Patent GB-768241-A (GB)
Title: New monoazo-dyestuffs and process for making them
IPC: C09B62/45
Filed: 1954-01-22
Abstract: 1 - Aryl - 3 - methyl - 5 - pyrazolones having a monoacylated sulphonamide group in the aryl nucleus are prepared by diazotizing an arylamine containing a monoacylated sulphonamide group, reducing the diazo compound to a hydrazine, for example with stannous chloride or sodium bisulphite, and condensing the hydrazine with an acetoacetic acid ester, the formation of the pyrazolone being completed without hydrolysis of the monoacylated sulphonamide group.  Thus, 3-aminobenzene-1-N-(benzene sulphonyl)-sulphonamide is diazotized, reduced with sodium bisulphite to the hydrazine, and the hydrazine condensed with ethyl acetoacetate to give 1-phenyl-3-methyl-5-pyrazolone - 31 - N - (benzene sulphonyl) - sulphonamide; 4-amino- or 3-amino-4-chloro- or 4 - amino - 3 : 6 - dichloro - benzene - 1 - N - (benzene sulphonyl)-sulphonamides may be treated similarly to give the corresponding substituted pyrazolones. Many similar compounds are listed. 1 - Methyl - 4 - aminobenzene - 2 - sulphonic acid - b  - (p - toluene sulphonyloxy) - ethylamide and 1 - methoxy - 2 - aminobenzene - 4 - sulphonic acid - b  - (p - toluene sulphonyloxy) - ethylamide are prepared by reacting 1-methyl-4-acetylaminobenzene - 2 - sulphonic acid - b  - hydroxyethylamide or 1 - methoxy - 2 - acetylaminobenzene - 4 - sulphonic acid - b  - hydroxyethylamide with p-toluene sulphonylchloride, followed by hydrolysis to split off the acetyl group.  The compounds described are used in the preparation of azo dyestuffs (see Group IV (c)).ALSO:The invention comprises monoazo dyestuffs, obtained from diazo components of the benzene series, which contain at least one monoacylated sulphonamide group and at least one group of the formula:-SO2 - (NH)n - 1-R - X (1) wherein R is an aliphatic residue, n is 1 or 2 and X is a labile sulphur-containing substituent (as hereinafter defined), the monoacylated sulphonamide group and the group of the stated formula being present, one in the residue of the diazo component and the other in the residue of the coupling component.  Labile sulphur-containing substituents are defined as substituents which are easily split off in an alkaline medium such as a sulphuric or sulphonic acid ester group.  The dyestuffs may be prepared by coupling the appropriately substituted diazo and coupling components in a not strongly alkaline medium.  Acyl residues present in the monocylated sulphonamide groups include acetyl, n-butyl, benzoyl, p - tert. - butyl - or chloro-benzoyl and methane - or ethane - or n - butane - or benzene - or naphthalene - b  - or p-methyl-benzene or o - or p - chlorobenzene - or 2:5 - dichlorobenzene - sulphonyl residues.  Specified components containing monoacylated sulphonamide groups are; diazo components:- 1 - aminobenzene - 3 - or - 4 - N - acetyl - sulphonamide, 4 - methyl - or - methoxy - 1 - aminobenzene - 3 - N - benzoyl - sulphonamide, 1 - aminobenzene - 2 - N - (methanesulphonyl) - sulphonamide, 1 - aminobenzene - 2 - or - 3 - or - 4 - N - (p - toluene sulphonyl) - sulphonamide, 2 - chloro - 1 - aminobenzene - 5 - N - (benzenesulphonyl) - sulphonamide, 4 - methyl - 1 - aminobenzene - 2 - N -(benzene sulphonyl) - sulphonamide, 1 - amino2 - methylbenzene - 5 - N - (benzene sulphonyl), sulphonamide and 1 - amino - 2:6 - dichloro-benzene - 4 - N - (benzene sulphonyl) - sulphonamide; coupling components:- 1 naphthol - 4 - or - 5 - N - (acetyl or benzene sulphonyl) - sulphonamide, 2 - naphthol - 4 - or - 5 - or -6 - or - 7 - or - 8 - N - benzoyl - sulphonamide, 2 - aminonaphtalene - 6 - N - (benzene sulphonyl) - sulphonamide, 2 - amino - 8 - hydroxynaphthalene - 6 - N - (p - toluenesulphonyl or benzene sulphonyl or 2:5 - dichlorobenzoyl) - sulponamide, 1 - (a  - naphthyl) - 3 - methyl - 5 - pyrazolone - 41 - N - acetyl-sulphonamide, 1 -phenyl - 3 - methyl - 5 - pyrazolone - 21 - or - 31- or - 41 - N - (p - toluene-sulphonyl or p - chlorobenzene - or benzene - or 211:511 - dichlorobenzene - sulphonyl) - sulphonamide, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 21 - chloro - 51 - N - (benzene sulphonyl) - sulphonamide, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 21:61 - or - 21:51 - dichloro - 41 - N - (benzene - sulphonyl) - sulphonamide and 1 - acetoacetylaminobenzene - 2 - or - 3 - or 4 - N - (benzoyl or benzene sulphonyl) - sulphonamide.  Specified components containing groups of formula (1) are; diazo components:-1 - aminobenzene-4 - sulphonic acid - b  - (ethane sulphonyloxy) - ethylamide, 1 - aminobenzene - 3 - or - 4 - sulphonic acid - b  - (benzene sulphonyloxy) - ethylamide, 1 - aminobenzene - 4 - sulphonic acid - g  - (benzene sulphonyloxy or p - toluene sulphonyloxy) - proplyamide, 4 - methyl - 1 - aminobenzene - 3 - sulphonic acid - b  - (p - toluene sulphonyloxy) - ethylamide, 2:5 - dichloro-1 - aminobenzene - 4 - sulphonic acid - b  - (benzene sulphonyloxy) - ethylamide, 2 - methoxy - 1 - aminobenzene - 5 - b  - (p - toluene sulphonyloxy) - ethylsulphone, 1 - aminobenzene - 2 - or 3 - or - 4 - b  - (p - toluene sulphonyloxy) - ethyl sulphone and 4 - methyl - 1 - aminobenzene - 3 - sulphonic acid - b -(benzenesulphonyloxy) - ethylamide; coupling components:-2 - aminonaphthalene - 6 - sulphonic acid - b  - (benzene sulphonyloxy) - ethylamide, 1 -naphthol - 4 - or - 5 - sulphonic acid - b  - (benzene sulphonyloxy) - ethylamide, 2 - naphthol - 6 - sulphonic acid - b  - (benzene sulphonyloxy) - ethylamide, 2 - naphthol - 6 - b  - (benzene sulphonyloxy) - ethyl sulphone, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 21 - or - 31 - or - 41 - sulphonic acid - b  - (benzene sulphonyloxy) - ethylamide, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - sulphonic acid - g  - (benzene sulphonlyoxy) - propylamide, 1-phenyl - 3 - methyl - 5 - pyrazolone - 31 - or - 41 - b  -(p - toluenesulphonyloxy) - ethylsulphone and 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - sulphonic acid - b  - (p - toluenesulphonyloxy) - ethylamide.  Dyestuffs containing a sulphonylated sulphonamide group may be made by reacting 1 mol of a dyestuff which contains a - SO2NH2 group and a hydroxyalkyl sulphone group or sulphonic acid N - hydroxylalkylamide group with at least 2 mols of a sulphonic acid halide such as tosyl chloride, benzene - or ethane - sulphonyl chloride so that the sulphonamide group and the hydroxy group are both acylated.  The dyestuffs may be used to dye nitrogenous natural or artificial fibres such as leather, wool, silk, superpolyamides and superpolyurethanes.  They dye wool in yellow shades.  In examples dyestuffs are prepared using some of the components specified above, the following additional components being specified; diazo components, 1 - methoxy - 2 - aminobenzene - 4 - sulphonic acid - b - (p - toluenesulphonyloxy) - ethylamide and 1 - aminobenzene - 4 - b (benzene sulphonlyoxy) - ethyl sulphone; coupling components, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - N - (311:411-dichlorobenzene sulphonyl)- sulphonamide and 1 - phenyl - 3 - methyl - 5 - pyrazolone-41 - N - (ethanesulphonyl)- sulphonamide.