the invention are indicated in the second column of the table.

Position of the bonds Compound from which B is derived of B Diphenyl 4, 4' 2,2'-dimethyl-diphenyl 4,4' 3,3'-dimethoxy-diphenyl 4,4' 3,3'-dichloro-diphenyl 4,4' 3,3'-dimethyl-diphenyl 4,4' 2,2'-disulpho-diphenyl 4, 4' diphenyl-ethane 4, 4 diphenyl ether 4,4' 2,2'-disulpho-diphenyl-methane 4,4' 2,2'-disulpho-diphenyl-ethane 4,4' 3,3'-disulpho-diphenyl-ethane 4,4' 2,2'-disulpho-diphenyl ether 4,4' 2-sulphamide-diphenyl-ethane. 4,4' 2,2'-di sulphamido-diphenyl-ethane 4,4' 2,2'-di-S-hydroxye thy Isulphamido-diphenyl-ethane 4,4' stilbene-2,2'-disulphonic acid 4,4' methyl-phenyl 4,# l-methyl-phenyl-3-sulphonic acid 4,# 1-ethyl-phenyl-2-sulphonic acid 4,# I-propyl-phenyl-3-sulphonic acid 4, co 5-methyl-naphthalene-1-sulphonic acid l, co 6-methoxy-dipheny lamine-2'-sulphonic acid 3,4' 4-methyl-diphenylamine-2'-sulphonic acid 3,4' diphenylketone-5, 5'-disulphonic acid 3, 3' diphenylketone-3'-sulphonic acid3, 4' diphenylfulphone 4,4' 4,4'-dichloro-diphenylsulphone 3, 3 4,4'-disulpho-diphenylsulphone 3,3' 4-methyl-5-sulpho-diphenylsulphone 3, 3' The optionally substituted radicals phenylene, naphthylene,

and preferred for B in the dyestuffs which can be manufactured according to the invention.

The optionally substituted mononuclear or dinuclear aromatic or araliphatic hydrocarbon radical represented by B appropriately contains at least one sulpho group or carboxyl group, but valuable dyestuffs can also be obtained with radicals of the general definition of B which contain no acid group conferring solubility in water.

Dyestuffs which can be manufactured according to the invention in which B is phenylene or phenylene which is substituted by one or two carboxyl groups or by one or two sulpho groups or a naphthylene radical which is substituted by one or two sulpho groups or a stilbenylene radical which is substituted by one or two sulpho groups, and in particular those in which B is a radical of the formula

the position shown here corresponding to the position in the general formula I, are particularly preferred.

R, denotes, in particular hydrogen, methyl, carboxymethyl, sulphomethyl or an alkyl radical with 2-4 C atoms which is optionally substituted by Cl, Br, OH, alkoxy with 1-6 C atoms, alkanoylamino with 1-6 C atoms, benzoylamino, alkanoyloxy with 1-6 C atoms,-COOH or-SO3H.

Divalent radicals B which carry no further substituents, except for carboxylic acid and sulphonic acid radicals, are particularly preferred.

Examples of amines of the formula VI are indicated in the following table:

HM-B-N-A X z A ? H H0 aS-C-CH2-CH2-C 1 H-j-N-0 lu ao3sSE S-c-c-cs2 ao3s2 ~Clt nu 2s7 -C1 3 Bu gui H-C, N cri Cl s n Cl 'OT JSO, CH, c cul 0 cri u 1 ì03S w H I HC. S t 3 1 , I

92N-B-N-A X z R? Ho-N- ? Cl :, x J S ' I N IYC 1 . g2 H-~C, N, C 1 OH H03 XN) C1 ) L-S N C 1 CH-S i .

?--" 3 22'T 0 CH S j C 1 HO s 3 $2I' . 1 N~ C 1 1 Cul HOS 6N Cri Ho3 s EZil i i S03 : i N X N-3 ifyx ci Fi W

'J^2N-B-t 7 SOU S03a' HO H Cl HO Cl CI , g ; i w 3' ; 2 H c 1 si 31i 1 SOH ci CI H I S03H N X C1 w ~ y u l, l It | N, N l C 1 Ho 3 Cl 1 N su in 2 N, . x c I z E jX nT '1 ' O-.

Hu 3 ti N N N x zizi a N N X

H2N-B-N-A X ! R7 H L ; ll3 HO ?-\"-0-CS "CH, H CH3 3SN NS N ~ ~ CaH3 H 0 S H-N Y N 3 N N N-CH2-CH2-,'- N1-'i SC3 N-N N 2 2 fr 3 L ci HCl H, 2 N so 3H N x Lu 3 Y C1 C3 1 H2. : S03H N X N Xl SOH Xl j HO, S N N EN, N 1 SO"H C3 N, i 2 At y X N-Iroc, , L 0 S H N 1 Ii H N. Id z 5 Cl SOH ? l 3 z

u2N-B-N-A x t R ? H2N i-H Y cri si Il H2It i N- 2 : C/ HO S 3 H HO3s H 1. 3 E03S2 c 4f l Hu3sS C1 H 2-3 Hots Cl H3 J'H-2-CH3 HOTS Zut Chez c l-Yk F w i .

CHg CZ'

HN-B-N-A X 7 F 2 5 lio3su HO s NYX rr// ? -i. NCC25 1"S C/ tT r H It I-.- ; S 4 3ii N \CF3aCL Fi0 S h N H -- H :, 2 S03H t Amines of the formula VI are manufactured in a manner which is in itself known by acylating diamines of the formula VIII with acylating agents of the formula XA according to the reaction equation

