Patent GB-988904-A (GB)
Title: New metallized azo dyestuffs
Inventor: BLACKHALL ALEXANDER
IPC: C09B62/477
Filed: 1962-02-07
Abstract: 3 - (g :g :g : - trichlorocrotonylamino) - 4-methyl phenol is obtained by reacting 3-aminophenol in aqueous solution with g :g :g -trichlorocrotonyl chloride.  4 - (g :g :g  - trichlorocrotonylamino) - aceto-acetanilide is obtained by acylating the corresponding amino compound with g :g :g -trichlorocrotonyl chloride.ALSO:The invention comprises metallized azo dyes which, in the form of the free acids, are represented by the formula <FORM:0988904/C4-C5/1> wherein A1 and A11 each independently represent substituted or unsubstituted arylene radicals, B1 and B11 each independently represent the residues of substituted or unsubstituted coupling components which couple in ortho or vicinal positions to a hydroxy or enolizable keto group, Z1 and Z11, which are attached to A1 and A11 respectively in ortho positions to the azo groups, each independently represent -O- or -COO-, M represents a chromium or cobalt atom, R represents a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms, Y represents a chlorine or bromine atom, R1 and R2 each represent a hydrogen, chlorine or bromine atom, and m represents 1, 2, 3 or 4 provided that each of the <FORM:0988904/C4-C5/2> group is attached directly to a carbon atom present in A1, A11, B1 or B11 and that A1, A11, B1 and B11 and free from sulphonic and carboxylic acid groups.  The dyes are prepared by (a) treating appropriate metallized azo dyes containing amino groups with appropriate acid halides, (b) treating one or two metallizable azo compounds of the formula <FORM:0988904/C4-C5/3> where A represents an optionally substituted arylene radical, B represents the residue of an optionally substituted coupling component which couples in ortho or vicinal position to the -OH group, T1 represents a hydroxy, carboxy, acyloxy or alkoxy group attached to A in ortho position to the azo link, with an agent or agents yielding chromium or cobalt, the metallizable azo compounds together containing 1-4 of the required acylamino groups, or (c) reacting an azo compound of the formula given in (b) above with a 1 : 1-chromium compound of the same or different azo compound of the above formula the azo compound and the 1 : 1-chromium complex together containing from 1 to 4 of the desired acylamino groups.  The dyes are useful for colouring nitrogen-containing textile materials, e.g. wool and silk, polyhexamethylene adipamide caprolactam polymer, polyurethane, polyacrylonitrile and modified polyacrylonitrile fibres and leather.  The dyes may be applied from neutral, acid or slightly alkaline dye-baths. In Example (1) the 1 : 2-cobalt complex of 1 - (21 - hydroxy - 31 - amino - 51 - sulphamylphenylazo) - 2 - naphthol is acylated with g  : g  : g  - trichlorocrotonyl chloride.  The dye employed as starting material is obtained by diazotizing 6 - nitro - 2 - aminophenol - 4 -sulphonamide and coupling with 2-naphthol metallizing the product with cobalt acetate and reducing the nitro group in the product with sodium sulphide.  A similar process is carried out using 2 : 4-dihydroxyquinoline as coupling component in Example (9).  Many additional examples are furnished.