Patent GB-821963-A (GB)
Title: New nitro dyestuffs
Inventor: SLINGER FRANK HAYHURST
IPC: C09B62/00
Filed: 1956-12-14
Abstract: The invention comprises nitro dyestuffs of the formula <FORM:0821963/IV(c)/1> where D is a benzene or naphthalene nucleus which may be further substituted, N is a nitrogen atom in ortho position to the nitro group, X is a hydrogen atom or an alkyl or substituted alkyl group, R is a non-acyl organic radical attached to the nitrogen atom N through a carbon atom which radical may be joined with X or to D in the other position ortho to the nitrogen atom N to form with N a heterocyclic radical, characterized in that the compounds contain a beta-halogenoalkyl sulphamyl group.  The radical R may be any acyclic or cyclic radical but not an acyl radical such as acetyl, benzoyl or s-triazinyl.  Radicals mentioned are alkyl groups such as methyl, ethyl, iso-propyl, t-butyl, hexyl, iso-octyl and dodecyl, alkenyl groups such as allyl, aryl radicals such as phenyl, alpha- and beta naphthyl, cycloalkyl radicals such as cyclopentyl and cyclohexyl, and heterocyclic radicals such as 2-benzthiazolyl and 2-benzoxazolyl.  Radicals formed by attachment of R to X are morpholinyl and piperazinyl and those formed by attachment of R to D are phenoxazinyl, phenothiazinyl and acridonyl. Substituents which may be present in nucleus D or in radical R or in radicals formed in part by R may be the groups -Y-B and -Y1-B1-Y-B where Y and Y1 may be direct links or -NH-, -SO2-, -S-, -O-, -SO2.NH-, -CO.NH-, -NH.SO2-, -NH.CO-, -CO-, -CH2- or -CH=CH-, and B and B1 are aryl, cycloalkyl or heterocyclic radicals.  Other substituents present in D, R, B and B1 may be chlorine, bromine, alkyl, sulphonic acid, carboxylic acid, carbamyl and substituted carbamyl, cyano, carboalkoxy, sulphamyl and substituted sulphamyl, ketonic, trifluoromethyl, sulphinic esters, nitro, sulphone, hydroxyl, alkoxy, amino and substituted amino, acylamido and sulphamido groups.  The radical X may be methyl, ethyl, iso-propyl, t-butyl, hexyl, iso-octyl and dodecyl and be substituted by cyano, hydroxy, methoxy, ethoxy and beta-ethoxyethoxy.  The invention also comprises a process for making the dyes by interacting a beta-halogeno-alkylamine and a compound of the formula <FORM:0821963/IV(c)/2> where D, X and R are as above. Halogenoalkylamines mentioned are beta-chloro- and -bromo - ethylamine, beta - bromo - n - butylamine, and beta - chloro - iso - propyl and -isobutylamines.  Compounds of Formula II specified are 2-nitro-diphenylamine-4-sulphonyl chloride, 2 - nitroacridone sulphonyl chloride, and 2 - nitrophenyl - cyclohexylamine - 4 - sulphonyl chloride.  The reaction may be effected at below 30 DEG  C. by stirring the reactants together in water, alcohol or a mixture of water and acetone in the presence of sodium bicarbonate or acetate. The invention further comprises a process for making dyes of Formula I where R is not joined to the nucleus D by heating a substituted or unsubstituted o-chloronitrobenzene or o-chloronitronaphthalene containing a beta - halogeno - alkylsulphamyl group with an amine of the formula X-NH-R. Chloronitro compounds mentioned are 2-chloro - nitrobenzene - 5 - sulphon - beta - chloro-and -bromoethyl- and -(11-chloro-21-butyl)-amides, and 4-chloro-5-nitro-2-methyl-benzene - sulphon - beta - chloroethylamide.  Amines specified are 2-methoxy-5-aminobenzene - sulphonic acid, 4 - amino - 41 - acetylaminodiphenylamine - 2 - sulphonic acid, aniline, o-, m- and p-toluidines, p-phenetidine, o-, m- and p-anisidines, o, m- and p-chloroanilines, metanilic acid, m - amino - benzotrifluoride, m-aminobenzoic acid, 2-naphthylamine, p  m-nitraniline, 2-nitro-4-amino-toluene, 4 - amino - diphenylamine, 1 - naphthylamino-6 - sulphonic acid, 4 - acetylaminoaniline, 2-aminobenzothiazole, 2 - aminobenzoxazole, 1-phenyl - 3 - amino - 5 - pyrazolone, 2 - (41-aminophenyl) - 6 - methylbenzthiazole, 3 - aminopyridine and cyclohexylamine.  The reaction may be carried out by heating the reactants in a solvent such as alcohol or aqueous alcohol in the presence of calcium carbonate or magnesium oxide.  The invention still further comprises a process for making the dyes of Formula I by treating a compound of Formula I where D, X and R have the meanings given above and which contains a beta-hydroxyalkyl sulphamyl group but no other alcoholic group with a halogenating agent such as thionyl chloride, phosphorus tribromide or methane sulphonyl chloride and pyridine at 50-100 DEG  C. Beta-hydroxyethyl sulphamyl compounds mentioned are 2-nitro-4-(beta-hydroxyethyl)-sulphamyl - diphenylamine, -N-cyclohexylaniline, or -N : N-diethylaniline, and 41-methoxy-31-sulpho - 2 - nitro - 4 - (beta - hydroxyethyl)-sulphamyl-diphenylamine.  The dyes are yellow, orange or red-brown reactive dyestuffs for dyeing and printing protein materials such as wool, silk and casein and ardein fibres, cellulose materials such as cotton, linen, viscose rayon and cellulose acetate and triacetate fibres, and polyamide materials such as fibres of polyhexamethylene adipamide, caprolactam polymers, polyurethanes and polyethylene terephthalate.  The dyestuffs are applied to cellulose textile materials as an aqueous solution and in conjunction with a prior, simultaneous or subsequent treatment with an acid binding agent such as caustic soda or sodium carbonate or in a printing paste which also contains sodium bicarbonate.  The dyestuffs may also be applied as a finely - divided aqueous dispersion.  Examples are given.ALSO:In examples: (1) 2-nitrodiphenylamine-4-sulphonyl chloride is made by treating the sodium salt of the corresponding sulphonic acid with a mixture of phosphorus pentachloride and phosphorus oxychloride; (2), o-chloronitrobenzene is heated with chlorosulphonic acid to give 3 - nitro - 4 - chloro - benzene sulphonyl chloride which on treatment with beta-chloroethylamine yields 3-nitro-4-chloro-benzene-sulphonbeta-chloro-ethylamide; (6) 1-nitro-(beta-chloroethyl)-sulphamyl acridone is made by heating 1-nitro-acridone with chlorosulphonic acid; (7) 4-chloro-3-nitrobenzene sulphonyl chloride is condensed with ethanolamine to give 4-chloro-3-nitrobenzene sulphon-beta-hydroxyethylamide, the latter being condensed either with aniline to yield 2 - nitro - 4 - beta - hydroxyethylsulphamyldiphenylamine or (12) with diethylamine to yield 2 - nitro - 4 - beta - hydroxyethylsulphamyldiethylaniline; (11) 2-amino-1-butanol hydrochloride is reacted with thionyl chloride to give 2-amino-1-butyl chloride which on condensation with 4-chloro-3-nitrobenzene sulphonyl chloride yields 4-chloro-3-nitro-benzene sulphon-(11-chloro-21-butyl)-amide.