In this equation X denotes a displaceable atom or group, which can be split off by the nucleophilic attack of the diamine. Examples of diamines VIII which lead to amines of the formula VI by the reaction according to the above equation are given by the following list: p-phenylenediamine, N-methyl-p-phenylenediamine, N carboxymethyl-p-phenylenediamine, m-phenylenediamine, N-ss-hydroxyethyl- m-phenylenediamine, 1,4-phenylenediamine-2-sulphonic acid, 1-amino-4 N-sulphomethylamino-phenylene-2-sulphonic acid, 1,4-phenylenediamine2,5- or-2, 6-disulphonic acid, 1-amino-4-N-methylamino-phenylene-2, 6disulphonic acid, 1,3-phenylenediamine-4-sulphonic acid, 1,3-phenylenediamine4,6-disulphonic acid, 2,4-diamino-toluene-5-or-6-sulphonic acid, 2,6diamino-toluene-4-sulphonic acid, 2,5-diamino-1,3,5-trimethylbenzene-4sulphonic acid, 2,6-diamino-1,3-diethylbenzene-4-sulphonic acid, 2,4 diamino-1-chlorobenzene-6-sulphonic acid, 2,4-diamino-1-tert.-butyl benzene-6-sulphonic acid, 2,4-diaminotoluene-5-or-6-sulphamide, 2,6diaminotoluene-4-ethanol or diethanol-sulphamide, 1,4-diaminophenylene-2 diethylsulphamide, 1,3-diaminophenylene-4-sulphanilide, 1,3-diaminophenylene 4-ss-hydroxyethylsulphone, N-ethyl-p-phenylenediamine, N-propyl-p- phenylenediamine, N-butyl-p-phenylenediamine, N-pentyl-p-phenylene- diamine, N-hexyl-p-phenylenediamine, N-ss-hydroxy-propyl-p-phenylene- diamine, N-ss-carboxy-propyl-p-phenylenediamine, N-y-chloro-butyl- p-phenylenediamine, N-3-methoxy-butyl-p-phenylenediamine, N-3- propoxy-butyl-p-phenylenediamine, N-, B-acetylamino-ethyl-p-phenylene- diamine, N-ss-butyrylamino-ethyl-p-phenylenediarnine, N-benzoylamino- ethyl-p-phenylenediamine, 1-N-methyl-3-amino-benzene-4-sulphonic acid, 1-N-butyl-4-amino-benzene-3-sulphonic acid, 2,4-diaminophenol6-sulphonic acid, 2,4-diamino-1-methoxybenzene-5-sulphonic acid, 1,5 diaminonaphthalene, 1,5-diaminonaphthalene-3-sulphonic acid, 1,5-diaminonaphthalene-4-sulphonic acid, 1,5-diaminonaphthalene-2-sulphonic acid, 1,6 acid, 1,4-diaminonaphthalene-5-sulphonic acid, 1,4-diaminonaphthalene-7sulphonic acid, 1,8-diaminonaphthalene-4-sulphonic acid, 2,6-diamino naphthalene-8-sulphonic acid, 2,6-diaminonaphthalene-4,8-disulphonic acid, 1,5-diaminonaphthalene-3,7-disulphonic acid, 1,4-diaminonaphthalene-5carboxylic acid, 1,4-diaminonaphthalene-2-carboxylic acid, 1,8-diamino naphthalene-3-carboxylic acid, 4,4'-diaminodiphenyl, 2,2'-dimethyl-4,4' diaminodiphenyl, 3,3'-dichloro-4,4'-diaminodiphenyl, 4,4'-diaminodiphenyl2,2'-disulphonic acid, 3,3'-dimethoxy-4,4'-diaminodiphenyl, 1-amino-4aminomethyl-benzene, 1-amino-4-aminomethyl-benzene-3-sulphonic acid, 1-amino-4-ss-aminoethyl-benzene-2-sulphonic acid, 1-amino-4-7 aminopropyl-benzene-3-sulphonic acid, 2-amino-5-aminomethyl- naphthalene-1-sulphonic acid, 4,4'-diamino-diphenylmethane-2,2'-disulphonic acid, 4,4'-diamino-diphenylethane-2,2'-disulphonic acid, 4,4' diamino-diphenylethane-mono-sulphamide, 4,4'-diamino-diphenylethanedisulphamide, 4,4'-diaminostilbene-2, 2'-disulphonic acid, 4,4'-diamino diphenylmethane, 4,4'-diamino-diphenylethane-di-, B-hydroyethylsulphamide, 4,4'-diamino-diphenyIamine-3-sulphonic acid, 3,4'-diamino-6-methoxy diphenylamine-2'-sulphonic acid, 3,4'-diamino-4-methyl-diphenylamine-2'sulphonic acid, 3,3'-diaminobenzophenone-5,5'-disulphonic acid, 3,4'-diamino benzophenone-3'-sulphonic acid, 4,4'-diamino-diphenylsulphone, 4,4'-dichloro3,3'-diamino-diphenylsulphone, 3,3'-diamino-4-rr, ethyl-diphenylsulphone5-sulphonic acid and 3,3'-diamino-diphenylsulphone-4,4'-disulphonic acid.

A large number of examples of acylating agents of the formula XA which can be reacted with diamines to give amines of the formula VI according to the above equation are described in the literature. The most important ones, representing the entire class, are mentioned in the following list: cyanuric chloride and cyanuric bromide, dihalogeno-mono-amino-triazines, it being possible for the amino group as the non-reactive substituent to be substituted analogously to the equation described above, such as 2,6-dichloro-4-amino-triazine, 2,6-dichloro-4-methylaminotriazine, 2,6-dichloro-4-hydroxyethylaminotriazine, 2,6-dichloro-4-phenylaminotriazine, 2,6-dichloro-4- {o-, m-or p-sulphophenyl)-aminotriazine or 2,6-dichloro-4- (2', 4'- or 2', 5'-disulphophenyl)-aminotriazine, dihalogeno- aLkoxy-syrn.-triazines and dihalogeno-aryloxy-sym.-triazines, such as 6- dichloro-4-methoxytriazine, 2, 6-dichloro-4-i-propoxytriazine, or 2,6 dichloro-4-phenoxytriazine, tetrahalogenopyrimidines, such as terrachloro-tetra- bromo or tetrafluoro-pyrimidine, 2,4,6-trihalogeno-pyrimidines, such as 2,4,6trichloropyrimidine, 2,4,6-tribromopyrimidine or 2,4,6-trifluoropyrimidine, 2, 4,6 trichloro-5-nitropyrimidine, 2,4,6-trichloro-5-methylpyrimidine, 2,4,6 trichloro-5-carbomethoxypyrimidine or 2,4,6-trichloro-5-cyanopyrimidine or 2, 6 difluoro-4-methyl-5-chloropyrimidine, 2,4-difluoro-pyrimidine-5ethylsulphone, 2,6-diíluoro-4-chloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine, 4,6-difluoro-2,5-dichloropyrimidine or 4,6-difluoro-2,5-dibromopyrimidine, 2-methylsulphonyl-4-chloro-6-methylpyrimidine, 2,6-bis methylsulphonyl-4, 5-dichloropyrimidine, 2-methylsulphonyl-4, 5-dichloro- 6-methylpyrimidine, 2-ethylsulphonyl-4, 6-dichloropyrimidine, derivatives of heterocyclic carboxylic or sulphonic acids, such as 3,6-dichloropyridazine-4carboxylic acid chloride, 2, 4-dichloropyrimidine-5-carboxylic acid chloride, 2, 4,6-trichloropyrimidine-5-carboxylic acid chloride, 2-methyl-4-chloro pyrimidine-5-carboxylic acid chloride, 2-chloro-4-methylpyrimidine5-carboxylic acid chloride, 2,6-dichloropyrimidine-4-carboxylic acid chloride, 2-methylsulphonyl-6-chloropyrimidine-4-carboxylic acid chloride or 2methylsulphonyl-6-chloropyrimidine-5-carboxylic acid chloride, 2-ethyl sulphonyl-6-chloropyrimidine-4-carboxylic acid chloride or 2-ethylsulphonyl6-chloropyrimidine-5-carboxylic acid chloride, 2,6-bis- (methylsulphonyl) pyrimidine-4-carboxylic acid chloride, 2-methylsulphonyl-6-methyl-4 chloropyrimidine-5-carboxylic acid chloride or bromide or 2-methylsulphonyl- 6-methyl-4-bromopyrimidine-5-carboxylic acid chloride or bromide, 2,6bis- (methylsulphonyl)-4-chloropyrimidine-5-carboxylic acid chloride, 2-or 3-monochloroquinoxaline-6-carboxylic acid chloride or 2-or 3-monochloro quinoxaline-6-sulphonic acid chloride, 2-or 3-monobromoquinoxaline-6 carboxyHc acid bromide or 2-or 3-monobromoquinoxaline-6-sulphonic acid bromide, 2,3-dichloroquinoxaline-6-carboxylic acid chloride or 2,3-dichloroquinoxaline-6-sulphonic acid chloride, 2, 3-dibromnaiiinoxaline acid bromide or 2,3-dibromoquinoxaline 6-sulphonic acid bromide, 1,4-dichlorophthalazine-6-carboxylic acid chloride or 1,4-dichlorophthalazine-6-sulphonic acid chloride and the corresponding bromine compounds, 2,4-dichloroquinazoline6-carboxylic acid chloride, 2,4-dichloroquinazoline-7-carboxylic acid chloride or 2,4-dichloroquinazoline-6-sulphonic acid chloride or 2,4-dichloroquinazoline7-sulphonic acid chloride and the corresponding bromine compounds, N-methyl N- (2,4-dichlorotriazinyl-6)-aminoacetyl chloride, 2-chlorobenzthiazole-5carboxylic acid chloride or 2-chlorobenzthiazole-6-carboxylic acid chloride or 2-chlorobenzthiazole-5-sulphonic acid chloride or 2-chlorobenzthiazole-6- sulphonic acid chloride and the corresponding bromine compounds, 2-methyl- sulphonyl-or 2-ethylsulphonyl-or 2-phenylsulphonyl-benzthiazole-5-sulphonic acid chloride or 2-methylsulphonyl-or 2-ethylsulphonyl-or 2-phenylsulphonylbenzthiazole-6-sulphonic acid chloride or aliphatic reactants, such as acrylic acid chloride, mono-, di-or tri-chloroacrylic acid chloride, 3-chloropropiorric acid chloride, 3-phenylsulphonyl-propionic acid chloride, 3-methylsulphonyl-propionic acid chloride, 3-ethylsulphonyl-propionic acid chloride, 3-chloroethane-sulphochloride, a-methylsulphonyl acrylic acid chloride and e-bromoacrylic acid chloride.

