Patent GB-775005-A (GB)
Title: Improvements relating to monoazo dyestuffs containing heavy metal and their use
IPC: C09B45/14
Filed: 1953-09-03
Abstract: The preparation, by conventional methods, of the following diazo and azo components 2-aminophenol-4-, 2-aminobenzoic acid-5-, 1-naphthol-3-and 2-naphthol-6-sulphonic acid-N-methylhydroxyethylamides and 2-aminophenol-4-sulphonic acid-N-ethylhydroxyethyl amide is described.  Specification 709,495, [Group IV (c)], is referred to.  Reference has been directed by the Comptroller to Specifications 637,404 and 745,641, [both in Group IV (c)].ALSO:The invention comprises dyestuffs of formula [D - M1 - D] M2 where M1 is Cr or Co, M2 is an alkali metal or ammonium cation and D is of formula <FORM:0775005/IV(b)/1> where A is a radicle of a diazo component of the benzene series, B is a radicle of an azo component coupled in the o - position to the hydroxyl group, X is an OH or COOH group in the o - position to the azo group or a substituent which under the conditions of the metallization can be converted into such a group, R and R1 are aliphatic hydrocarbon radicles neither containing more than 6 carbon atoms, which together have not more than 8 carbon atoms, and n is 1 or 2 the sulphonic acid amide groups being aromatically bound and A and B may contain non salt-forming substituents.  They may be made by treating with chromium - or cobalt - yielding substances dyestuffs of the above formula in which X may also be a group convertible to OH or COOH during the metallization: substantially 1 atom of metal is present for two unmetallized dyestuff molecules, non salt-forming groupings mentioned are halogen, alkyl, alkoxy, aryloxy, nitroacylamino, alkylsulphonyl, arylsulphonyl, sulphonic acid dialkylamide, or sulphonic acid aryl ester and carboxylic acid ester and amide groups. Unmetallized dyestuffs may be made by alkaline coupling a diazotized o - hydroxy, o - carboxy - or o - alkoxy - amino compound of the benzene series with a component of the aliphatic, aliphatic-aromatic, aromatic-isocyclic or aromatic-heterocyclic series which couples in the o - position to a phenolic or enolic hydroxyl group, especially acylacetic acid arylamides, phenols, naphthols and 5 - pyrazolones. Preferably the sulphonamide group is derived from a methylamino or ethylamino alkanol where the alkanol contains 2-6C atoms and advantageously the hydroxyl and amino groups are adjacent to one another. Metallization is advantageously effected in aqueous solution or suspension in the warm with salts of cobalt or trivalent chromium. Preferably alkali metal salts of chromosalicylic acid are used. Dispersing agents or diluents may be present, turkey red oil, formamide, dimethyl formamide and a urea melt being specified.  The metallised dyestuffs dye wool and synthetic polypeptide fibres in yellow, red and blue shades.  In examples 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid - N - methyl - hydroxyethylamide is diazotised and coupled with (1) 1 - (31 - chloro -) - or (31, 41 - dichloro) - phenyl - 3 - methyl - 5 - pyrazolone and the products chromed, (2) 1 - (31 - chloro) - phenyl - 3 - methyl - 5 - pyrazolone and the product cobalted, (3) 1 - carbomethoxyamino - or - acetylamino - 7 - hydroxynaphthalene or 7 - hydroxy - naphthyl - (1) - carbamic acid methoxy ethyl ester and the products chromed, (4) b - naphthol and the product chromed, (5) b  - naphthol and the product cobalted, (6) acetoacetic acid anilide or 21 - chloranilide and the product cobalted, (7) 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - sulphonic acid - N - methyl - hydroxyethylamide and the product chromed, (8) 4 - methyl - 6 - nitro - 2 - amino - 1 - hydroxy - benzene is diazotized and coupled with 1 - phenyl - 3 - methyl - 5 - pyrazolone - 31 - sulphonic acid - N - methyl - hydroxyethylamide the product being chromed, (9) 2 - aminobenzoic acid - 5 - sulphonic acid - N - methyl - hydroxyethylamide is diazotized and coupled with 1 - (31 - chloro-) - phenyl - 3 - methyl - 5 - pyrazolone and the product chromed, (10) 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid - N - ethyl - hydroxyethyl - amide is diazotized and coupled with 1 - (31 - chloro) - phenyl - 5 - pyrazolone - 3 - carboxylic acid amide and the product chromed, (11) 4 - chloro - 2 - amino - 1 - phenol is diazotized and coupled with 1 - naphthol - 3 - sulphonic acid - N - methyl - hydroxyethylamide and the product chromed and (12) 4 - chloro - 2 - amino - 1 - phenol is diazotised and coupled with 2 - naphthol - 6 - sulphonic acid - N - hydroxyethylmethylamide and the product chromed.  A table is provided of metallized dyestuffs the following diazo components additional to those already specified being given 5 - chloro - 2 - amino - 1 - phenol - 4 - sulphonic acid - N - methyl - hydroxyethylamide, 4 - methyl - 2 - amino - 1 phenol - 5 - sulphonic acid - N - methyl - hydroxyethylamide, 4 - chloro - 2 - amino - 1 - phenol - 6 - sulphonic acid - N - methyl - hydroxyethylamide, 4 - nitro - 2 - amino - 1 - phenol - 6 - sulphonic acid - N - ethyl - hydroxyethylamide, 4 -, 5 - and 6 - nitro - 2 amino - 1 - phenol, 4 - chloro - 5 - and - 6 - nitro - and 4, 6 - dinitro - 2 - amino - 1 - phenol, 2 - amino - 1 - phenol - 5 - sulphonic acid - N - methyl - hydroxyethylamide anthranilic acid and 2 - amino - 1 - phenol - 4 - sulphonic acid - N - dimethylamide together with the following additional coupling components 1 - phenyl - 3 - methyl - 5 - pyrazolone, 3, 4 - dimethyl-, 3 - methoxy - 4 - methyl - and 4 - amyl - 1 - phenol, 1 - hydroxy - naphthalene - 3 -, - 4 - and - 5 - sulphonic acid - N - methyl - hydroxyethylamides, 2 - hydroxynaphthalene - 4 - and 8 - sulphonic acid - N - methyl - hydroxyethylamides and 1 - (31 - sulphonic acid - N - methyl - hydroxyethylamidophenyl) - 3 - methyl - 5 - pyrazolone. Specification 709,495 is referred to.  Reference has been directed by the Comptroller to Specifications 637,404 and 745,641.