Patent GB-779880-A (GB)
Title: Functional derivatives of azo-dyestuffs containing sulphonic acid groups and processfor making them
IPC: C09B43/32
Filed: 1954-03-01
Abstract: The invention comprises o : o1 - dioxy - azo - dyestuffs which contain at least one sulphonic acid halide group and aryl derivatives of such dyestuffs and a process for the manufacture of functional derivatives of azo - dyestuffs containing sulphonic acid groups wherein an acyl derivative of an o : o1-dioxy azo - dyestuff containing at least one sulphonic acid group is reacted in an inert solvent or diluent with a compound of pentavalent phosphorus containing at least 3 halogen atoms, and, if desired, converting an acid halide group in the resulting product into a sulphonic acid amide or ester group.  The acylated starting materials may be made by acylating the appropriate o : o1 - dioxy - azo - dyestuff which may contain substituents but preferably, apart from the o-hydroxy groups, none which react with the phosphorus halides unless such reaction is desired e.g. by this means a carboxy group may be converted to the acid halide. The free acid or an alkali metal salt thereof may be used for the acylation.  Dyestuffs mentioned are those made by coupling anilines with naphthols and 1-phenyl - 3 - methyl - 5 - pyrazolones and the diazo components may contain nitro, ethyl, methyl, ethoxy, methoxy, carboxylic acid, aryl sulphone, aryloxy and trifluoromethyl groups and fluorine, bromine and especially chlorine atoms, other indicated dyestuffs being of the naphthalene - azo - naphthalene and naphthalene - azo - pyrazolone series and those obtained by coupling an o-oxy-diazo compound with a phenol, an acetoacetylamino - compound, 2,4 - dioxyquinoline and barbituric acid.  Since the acyl groups are usually subsequently removed preferably a simple acylating agent is used, e.g. acetyl, propionyl and butyryl chlorides and acetic anhydride. Naphthalene - azo - naphthalene dyestuffs are preferably dibenzoylated.  Advantageously the acylation is effected in the dry state at about 70-100 DEG C. in the presence of a diluent, preferably an organic diluent or solvent. Water present in the starting-dyestuff may be removed by azeotropic distillation. Treatment with phosphorus halide may be effected with or without separation of the intermediate dyestuffs.  Specified phosphorus halides are the oxy-bromide and - chloride the penta - bromide and - chloride being preferred.  The acid halides may be isolated by usual methods and recrystallized from a variety of solvents.  In some cases the acyl groups are split off during isolation. Advantageously acid halides containing more than one sulphonic acid halide group or one such group and a carboxylic acid halide group are reacted with monamines and di- or polyamines with monosulphonic acid halides containing no further reactive halogen atoms.  Specified amines are mono - methyl - and - ethyl - amine, monoethanolamine, glycocoll, N - methyl - aminoacetic acid, taurine and aniline - 4 - sulphonic acid when the final dyestuff is to be soluble in water, and aniline or aminonaphthalenes and their N - ethyl or - methyl derivatives when pigment dyestuffs are required when also monosulphonic acid halides may be reacted with diamines in a mol ratio of 2 : 1, diamines specified being 1,4-diaminobenzene, 1,4 - diamino - 2,5 - dialkoxy - benzenes, 4,41 - diaminodiphenyl, 3,31 - dichloro -, - dimethyl - and - dimethoxy - 4,41 - diaminodiphenyl, 4,41 - diamino - diphenyl sulphone, 3,31 - diaminodiphenyl ketone, 3,31 - diamino - 4,41 - dichlorodiphenyl methane and amines in which benzene nuclei are linked by -NH-CO-, -NH - CO - NH-, - SO2 - NH2 -, -CH=CH-, -CH2-CH2-, -NH- or -N=N- rgoups and 2,6- or 1,5 - diaminonaphthalene and 2 - (41 - aminophenyl) - 6 - aminobenzthiazole.  Condensation of the sulphonic acid halides and ammonia or amines is effected in the usual way and in some cases when a strongly basic amine is used hydrolysis of the o-acyl group occurs. Specified hydroxy compounds for reaction with the sulphonyl halides are phenol, 4 - methyl and - nitro - phenol, 4 - methyl - 2 - nitrophenol, 1- and 2-naphthol, oxydiphenyl, 3-oxydiphenylene oxide and sulphide and N- 3 - oxycarbazole. Monosulphonyl halides may be condensed with dioxy compounds in the mol ratio 2:1 or with a compound containing n-hydroxy groups in the mol. ratio n:1. Specified dioxycompounds are 1,3 - and 1,4 - dioxybenzene and 1,5 and 2,6 - dioxynaphthalenes. Condensation of the sulphonyl halides with oxy-compounds is effected in the usual way.  Examples illustrate the preparation of fractional derivatives of dyestuffs derived from the following diazo components:- 4-chloro-2-aminophenol and its 6-sulphonic acid, 2 - aminophenol - 4 - sulphonic acid, 6 - nitro - 1 - amino - 2 - naphthol - 4 - sulphonic acid, 2 - amino - 5 - nitrophenol, 1 - amino - 2 - naphthol - 4 - sulphonic acid and 4 - nitro - 2 - aminophenol - 6 - sulphonic acid and the following azo components:- 5,8 - dichloro - 1 - naphthol, 2 - naphthol and its 6 - sulphonic acid, 1 - naphthol - 4 - and - 5 - sulphonic acid, 1 - acetoacetylamino - 2 - chlorobenzene and its 4 - sulphonic acid, 1 - phenyl-3 - methyl - 5 - pyrazolone and its 4 - sulphonic acid and 1 - (21 - and 41 - chloro-) phenyl - 3 - methyl - 5 - pyrazolones, p - chlorobenzyl and benzene - and methane sulphonyl chlorides are additional acylating agents and isopropylamine, dimethylamine, 1 - amino - 2 - and - 4 - methoxybenzene, 1 - amino - 4 - ethoxy - benzene and morpholine are additional amines to those specified above.  Specification 779,879 is referred to.