The acylation of diamines of the formula VIII with the compounds of the formula XA according to the above equation is carried out in a manner which is in itself known in an aqueous, aqueous-organic or organic solvent by means of a Schotten Baumann reaction at temperatures between 0 and 80 C, preferably between 10 and 25 C, the acid liberated appropriately being neutralised or buffered off by adding alkali, for example, sodium bicarbonate, sodium carbonate, sodium hydroxide solution or sodium acetate. Possible organic solvents are, above all, acetone, chlorinated hydrocarbons, such as ethylene chloride or chlorobenzene, or also aprotic polar solvents, such as dimethylformamide.

The diazotisation of amines of the formula VI is carried out in a manner which is in itself known in an aqueous medium by reacting the amines with 1 mol of nitrous acid, or of an agent which releases nitrous acid, in the presence of at least 2 equivalents, preferably approximately 2.5 equivalents, of a strong acid, per 1 mol of amine A salt of nitrous acid, in particular an alkali metal salt, such as sodium or potassium nitrite, is generally employed, in a mineral acid medium, as an agent which releases nitrous acid.

If the diazonium compound of an amine of the formula VI is coupled to the pyrazolone V in the manufacturing process according to the invention, the manufacture according to the invention of water-soluble, fibre-reactive phthalocyanine azo dyestuffs, had ended after the coupling reaction has ceased. This embodiment of the process according to the invention is preferred.

The dyestuff can then be isolated from the aqueous solutions thus obtained of the phthalocyanine azo dyestuffs by salting-out, or it can be obtained in the form of a solid dyestuff preparation by spray-drying the solutions.

In the manufacture according to the invention of the dyestuffs it is also possible to couple to the pyrazolone V, by known processes, diazonium compounds of amines of the formula VI HN-B-W wherein B has the meaning given above and W is a group which is a precursor of, i. e. can be converted to, a group of the formula-NR,-A. Suitable groups for W are, for example, acylamino groups of the formula IX

-N-acyl R, IX wherein acyl is any desired aliphatic or aromatic acyl group which can be split off by saponification. Aliphatic acyl groups appropriately have no more than 3 C atoms, preferably 2 C atoms ; aromatic acyl groups are appropriately derivatives of the benzoyl group preferably benzoyl itself.

If W represents an acylamino group of this type, the dyestuffs are saponified, appropriate'; hy warming with alkalis, such as, for example, 2-10 /, strength sodium hydroxide solution, to temperatures from 80 to 120 C and the dyestuffs thus obtained of the formula la

wherein B, Pc, ar, R"R2, Rs, R"R"k, I and m have the meanings given above, are acylated with an acylating agent of the formula X-A wherein A is a fibrereactive radical and X is a displaceable atom or group. The same reaction conditions and compounds X-A which are in themselves known and which were indicated above for the manufacture of amines of the formula VI, are suitable for this.

Furthermore, it is possible to employ amines of the formula VI in which W denotes a nitro group in the manufacture according to the invention of dyestuffs in which R, is H. The phthalocyanine azo dyestuffs thus obtained are reduced in a manner, which is in itself known and the dyestuffs of the formula Ib then present

wherein B, Pc, ar, R,, R2, Rs, R"k, I and m have the meanings given above, are then acylated in a manner which is in itself known with an acylating agent of the formula XA, fibre-reactive dyestuffs of the formula I being obtained.

The water-soluble fibre-reactive phthalocyanine dyestuffs which can be manu factured according to the invention are outstandingly suitable for dyeing and printing cellulose materials, cellulose-containing materials and natural and synthetic polyamide materials. They are distinguished by a high degree of fixing, in particular during printing processes and fixing by dry heat, and good washing-out of the non-fixe portion of dyestuff and give yellowish-tinged to bluish-tinged green dyeings and prints of high brilliance and depth of colour with very good fastness to light, good fastness to wet processing, such as washing at 60 C and 95 C, fastness to sea water, fastness to acid and alkaline perspiration, fastness to chlorinated water, fastness to peroside and fastness to flue gas.

Mixtures of dyestuffs which can be manufactured according to the invention, in particular those in which the meanings of k and/or 1 and/or m in the individual components are different, are outstandingly suitable for dyeing and printing cellulose materials and have the same advantageous properties as the individual dyestuffs.

Mixtures of this type are obtained, for example, if amines of the formula II having individual components which are different to one another with respect to the meanings of k and/or 1 and/or m are used as starting materials in the manufacture, according to the invention, of mix es Mixtures of amines of the formula II in which one component is generally substantially predominant, are usually obtained when they are manufactured by reacting phthalocyanine sulphochlorides with amines.

Example 1.

188 g of m-phenylenediamine-sulphonic acid are dissolved in about 6,000 ml of water to give a neutral solution. 190 g of cyanuric chloride, dissolved in acetone, are added to this solution at 0-5 C and the pH is simultaneously kept between 6 and 7 with about 100 ml of 10 N sodium hydroxide solution. When no further mphenylenediamine-sulphonic acid can be detected, 70 g of sodium nitrite are added to the neutral solution and the mixture is then stirred into 250 ml of 10 N hydrochloric acid at 0-3 C. When the diazotisation ceases, the diazo suspension is added to a solution of N- [3- (3-carboxy-5-hydroxy-1-pyrazolyl)-4-sulpho- phenyll-Ni-trisulpho-phthalocyaninylsulphonamide, to which 100 g of bicarbonate have previously been added. The coupling ceases in a few minutes.

The green phthalocyanine azo dyestuff formed can be isolated by salting out or spray-drying.

