Patent GB-766018-A (GB)
Title: Improvements relating to disazo dyestuffs and complex heavy metal compounds thereof,and to their use
IPC: C09B35/28
Filed: 1954-09-16
Abstract: The invention comprises dyestuffs of the formula <FORM:0766018/IV(b)/1> where A1 and A2 are residues of a phenolic, naphtholic or enolic coupling component containing the OH group adjacent to the azo links, B1 and B2 are benzene residues containing the azo links #s to the bridging member of both rings and R1, R2, R3 and R4 are H, alkyl groups or members of a carbocyclic ring and chromium- and cobaltcomplexes thereof.  The metal-free dyestuffs may be made by coupling a diazoamine compound of formula <FORM:0766018/IV(b)/2> with an appropriate phenolic, naptholic or enolic component. Metallization is effected in conventional fashion on the fibre or preferably in substance and advantageously so that there is at least one metal atom per dyestuff molecule.  Aromatic rings may contain substituents, e.g. halogen, alkyl, alkoxy, nitro, acylamino, carboxyl, sulpho, sulphonamido N-substituted sulphonamido, aryl, aralkyl and rayl sulphonyl groups.  The dizonium compounds may be made by reacting an #s - nitrophenyl sulphonic acid halide with a monoacyl - a  b  - diaminoalkane, cycloalkane or phenylene diamine compound in the presence of acid binding agents, reducing the nitro and saponifying the acylamino groups in the compound thus obtained and treating it with an #s - nitrophenyl sulphonic acid halide to yield an a  - o - nitrophenyl sulphonylamino - b  - #s - aminophenyl sulphonyl amino - alkane, cycloalkane or phenylene diamine compound which may either be diazotized and coupled with an appropriate azo component and the nitro group reduced and the latter diazotized, or it may be acetylated and the nitro group reduced, diazotized, coupled with the desired azo component and the acetylamino groups saponified and diazotized.  They may also be made by diacylating an a b  - diaminoalkane, - cycloalkane or #s - phenylene diamine with an #s - nitrophenyl sulphonic acid halide, reducing the nitro groups in and tetrazotizing the compound thus produced and coupling with one mol of an appropriate azo component. Alternatively the tetrazotized compound may be coupled with 2 mols of an appropriate azo coupling component to give the metal-free dyestuffs of the invention.  5-pyrazolones, dihydroxy - quinolines, phenols and naphthols are indicated as components corresponding to A1 and A2 and they may contain halogen, alkyl, alkoxy, nitro, acylamino and alkyl-, dialkyl- and phenylamino and particularly sulphonic acid and sulphonamide groups the latter optionally being organically N-substituted and alkyl-sulphonyl groups.  The metal dyestuffs dye wool and other natural or synthetic proteinaceous fibres in yellow, brown, red, blue and green shades. Metal containing dyestuffs which draw on to keratin fibres from a neutral to weakly acid medium are chosen so that no water solubilizing groups which dissociate acid in neutral water are present and thus suphonamido, N-organically substituted-sulphonamide, low molecular alkylsulphonyl and acylamino groups may be present. The dyestuffs should contains at least one sulphonic acid group if they are to draw from an acid bath.  Examples and a table illustrate the preparation of symmetrical and unsymmetrical metal-free and metallized dyestuffs and the use of the latter in dyeing wool, specified components derived from a , b - diamines being bis (2 - aminobenzene sulphonic acid) ethylene -, a  - methyl and a , a - and b b -dimethyl-ethylene, #s-phenylene and 1, 4 - cyclohexyl - diamides, bis (2 - amino - 4 - chloro - and - 5 - nitro - benzene suphonic acid) ethylene - diamide and a  - (2 - acetylamino - and - aminobenzene sulphonic acid) - b (2 - amino - 4 - chlorobenzene sulphonic acid) ethylene - diamides, and components corresponding to A1 and A2 are tert p - amyl and 3, 4 - dimethyl-phenols, 2 - naphthol and its 6-sulphonic acid and the amide thereof, 5, 8 - dichloro - 1 naphthol, carbomethoxyamino-naphthol - 1, 7 and 1 - phenyl-, -(31 - sulphonamideo - and - chloro - phenyl) and - (21 - tolyl - 51 - methyl - sulphonyl) -3 - methyl - 5 - pyrazolones.