Patent GB-746944-A (GB)
Title: Manufacture of azo-dyestuffs
IPC: C09B45/14
Filed: 1952-07-21
Abstract: 1 - n - Butyl - 3 - methyl - 5 - pyrazolone is made by treating hydrazine sulphate with n-butyl bromide to yield n-butyl-hydrazine (isolated as the sulphate) which yields the desired pyrazolone on treatment with acetoacetic acid amide in the presence of acetic acid and sodium acetate.  5 - Pyrazolone - 3 - carboxylic acid - n - butylamide is made either by heating 5-pyrazolone-3-carboxylic acid ethyl ester with n-butylamine or by treating the corresponding free acid suspended in chlorobenzene with phosphorus trichloride and simultaneously or subsequently with n-butylamine, the acid chloride intermediate not being isolated. 4-Nitro-2-amino - 1 - oxybenzene - 6 - sulphonic acid - N - methylamide is made by reacting sodium 2,4-dinitro - 1 - chlorobenzene - 6 - sulphonate with chlorosulphonic acid to yield 2,4-dinitro-1-chlorobenzene - 6 - sulphonic acid chloride which on treatment with aqueous methylamine solution yields the corresponding -N-methylamide which treated with calcium hydroxide gives 2,4 - dinitro - 1 - oxybenzene - 6 - sulphonic acid - N-methylamide which reduced with sodium hydrosulphide yields the above nitroaminophenol.  The corresponding N-phenylamide may be made by using aniline instead of methylamine.  The products are dyestuff intermediates, c.f. Group IV (c).ALSO:The invention comprises complex cobalt or chromium compounds of monoazo dyestuffs in which the ratio of the number of atoms of cobalt or chromium bound in complex union to the number of monoazo dyestuff molecules in the complex is smaller than 1:1 and is advantageously about 1:2 and in which there are present one or two dyestuffs free from sulphonic or carboxylic acid groups and of formula <FORM:0746944/IV(c)/1> in which R1 is a benzene residue bound to the azo linkage in ortho-position relatively to the hydroxyl group, Pz is a 5-pyrazolone residue bound in the 4-position to the azo linkage, X1 is an aliphatic, alicyclic or araliphatic residue, and X2 is H or an aliphatic residue or together with X1 and N is a heterocyclic residue, or two dyestuffs one of which is of the above formula and the other of the benzene-azo-naphthalene series. They are made by treating the corresponding ortho: ortho1 - dioxy - monoazo - dyestuff or dyestuff mixture with agents yielding cobalt or chromium in conventional fashion so that the resulting metalliferous complex contains less than one atom of metal per molecule of dyestuff.  Mixtures of cobalt and chromium-yielding agents may be used in metallization or a 1:1 chromium complex may be reacted in an alkaline to neutral medium with an appropriate metal-free dyestuff to yield dyestuffs of the above formula.  The monoazo dyestuffs of the above formula may be made by coupling appropriate 5-pyrazolones and ortho-oxy-diazo-compounds of the benzene series.  R1 may be substituted by halogen e.g. chlorine atoms, alkoxy e.g. methoxy groups, alkyl e.g. methyl groups, nitro groups, -CO-alkyl e.g. -CO-CH3, groups, and acylamino e.g. acetylamino, groups. Specified components containing R1 are 4 - methoxy - 2 - amino - 1 - oxybenzene - 5 - sulphonic acid - N - methyl- or - N - diethylamide, 6 - nitro - 2 - amino - 1 - oxybenzene - 4 , sulphonic acid - N - methylamide, 4 - nitro - and 4 - chloro - 2 - amino - 1 - oxybenzene - 6 - sulphonic acid - N - methylamide, 4 - chloro - 2 - amino - 1 - oxybenzene - 5 - sulphonic acid , N - methylamide, 2 - amino - 1 - oxybenzene - 4 - sulphonic acid - N - methyl-, - N - ethyl-, - N - isopropyl-, - N - n - butyl-, - N - b  - oxyethyl-, - N - b  - methoxyethyl-, - N - b  - chloroethyl-, - N - octyl-, - N - cyclohexyl-, - N - dimethyl-, - N - diethyl-, and the corresponding 5-sulphonamides, 2-amino - 1 - oxybenzene - 4 - or - 5 - sulphonic acid - N - benzylamide and pyrrolidide.  Specified pyrazolones are 5 - pyrazolone, 1 - methyl-, - n - propyl-, isopropyl-, - n - butyl-, - n - hexyl-, - n - octyl-, - cyclohexyl-, -   - naphthyl-, - phenyl-, - 21-, - 31 - or 41 - chloro- or methyl-phenyl-, - 31 - or - 41 - nitrophenyl-, - 41 - tert amylphenyl-, - 21 - or - 41 - fluorophenyl-, - 21, 51 - dichloro - or - dibromophenyl-, - 21 - methyl - 4 - chlorophenyl - and - 31 - trifluoromethylphenyl - 3 - methyl - 5 - pyrazolones, 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - or - 4 - sulphonic acid amide, 5 - pyrazolone - 3 - carboxylic acid anilide, p - chloroanilide, methyl-, ethyl-, isopropyl-, n-butyl-, cyclohexyl-, and N - dimethyl - or diethyl - amides, 1 - phenyl - 5 - pyrazolone - 3 - carboxylic acid amide and the methyl-, ethyl-, isopropyl-, n - butyl - or dimethyl - amides thereof and 1 - (41 - chloro) - phenyl - 5 - pyrazolone - 3 - carboxylic acid amide.  Advantageously the dyestuff of the benzene - azo - naphthalene series is of formula HO-R2-N=N-R3-OH where R2 is a benzene residue advantageously containing a sulphonamide group bound to the azo link in ortho position to the hydroxy group and R3 is a naphthalene residue bound to the hydroxy group in the 1- or preferably the 2- position and to the azo link in the other of these two positions.  The benzene azo-naphthalene dyestuffs may be made by coupling appropriate ortho-oxy-diazo benzenic compounds with the required naphthols.  Ortho-oxy-diazo benzenic compounds specified are those obtainable from the following amines: 6 - acetylamino -4 - nitro-, 4 - or 5 - nitro-, 4, 6 - dinitro - or - dichloro-, 4 - nitro - 6 - chloro-, and 6 - nitro - 4 - acetylamino - 2 - aminophenol, 2 - amino- 4 - methyl sulphone and the above specified 2 - amino - phenol sulphonic acid amides.  Specified naphthols are 5 - chloro-and 5, 8 - dichloro - 1 - naphthol, 2 - naphthol, 6 - methoxy - or - bromo - 2 - naphthol, 1 - acetyl-, - n - butyryl - or - benzoylamino - 7 - napthol the use of b  - naphthols being preferred.  Preferably both dyestuffs are of the first of the above formulae particularly preferred being those of formula <FORM:0746944/IV(c)/2> where R2 is an alkyl or aryl residue and X1 and X2 are as above.  The chromium containing dyestuffs dye silk, leather, wool and super-polyamides and -polyurethanes in orange shades the corresponding cobalt complexes yielding brown dyeings.  Examples are provided illustrating the use of certain of the above components in the preparation of dyestuffs an additional pyrazolone used being 5 - pyrazolone - 3 - carboxylic acid N - 21 - methyl - 41 - chlorophenylamide. Specifications 637,404, 697,056 and 706,370 are referred to.