The solution of the phthalocyaninepyrazolone, required for the coupling reaction, can be obtained in the following manner: 1,060 g of 3- (3-amino-4-sulpho-phenyl)-amino-sulphonyl-nickel phthalocyanine-3', 3", 3"'-trisulphonic acid, manufactured in the customary manner by condensation reaction of nickel phthalocyanine sulphochloride with 1,3-diaminobenzene-4-sulphonic acid, are stirred with 7, 000 ml of water and dissolved by adding 400 ml of 10 N sodium hydroxide solution. 72 g of sodium nitrite are added to this solution and the mixture is then stirred into a mixture of 2,000 g of ice and 300 ml of concentrated hydrochloric acid in the course of 30 minutes. A temperature of 0 to 5 C is maintained by adding a further 2,000 g of ice. After a short time, any possible excess of nitrite is decomposed by adding aminosulphonic acid. 21 g of acetylsuccinic acid dimethyl ester are poured into the diazo suspension thus obtained.

The pH value is subsequently initially kept at 5. 5 by sprinkling in approximately 13 g of sodium carbonate, and then at 5 to 6 with approximately 21 g of sodium bicarbonate. The mixture is subsequently stirred for approximately 1 hour. The end of the reaction can be recognised as being when the pH remains constant and when no change in shade occurs if a solution of H-acid in 2 N sodium carbonate is added to a sample.

350 ml of 10 N hydroxide solution are added to the solution thus obtained of 3- (nickel-trisulpho-phthalocyaninyl-sulphonylamino)-6-sulpho-phenyl- hydrazone of oxalacetic acid dimethyl ester, whereby the pH rises to values of 12 to 13. The mixture is stirred for several hours, preferably overnight, at room temperature.

The rearrangement to give N- [3- (3-carboxy-5-hydroxy-1-pyrazolyl)-4 sulpho-phenyl]-nickel-trisulpho-phthalocyaninyl-sulphonamide is then com- plete ; the pH is adjusted back to 8 with a little hydrochloric acid and the resulting crude solution is employed direct in the coupling reaction.

If the cyanuric chloride in the manufacture of the diazo component is replaced by a molar amount of one of the acylating agents in the following and the procedure followed is otherwise as described above, valuable green reactive dyestuffs are likewise obtained: 2,4,6-trisulpho-1,3,5-triazine, B-chloropropionic acid chloride, a dibromopropionic acid chloride, ss-phenylsulphenylpropionic acid chloride, B- pyridiniumpropionic acid chloride, ss-sulphatopropionic acid chloride, acrylic acid chloride, a-bromoacrylic acid chloride, 3-, B-chloroethylsulphonylbenzoic acid chloride, 4-vinylsulphonylcyclohexanecarboxylic acid chloride, 4-/ ?-chloroethy !- sulphonyl-2,5-endomethylene-cyclohexanecarboxylic acid chloride, - (ss- chloroethylsulphonyl)-butyric acid chloride, 2,4-dichloro-pyrimidine-5carboxylic acid chloride, 2,4-dibromo-pyrimidine-5-carboxyhc acid bromide, 2,4-difluoro-pyrimidine-5-carboxylic acid chloride, 2,6-dichloro-pyrimidine4-carboxylic acid chloride, 2,3-dichloroquinoxaline-6-carboxylic acid chloride, 2,3-dichloroquinoxaline-6-sulphonic acid chloride, 1,4-dichloro-phthalazine6-sulphonic acid chloride, 1,4-dichloro-phthalazine-6-carboxylic acid chloride, 2-methylsulphonyl-6-chloro-pyrimidine-4-carboxylic acid chloride, 3,6 dichloro-pyridazine-4-carboxylic acid chloride, 2-methylsulphonyl-6-chloro- pyrimidine-5-carboxylic acid chloride and 2,6-bis- (methylsulphonyl)pyrimidine-5-carboxylic acid chloride.

If the condensation product of nickel phthalocyanine sulphochloride and one of the amines mentioned in the following is used in the manufacture of the coupling component instead of the condensation product mentioned above of nickel phthalocyanine sulphochloride and 1, 3-diaminobenzene-sulphonic acid and the procedure followed is otherwise as described, valuable green reactive dyestuffs are likewise obtained: 1,4-phenylenediamine-2-sulphonic acid, 1,3-phenylenediamine-4,6disulphonic acid, 1,4-phenylenediamine-2,5-disulphonic acid, 1,4-phenylenediamine-2, 6-disulphoriic acid, 2,4-diaminotoluene-6-sulphonic acid, 2,6 diaminotoluene-4-sulphonic acid, 2,4-diamino-1,3,5-trimethylbenzene-6sulphonic acid, 2,6-diaminonaphthalene-4,8-disulphonic acid, 1,5-diamino naphthalene-2-sulphonic acid, 2, 6-diaminonaphthalene-8-sulphonic acid, 1 amino-4-aminomethyl-benzene-3-sulphonic acid, 2-amino-5-amino- methyl-naphthalene-1-sulphonic acid, 4,4'-diamino-diphenylamine-3 sulphonic acid, 3,3'-diamino-4-methyl-diphenylsulphone-5-sulphonic acid, 1,3-phenylenediamine (acetyl derivative, subsequently saponified), 2,4-diaminotoluene (acetyl derivative, subsequently saponified), 1,4-phenylenediamine (acetyl derivative, subsequently saponified), 4,4'-diamino-diphenylethane-2-2'-disulphonic acid, 4,4'-diamino-diphenylethane-mono-sulphamide, 4,4'-diamino diphenylethane-disulphamide, 4,4'-diaminostilbene-2-2'-disulphonic acid, 4,4'-diamino-diphenylethane-di-, B-hydroxyethylsulphamide, 4,4'-diamino diphenylamine-3-sulphonic acid, 3,4'-diamino-6-methoxy-diphenylamine2'-sulphonic acid, 3-4'-diamino-4-methyl-diphenylamine-2'-sulphonic acid, 3,3'-diaminobenzophenone-5-5'-disulphonic acid, 3,4'-diaminobenzo phenone-3'-sulphonic acid, 4,4'-diamino-diphenylsulphone, 4,4'-dichloro 3-3'-diamino-diphenylsulphone, 3,3'-diamino-4-methyl-diphenylsulphone5-sulphonic acid and 3,3'-diamino-diphenylsulphonic-4-4'-disulphonic acid.

Example 2.

268 g of p-phenylenediamine-2,6-disulphonic acid are reacted in the customary manner with 183 g of methoxy-dichloro-triazine. After adding 70 g of sodium nitrite, the solution of the resulting condensation product is allowed to run into 250 ml of 10 N hydrochloric acid, and the diazo suspension thus obtained is subsequently added, we described in Example 1, to a solution of bispyrazolone manufactured as described below from 535 g of 3,3'-bis- [ (4-aminophenvl)- aminosulphonyl]-nickel-phthalocyanine-3", 3"'-disulphonic acid. The pH is subsequently adjusted to 7-7. 2 with 4 N sodium carbonate solution and the green dyestuff formed is isolated by salting out or spray-drying.

