Patent GB-388332-A (GB)
Title: The manufacture of azo dyestuffs containing copper
IPC: C09B45/34
Filed: 1932-09-27
Abstract: Azo dyes, copper compounds of.--Azo dyes containing copper are obtained by coppering in a caustic alkaline medium at an elevated temperature azo dyestuffs containing at least once the grouping <FORM:0388332/IV/1> in which R1 and R2 represent benzene or naphthalene radicles until by substitution of the Cl atom by the OH group the copper compounds of the corresponding o-oxyazo dyestuffs are formed.  The radicles R1, R2 may be further substituted, e.g. by halogen or by groups such as sulphonic, carboxylic, alkyl, hydroxy, alkoxy, hydroxyalkyl, aryl (as when using dichlorobenzidine as tetrazo component), aralkyl (as when using an o-chloroaminodiphenyl methane as diazo component or a hydroxyldiphenylmethane as coupling component), amino, acylamino (as acetylamino or benzoylamino), alkylamino (as methyl- or ethyl-amino), aralkylamino (as benzylamino), arylamino (as phenylamino), or nitro groups.  As agents yielding copper may be used finely divided copper, copper oxide or hydroxide, copper salts such as cupric sulphate or chloride, complex compounds of copper with bases such as those of cupric sulphate with ammonia, pyridine or ethylenediamine, or the complex copper compounds of organic hydroxy compounds such as glycerol or tartaric acid.  The process enables the preparation of copper compounds of azo dyestuffs not obtainable or obtainable only with difficulty by other methods. The following examples are specified: (1) A caustic soda solution containing the dyestuff 2-chloraniline-5-sulphonic acid --> b -naphthol, ammonia and tetrammine cupric sulphate is heated for 1 hour at 80 DEG  C., and the desired copper compound is obtained by neutralizing the excess of soda, cooling and salting out.  (2) The same product is obtained by heating for 1 hour at 95 DEG  C. a caustic soda solution containing the dyestuff, sodium acetate and copper sulphate.  (3) A caustic soda solution containing the dyestuff 3 : 3<1>-dichlorobenzidine \sQ 2-naphthol-3 : 6-disulphonic acid (2 mols.), ammonia and copper sulphate is heated for 1 hour at 85 DEG C., cooled and acidified with acetic acid and the desired copper compound is salted out.  (4) A caustic soda solution containing the dyestuff 3-chloro-2-aminotoluene-5-sulphonic acid --> resorcin, copper sulphate and glycerol is heated from 80 DEG  C. to 95 DEG  C. in 4 hours and acidified with acetic acid and the desired copper compound is salted out; the glycerol may be replaced by tartaric acid or pyridine, the diazo component of the dyestuff by 2-chloraniline-5-sulphonic acid or 1-chloro-2-aminonaphthalene-6-sulphonic acid and the resorcin by m-aminophenols coupling in o-position to the hydroxy group.  (5) A caustic soda solution containing the dyestuff aniline-2 : 5 - disulphonic acid --> p - xylidine --> (alkaline) 1 - chloro - 2 - amino - 5 - naphthol - 7 - sulphonic acid --> 2 : 6-naphtholsulphonic acid, copper sulphate and glycerol is heated for several hours at 100 DEG  C.; the product dyes cotton green from a Glauber's salt-soda bath.  (6) A caustic soda solution containing the dyestuff 2 : 3 - dichloro - 4 - aminotoluene --> 1-naphthol-3 : 6-disulphonic acid, copper sulphate and glycerol is heated for 3 hours at 100 DEG  C.; the similar coppering of the dyestuff 2 : 5 : 6 - trichloraniline - 3 - sulphonic acid --> 1 : 5-naphtholsulphonic acid requires only \ba1/4\be hour at 80 DEG  C.; the coppering may also be effected in some cases under pressure. (7) A caustic soda solution containing the dyestuff 1-chloro-2-amino-5-naphthol-7-sulphonic acid --> 1-naphthol-3 : 6-disulphonic acid, copper sulphate and glycerol is heated for 5 hours at 90 DEG  C.; the product may be further coupled with a diazo or diazoazo compound (1 mol.) such as diazotized benzidine --> salicylic acid or diazotized aminobenzene-azo-salicylic acid.