The bispyrazolone employed as the coupling component was manufactured in the following manner : 533 g of 3, -bis [ (4-aminoghenyl)-amino-suIphvnyl-nickel-pfithalo- cyanine-3, 3"-disulphonic acid, manufactured in the customary manner by condensation of 0.5 mol of nickel phthalocyanine tetrasulphochloride with 1 mol of acetyl-p-phenylenediamine and saponification of the condensation product, are stirred with 3,500 ml of water and dissolved by adding 200 ml of 10 N sodium hydroxide solution. 70 g of sodium nitrite are added to this solution and the mixture is then stirred into a mixture of 2, 000 g of ice and 300 ml of concentrated hydrochloric acid in the course of about 30 minutes. The temperature is kept between 0 and 5 C by adding a further 100 g of ice. The mixture is subsequently stirred for about 10 minutes and any possible slight excess of nitrite is then removed with aminosulphonic acid. 135 g of acetylsuccinic acid diethyl ester are added to the diazo suspension thus obtained. The pH is adjusted to about 6 with approximately 250 g of sodium carbonate and kept at this value until no further diazo compound can be detected. A solution of turquoise-coloured 3,3'-bis- [4- (1,2-bis-ethoxy carbonyl-ethylidene)-hydrazino-phenyl-amino-sulphonyl-nickel-phthalo- cyanine-3", 3"'-disulphonic acid is thus obtained, which is converted direct to the corresponding bispyrazolone by the action of alkali by adding about 400 ml of 10 N sodium hydroxide solution and stirring the mixture at room temperature for approximately 4 hours.

If the corresponding 4,4', 4", 4"'-derivative is used instead of the amine employed above, valuable phthalocyanine hydrazones are likewise obtained.

If the condensation product of nickel phthalocyanine sulphochloride and two mols of one of the amines mentioned in the table which follows is used as the diazo component for the pyrazolone step instead of the amine employed above and the procedure followed is otherwise as described above, green phthalocyanine azo dyestuffs are likewise obtained. 1,3-phenylenediamine (acetyl derivative, subsequently saponified),', 4-diaminotoluene (acetyl derivative, subsequently saponified), 2,4 diaminoanisole (acetyl derivative, subsequently saponified), 1,4-phenylenediamine2-sulphonic acid, 2,4-diaminotoluene-6-sulphonic acid, 4-amino-benzyl- amine (4-acetyl derivative, subsequently saponified), 4,4'-diaminostilbenedisulphonic acid, 4,4'-diaminomethanedisulphonic acid or 4,4'-diamino-diphenylamine-3-sulphonic acid.

If the acetylsuccinic acid diethyl ester employed as the coupling component for the pyrazolone step is replaced by one of the following derivatives of succinic acid, arylhyc-azones which can be processed according to the invention to give valuable azo phthalocyanine dyestuffs are likewise obtained.

R, R. Z -CH3 -CH3 -H -CH3 -C2H4Cl -CH3 -CH,-i-C, H,-CH, -CH,-i-C, H q-COO-CH, -CH3-i-C6Hm-COO-C, Hs -CH3 -C2H4-OH -CH3 -CH3 -C3 H.-OCH,-COO-C. H, -CH,-C, H,-COO-C. H, -C3H7 -C2H5 -C3H7 -C5H11 -C2H5 -CH2-C6H5 -C9H19 -C2H5 -COO-CH3 -CtsH3s-CaHs-C6H6 -C, H,-O-CzHs-CzH,-C6H,-CH, If methoxydichlorotriazine is replaced by one of the reactive components mentioned in the following during the acylation of p-phenylenediamine-2, 6-disulphonic acid, soluble dyestuffs are likewise obtained. 2-amino-4, 6-dichloro-1,3,5triazine, 2-phenoxy-4,6-dichloro-1,3,5-triazine, 2-phenylamino-4,6dichloro-1,3,5-triazine, 2-N-methyl-N-phenylamino-4,6-dichloro-1,3,5triazine, 2-butylmercapto-4,6-dichloro-1,3,5-triazine, 2-ss-methoxyethoxy- 4,6-dichloro-1,3,5-triazine, 2- (2'-carboxyphenoxy)-4, 6-dichloro-1,3,5triazine, 2-carboxymethylthio-4, 6-dichloro-1, 3,5-triazine, 2-phenylthio4,6-dichloro-1,3,5-triazine, condensation product of 1 mol of cyanuric chloride and 1 mol of 2-ss-amino-ethylamino-4- (2', 5'-disulphophenylamino)-6- chlorotriazine-1,3,5, condensation product of cyanuric chloride and 1 mol of 24'-amino-3'-sulpho-phenylamino-4- (2"-carboxyphenylamino)-6-chlorotriazine-1,3,5, condensation product of cyanuric chloride and 1 mol of 2-3'-amino 4'-sulpho-phenylamino-4-n-butoxy-6-chlorotriazine-1, 3,5,2,4-disulpho6-chloro-1,3,5-triazine, tetrachloropyrimidine, 2,4,6-trichloropyrimidine, 5- cyano - 2, 4,6-trichloropyrimidine, 5-nitro-2,4,6-trichloropyrimidine, 2,4 difluoro-6-chloropyrimidine, 2-methylsulphonyl-4-methyl-6 chloropyrimidine, condensation product of cyanuric chloride and 2 - methoxy - 4 - ss hydroxyethoxy-6-chloro-1, 3,5-triazine, 2-methylsulphonyl-4, 6-dichlero- pyrimidine, 2,3-dichloroquinoxyline-5-carboxylic acid chloride, 2,3-dichloro quinoxyline-6-carboxylic acid chloride, 2, 3-dichloroquinoxaline-5-sulphonic acid chloride, 2,3-dichloroquinoxaline-6-sulphonic acid chloride, 2, 4 - dichloroquinazoline-6-carboxylic acid chloride, 2,4-dichloroquinazoline-6-sulphonic acid chloride, 2,4-dichloroquinazoline-7-sulphonic acid chloride, 1,4-dichloro phthalazine-6-carboxylic acid chloride, 3, 6 - dichloropyridazine - 4 - carboxylic acid chloride 2,4-dichloropyrimidine-5-carboxylic acid chloride or 2, 4 - difluoro Example 3.

If the corresponding molar amount of one of the amines mentioned in the table which follows is used instead of the amine indicated in Example 1, that is to say 3- [ (3-amino-4-sulpho-phenyl)-amino-sulphonyl]-nickel-phthalo- cyanine-3', 3", 3'-trisulphonic acid, and the procedure followed is otherwise as indicated therein, valuable hydrazones of oxalacetic acid methyl ester which can be further processed to correspondingly substituted pyrazolones

are likewise obtained.

R Rg ar k j ["L ~,. ~ ~.,. ~. ?. ~ ~~ ~~ -CH3 H q SO3E ? 1 1 -CH2-COOH H 2 1 1 -H-CI-SO CH )-1 1 2 -C2H4c 1 H 2 1 1 -C2Fi40J3 C2R J CH3 2 1 S3R S C2u4 0 C2H5 C2n5 < 2 1 1 H03S 0 3fi "3-C. COCI33 H -2 1 1 HOTS

R R R 8r k 1 r 0 3H -H-C6H0-h'Fi--COCH H1 1 Lions " .-H-C2HA-SOb-C2H-0-C2tla-N -2 1 1 -0 1 -H C2Hg SO3E-C2H4-0-C2} 1 o1 1 . J 'C613 \ S03R 2 1 1 -C6R13 S QSO3R 2 1 1 soufi SOH -H-c6i v z x x SOB S03 if .. H.. C20Bli H a ? X S03H

SpH R1 R2 R3 | ar k ll L m . ~. ~~ ~~... ~..~~~~ ~.

-H &verbar;-C4H9 I H 1 CH2bH &verbar; 2 1 1 1 -C3H7 B-CH2tE ! 2 1 1 S H .-H ~H9 g H2/\ 2 1 l 1 4 9 2 SU 3H S03H HOS 3 503H C2H5-C2HS CH3 H-/ 2 1 1 hots 03 s -C5-CsHs CHg . 2 1 1 OH OH 3 soin

R2 R3 ar k su H SOH -C2H4Br-C2H-Cfl2-S (13H \. 2 1 1 'S03H -C2H !-0--C2H5-CH2CH2-COOH < 3 2 1 1 -CISOH-C-CHCH-CCOtt--2 1 1 -c4-p, 8-cooll-C2 H5-CH3 C 3H, 2 -C ? H40i-C2H5-CH3--Cl 2 1 i -c2R 40 El-C2 H. 11 OH-CH3 2 OH I E | o

RA 2 R R r k 1 m -CZT, OK-C2OH fi- x 1 2 so 3H "c2H4-SO3H H 1 2 1 H03S N-C2H-S03fI H 1 1 1 H OR 1 2 1 H 0 0 3 25-COCHg 1 0 2 ~. J

RR R a r I k I I m OH so3H 1 1 2 SO. H H IN 0 0 3 \--i i 0004 Example 4.

If an at least molar amount of one of the compounds, mentioned in the following, which contain an amino group which can be acylated is added to the dyestuff manufactured according to Example 1 and the mixture is then warmed, in each case for one hour, to 30 , 40 and 50 , the pH being kept between 4 and 7 by adding alkali, such as sodium bicarbonate, sodium carbonate or sodium hydroxide solution, valuable green reactive dyestuffs are likewise obtained. In the case of ammonia or aliphatic amines, the alkali can be replaced by a second mol of amine. Ammonia, methylamine, diethylamine, isopropylamine, ethanolamine, diethanolamine, N, N-dimethylhydrazine, aniline, o-, m-or p-toluidine, N-methylaniline, aniline-2-, aniline-3-or aniline4-sulphonic acid, 2-, 3-or 4-aminobenzoic acid, aniline-methanesulphonic acid, , 8 aminoethanesulphonic acid, N-methyltaurine, aminoacetic acid, aniline-2,4or aniline-2,5-disulphonic acid or the condensation product of: p-phenylenediamine, cyanuric chloride and aniline-3-sulphonic acid, ethylenediamine, cyanuric chloride and aniline-2, 4-disulphonic acid, 1,4-phenylenediamine-2,5-disulphonic acid and iso-propoxy-dichlorotriazine, 1-3-phenylenediamine-4- sulphonic acid and ss-ethoxyethoxydichlorotriazine, p-phenylenediaminesulphonic acid and cyanuric chloride, p-phenylenediaminesulphonic acid and tetrachloro- pyrimidine, p-phenylenediaminesulphonic acid and 2,3-dichloroquinoxaline carboxylic acid chloride, p-phenylenediaminesulphonic acid and 2,6-dichloro pyrimidine-4-carboxylic acid chloride or p-phenylenediaminesulphonic acid and 3,6-dichloropyridazine-4-carboxylic acid chloride.

Example 5 : The diazo component employed in Example 1, that is to say 2-amino-4dichlorotriazinylamino-benzenesulphonic acid, is replaced by an equivalent amount of 2-amino-4-acetylamino-benzenesulphonic acid and the procedure followed is otherwise as described in Example 1.

200 ml of 10 N sodium hydroxide solution are subsequently added to the solution of the green azo phthalocyanine dyestuff formed and the mixture is stirred for five hours at 9S until the acetyl group is completely saponified.

The dyestuff solution thus obtained is neutralised with about 100 ml of 10 N hydrochloric acid and a solution of 190 g of cyanuric chloride in acetone is then added at 0-5 C. The pH value is simultaneously kept between 5. 0 and 6.5 by adding about 80 g of sodium bicarbonate in portions. The reaction has ended when no further amino groups which can be diazotised can be detected.

The dyestuff thus obtained is identical to that manufactured according to Example 1.

Hydrazones conforming to formula IV herein have been described and claimed per se in our contemporaneous Application No. 15757/77 (Serial No. 1550 527) (cf. formula I in the latter, hi which, however, R, takes the place of the R4'in the present formula IV).

Claims (46)

1. WHAT WE CLAIM IS :- 1. Process for the manufacture of water-soluble fibre-reactive phthalocyanine azo dyestuffs of the formula I

   wherein A is a fibre-reactive radical, B is a radical of an optionally substituted, mononuclear or dinuclear, aromatic hydrocarbon or araliphatic hydrocarbon the alkylene chain of which is bonded to the

   group, Pc is the radical of a metal-containing or metal-free phthalocyanine, ar is the radical of an optionally substituted, mononuclear or dinuclear, aromatic hydrocarbon or araliphatic hydrocarbon the alkylene chain of which is bonded to the

   group, R, is hydrogen, optionally substituted alkyl having 1--6 C atoms, phenalkyl or naphthalkyl having 1-3 C atoms in the aliphatic chain, phenyl or naphthyl, the aromatic nuclei being optionally substituted or further substituted, R : is hydrogen, optionally substituted alkyl having 1-6 C atoms or unsubstituted alkyl having 7-20 C atoms, R, is hydrogen or optionally substituted alkyl having 16 C atoms, R4 is hydrogen or optionally substituted alkyl having 1-6 C atoms or unsubstituted alkyl having 7-18 C atoms, R, is hydrogen or optionally substituted alkyl having 1-4 C atoms and k is 0,1,2 or 3,1 represents 0,1 or 2 and m represents 1,2,3 or 4 and the sum of k, I and m is 3 or 4, or an alkali metal, ammonium or alkaline earth metal salt thereof, in which process : (a) an amine of the phthalocyanine series of the general formula II

   in which the amino group substituent on the ar radical is bonded to an aromatic C atom of said radical ar and wherein Pc, ar, Ri, R, , R,, k, I and m have the same meaning as defined above in formula I, is diazotised and coupled in an aqueous medium at a pH value between 3 and 8 with a succinic acid derivative of the formula III

   wherein Ek'denotes optionally substituted alky ! having :-6 C atoms or unsubstituted alkyl ! having 7-'18 C atoms, R, denotes optionally substituted alkyl having 1^6 C atoms or unsubstituted alkyl having 7-18 C atoms and Z denotes hydrogen, an optionally substituted alkyl radical having 1-10 C atoms, an optionally substituted phenyl radical or alkoxycarbonyl having 2-6 C atoms, so as to form a hydrazone of the formula IV

   wherein Pc, ar, R"RZ, R3, R,', k, I and m have the same meaning as defined above in ftl1nnula 1 and R, has the same meaning as defined above in formula III ;

   wherein Pc, ar, R,, R2, Rs, R"k, 1 and m have the same meaning as defined above in formula I ; and (c) The pyrazolone of formula V is coupled with the diazonium compound of an amine of the general formula VI H2N-B-W wherein B has the same meaning as defined in formula I and W is a group of the formula-N (R,) A, wherein RT and A have the same meaning as defined above in formula I, or a precursor of said group-N (R,) A ; and when W is said precursor it is subsequently submitted to one or more reactions effective to convert it into the said group of the formula-N (R,) A; so as to produce said dyestuff compound of the formula I.
2. 2. A process as claimed in claim 1 wherein in the amine of formula II Pc is the radical of a metal-containing or metal-free phthalocyanine, ar is the radical of a mononuclear or dinuclear, aromatic or araliphatic hydrocarbon which is optionally substituted by aSOsH group and each nucleus being optionally further substituted, by alkoxy having 1 to 4 C atoms,-SO2-Re or additional-SO, H group, by one or two identical or different substituents selected from halogen,

   and-COOH, or denotes a phenylene radical which is optionally substituted by a -SOH group and which can be additionally substituted by one to three identical or different alkyl radicals having 1-4 C atoms, Ri and R,'can be the same or different and each represents hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which contains 2-6 C atoms and which is optionally substituted by CI, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, alkanoyloxy having 1-6 C atoms,-COOH or-SO, H, a phenalkyl or naphthalkyl radical having 1-3 C atoms in the aliphatic chain or phenyl or naphthyl, the aromatic nuclei being optionally substituted or further substituted by one or more of Cl, Br, OH, alkyl and/or alkoxy each having 1-6 C atoms, alkanoylamino having 1-6 C atoms,-COOH or-SOgH, R : and R :' can be the same or different and denote hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical which contains 2-6 C atoms and is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms,-COOH or-SO, H, or an unsubstituted alkyl radical having 7-20 C atoms, R3 is hydrogen, methyl, carboxymethyl, sulphomethyl, or an alkyl radical which contains 2-6 C atoms and is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 16 C atoms,-. COOH or-S03H, and R, is methyl, carboxymethyl, alkyl having 2 or 3 C atoms, or benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstituted by-COOH or-SO3H k represents the numbers 0,1,2 or 3,1 represents 0,1 or 2 and m represents 1,2,3 or 4 and the sum of k, landmis3or4.
3. 3. A process as claimed in claim 2 wherein R1 and/or R,'is alkyl having 2 to 6 carbon atoms and substituted by acetylamino, benzoylamino or acetoxy.
4. 4. A process as claimed in any of claims 1 to 3 wherein in the amine of formula II Pc is the radical of cobalt phthalocyanine, copper phthalocyanine or nickel phthalocyanine.
5. 5. A process as claimed in claim 4 wherein Pc is the radical of nickel phthalocyanine.
6. 6. A process as claimed in any of claims 1 to 5, wherein in the amine of formula II ar is an optionally substituted phenylene, mono-methylene-phenylene or poly-

   wherein n denotes an integer from 1 to 10, or naphthylene or monomethylenenaphthylene or polymethylene-naphthylene radical of the general formula

   wherein n denotes an integer from 1 to 3, or an optionally substituted radical of the formula
7. 7. A process as claimed in any of claims 1 to 6, wherein in the amine of formula II ar is an optionally substituted phenylene or naphthylene radical or an optionally -Jubstituted radical of the formula
8. 8. A process as claimed in any of claims 1 to 7, wherein in the amine of formula II ar is a phenylene radical which is optionally substituted by one or two carboxyl groups or by one or two sulpho groups, or a naphthyl radical which is substituted by one or two sulpho groups, or a stilbenylene radical which is substituted by one or two sulpho groups.
9. 9. A process as claimed in any of claims 1 to 8, wherein in the amine of formula II ar is a radical of the formula
10. 10. A process as claimed in claim 2 or any of claims 3 to 9 when dependent on claim 2 wherein in the amine of formula II R, and R,'are the same or different and each is hydrogen, alkyl having 2 to 3 C atoms, optionally substituted by OH, alkoxy having 1-3 C atoms,-COOH or-S03H, methyl, carboxymethyl or sulphomethyl.
11. 11. A process as claimed in claim 2 or any of claims 3 to 10 when dependent on claim 2 wherein in the amine of the phthalocyanine series of the formula II R2 ,, rl P-t Pri, the Rame or different and each is hydrogen, methyl, carboxymethyl, alkyl -COOH or-SOH, or unsubstituted alkyl having 1-20 C atoms.
12. 12. A process as claimed in claim 11 wherein R2 and R2'are the same or different and each is hydrogen, methyl, carboxymethyl or alkyl having 2 to 3 C atoms optionally substituted by OH.
13. 13. A process as claimed in any of claims 10 to 12 wherein R, and R2 as well as Rl'and R2'are the same or different and each is hydrogen, methyl or ss-hydroxyethyl.
14. 14. A process as claimed in any of claims 1 to 13, wherein in the amine of formula 11 R, is hydrogen, methyl, carboxymethyl, sulphomethyl or an ethyl radical which is optionally substituted by Cl, OH, alkoxy having 1 or 2 C atoms,-COOH or-SO, H.
15. 15. A process as claimed in any of claims 1 to 14, wherein in the amine of the phthalocyanine series of the formula II, 1 is 0, k is 2 or 3 and m is 1 or 2 and the sum of k+m is 4.
16. 16. A process as claimed in any of claims 1 to 15, wherein in the amine of formula II the substituents on the Pc radical are in the 3-positions and/or 4-positions of the phthalocyanine.
17. 17. A process as claimed in claim 16 wherein the substituents on the Pc radical are in the 3-positions of the phthalocyanine.
18. 18. A process as claimed in any of the preceding claims wherein in the succinic acid derivative of the formula III R,'and R5 are the same or different and each is alkyl having 2-6 C atoms substituted by Cl, Br, OH or alkoxy having 1-4 C atoms, or unsubstituted alkyl having 1-18 C atoms, and Z denotes hydrogen, alkyl having 1-10 C atoms optionally substituted by alkoxy having 1-4 C atoms, or alkoxycarbonyl having 2~6 C atoms, a phenyl radical optionally substituted by Cl, Br or alkyl or alkoxy having 1-4 C atoms, or alkoxycarbonyl having 2-6 C atoms.
19. 19. A process as claimed in claim 18 wherein R,'denotes ethyl substituted by Cl, OH or alkoxy having 1-2 C atoms, or unsubstituted alkyl having 1-b C atoms.
20. 20. A process as claimed in claim 18 or claim 19 wherein R,, is ethyl substituted by Cl, OH or alkoxy having 1-2 C atoms, or unsubstituted alkyl having 1-18 C atoms.
21. 21. A process as claimed in any of claims 18 to 20 wherein R, and Rs are identical and denote methyl or ethyl.
22. 22. A process as claimed in any of claims 18 to 21 wherein Z denotes hydrogen, alkyl having 1-3 C atoms, phenyl, methyl-phenyl or alkoxycarbonyl having 2 or 3 C atoms.
23. 23. A process as claimed in claim 22 wherein Z denotes methyl.
24. 24. A process as claimed in any of the preceding claims wherein in the diazonium compound of the amine of the general formula VI, A is a fibre-reactive radical which contains a radical which can be split off as an anion or as a neutral radical or a double bond which is capable of an addition reaction, B is a radical of a mononuclear or dinuclear, aromatic or araliphatic hydrocarbon which is optionally substituted by one -S03H group and each nucleus being optionally further substituted, by alkoxy having 1-4 C atoms,-SOR,,'or an additional-S03H group, by one or two identical of different substituents selected from halogen,

    or-COOH or by one to three identical or different alkyl radicals having 1-4 C atoms, Rl"denoting hydrogen, methyl, carboxymethyl, sulphomethyl, an alkyl radical having 2-6 C atoms which is optionally substituted by Cl, Br, OH, alkoxy, alkanoylamino or alkanoyloxy each having 1-6 C atoms,-COOH or-SOsH, a.'"enalky ! or naphthalkyl radical having 1-3 C atoms in the aliphatic chain, or p. ienyl or naphthyl, the aromatic nuclei being optionally substituted or further substituted by one or more of Cl, Br, OH, alkyl and/or alkoxy each having 1-6 C atoms, alkanoylamino having 1-6 C atoms,-COOH or-SO, H, R/'denoting hydrogen, methyl, carboxyunethyl, sulphomethyl, an alkyl radical having 2-6 C atoms which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms,-COOH or-S03H @@ @@ @@@@@@@@@@@@@ @@@@@ radical having 7-@@ C atoms, R' denoting methyl carboxy- methyl, alkyl having 2 or 3 C atoms, benzyl or phenyl, the aromatic nuclei being optionally monosubstituted or disubstituted by-COOH or-SO, H and R ; is hydrogen, methyl, carboxymethyl, sulphomethyl or an alkyl radical having 2-4 C atoms which is optionally substituted by Cl, Br, OH, alkoxy having 1-6 C atoms, alkanoylamino having 1-6 C atoms, benzoylamino, alkanoyloxy having 1-6 C atoms, -COOL or-SO, H.
25. 25. A process as claimed in claim 24 wherein Rl"is allcyl having 2 to 6 carbon atoms substituted by acetylamino, benzoylamino or acetoxy.
26. 26. A process as claimed in any of the preceding claims wherein in the diazonium compound of the amine of the general formula VI, A is the radical of an aliphatic carboxylic or sulphonic acid which contains a substituent which can be nucleophilically replaced; or is an a, ss-unsaturated aliphatic carboxylic or sulphonic acid; or is the radical of an aliphatic carboxylic or sulphonic acid which is convertible to the radical of an a unsaturated aliphatic carboxylic or sulphonic acid with the splitting off of a neutral or anionic group.
27. 27. A process as claimed in any of claims 1 to 25 wherein in the diazonium compound of the amine of the general formula VI, A is the radical of a heterocyclic carboxylic or sulphonic acid which contains a substituent which can be nudeophilically replaced.
28. 28. A process as claimed in any of claims 1 to'9'5 wherein in the diazonium compound of the amine of the general formula VI, A is the radical of a six-membered heterocyclic compound having 2 or 3 N atoms and at least one substituent which can be nudeophilically replaced.
29. 29. A process as claimed in claim 28 wherein said six-membered heterocyclic compound additionally has a non-labile substituent which in turn contains no fibrereactive radical having a radical which can be split off as an anion or as a neutral radical or a double bond which is capable of an addition reaction.
30. 30. A process as claimed in any of claims 1 to 24 wherein A is the radical of s-triazine.
31. 31. A process as claimed in claim 20 wherein said six membered heterocyclic compound additionally has a non-labile substituent of the general formula -Het-BR-Het'-A'wherein Het and Het'ar. the same or different and each is an oxygen or sulphur atom or optionally substituted-N'H-group, BR is a divalent aliphatic, aromatic or araliphatic radical and A'has the same meaning as any of the values given for A in any of claims 23 to 30.
32. 32. A process as claimed in any of the preceding claims wherein in the diazonium compound of the amine of the general formula VI, B is an optionally substituted phenylene, monomethylene-phenylene or polymethylene-phenylene radical of the general formula

    wherein n denotes an integer from 1 to 10, a naphthylene or monomethylene- naphthylene or polymethylene-naphthylene radical of the general formula

    wherein n denotes an integer from 1 to 3, or an optionally substituted radical of the formula
33. 33. A process as claimed in claim 32 wherein B is an optionally substituted phenylene or naphthylene radical or an optionally substituted radical of the formula
34. 34. A process as claimed in claim 33 wherein B is a phenylene radical optionally substituted by one or two carboxyl groups or by one or two sulpho groups, or a naphthyl radical which is substituted by one or two sulpho groups or a stilbenylene radical which is substituted by two sulpho groups.
35. 35. A process as claimed in claim 34 wherein B is a radical of the formula
36. 36. A process as claimed in any of the preceding claims wherein the diazonium compound of the amine of the general formula H2N-B-W, W is a group of the formula

    -N-acyl, r > R, having the same meaning as defined above and"acyl"being an aliphatic acyl group having 1 to 3 C atoms, or an optionally substituted benzoyl group, and after coupling of said amine of the general formula H2NBW to the pyrazolone of the formula V, the resulting phthalocyanine azo dyestuff is saponified and the resulting dyestuff of the formula la

    wherein B, Pc, ar, Ri,R:,R,R,R,k,! and m have the same meaning as defined above in formula I, is acylated with an acylating agent of the formula X-A, wherein A has the same meaning as defined above in formula I and X is a displaceable atom
37. 37. A process as claimed in claim 36 wherein said"acyl"is acetyl or unsubstituted benzoyl.
38. 38. A process as claimed in any of claims 1 to 35 wherein in the diazonium compound of the amine of the general formula HN-B-W, W is a nitro group and after coupling of said amine of the general formula H2N-B-W to the pyrazolone of the formula V, the resulting phthalocyanine azo dyestuff is reduced and the resulting dyestuff of the formula lob

    wherein B, Pc, ar, R"R2, Rs) R4, k, I and m have the same meaning as defined above in formula I, is acylated with an acylating agent of the formula X-A wherein X is a displaceable atom or group.
39. 39. A process as claimed in any of claims 36 and 37 or 38 wherein X is a group which can be split off by the nucleophilic attack of the secondary or primary amino group, respectively, of the dyestuff of formula la or Ib, respectively.
40. 40. A water-soluble fibre-reactive phthalocyanine azo dyestuff compound of the formula I when prepared by a process according to any of the preceding claims.
41. 41. A mixture of water-soluble fibre-reactive phthalocyanine azo dyestuff compounds of the formula I when prepared by a process according to any of claims 1 to 39.
42. 42. A method of dyeing and printing a cellulose material, cellulose-containing material, or a natural or synthetic polyamide material wherein is used a water-soluble fibre-reactive phthalocyanine azo dyestuff compound according to claim 40.
43. 43. A method of dyeing and printing a cellulose material or cellulose-containing material wherein is used a water-soluble, fibre-reactive phthalocyanine azo dyestuff compound according to claim 40.
44. 44. A process for the preparation of a phthalocyanine azo dyestuff compound of the general formula I as defined in claim 1 in which a hydrazone of the formula IV as defined in claim 1 is converted by the action of an alkali into a pyrazolone of the general formula V as defined in claim 1 and said pyrazolone of formula V is coupled with the diazonium compound of an amine of the general formula H, N-B-W as defined in claim 1 so as to form the dyestuff compound of formula I,
45. 45. A water-soluble, fibre-reactive phthalocyanine azo dyestuff compound of the formula I when prepared by a process according to claim 44.
46. 46. A method of dyeing and printing a cellulose material, cellulose-containing material, or a natural or synthetic polyamide material, wherein is used a water-soluble, fibre-reactive phthalocyanine azo dyestuff compound according to claim 44.