Patent GB-335896-A (GB)
Title: Manufacture of new dyestuffs
IPC: C09B45/18
Filed: 1929-06-25
Abstract: 335,896. Groves, W. W., (Soc. of Chemical Industry in Basle). June 25, 1929. Azo dyes; azo dyes, forming on the material.- Azo dyes for dyeing wool, silk or cotton, viscose and varnishes are made in substance or on the fibre by coupling any diazo compound with an azine of the general formula: (in which one y is an OH-group and the other y a hydrogen atom, one z an SO3H-group and the other z a hydrogen the SO3H group and the OH-group being in m-position to one another, and in which the two carbon atoms @ belong to an aryl residue which may be substituted and in some cases treating the dyestuff with an agent yielding metal, or the dyeings may be after-treated with metal salts or the material dyed in presence of metal salts. The use of 5 : 5<1>-dioxy-7 : 7<1>-disulpho- 1 : 2<1> :1<1> : 2-dinaphthazine obtainable from J acid according to Specification 318,839 is excluded. In examples, (1) 2-sulpho-4-oxy-a: #- naphthophenazine is coupled with diazotized oanisidine, p-nitraniline, sulphanilic acid, pnitraniline-o-sulphonic acid, or 4-nitro-2-amino-1- phenol-6-sulphonic acid; cotton is dyed olive green in the presence of chromium salts with the last-mentioned dyestuff, (2) the first dyestuff in (1) is treated with chromium fluoride and the chromium compound salted out, (3) the dyestuff 4-nitro-2-aminophenol-6-sulphanic acid # 2- sulpho-4-oxy-alpha : #-naphthophenazine (or 2-sulpho- 4-oxy-alpha: #-naphtho-10-tolazine) is treated with copper or nickel sulphate, (4) the dyestuff anthranilic acid # 2-sulpho-4-oxy-a : #- naphtho-10-tolazine is treated with copper sulplate, (5) 5: 5<1> - dioxy - 7 : 7<1> - disulpho-1 : 1<1>- 2<1>: 2-dinaphthazine is coupled with 4-nitraniline- 2-sulphonic acid or 4-nitro-2-aminophenol-6-sulphonic acid and the latter product treated with ammoniacal copper oxide or chromium fluoride; 4-nitro-2-aminophenol and 4-chlor-2-aminophenol- 6-sulphonic acid are also specified as diazo components, (6) cotton is grounded in a bath made by reducing 5 : 5<1>-dioxy-7 : 7<1>-disulpho-1 : 1<1> : 2<1> : 2- dinaphthazine to the dihydroazine with hydrosulphite, the dihydroazine oxidized and the colour developed with diazotized p-nitraniline or 2- amino-4-chlorobenzene-1 : 1<1>-phenylether. Azines of the above formula are made from N- substituted 2 : 5 : 7- or 2 : 8 : 6-acids by coupling with a diazo compound in an acid medium and decomposing with an acid the o-aminoazo dyestuff thus obtained. The N-phenyl, p-tolyl, p<1>- anisidyl, m<1>-chlorphenyl, o<1>- and p<1>-xylyl, o<1>, m<1> - and p<1>-carboxyphenyl, p<1>-oxy-m<1>-carboxyphenyl and naphthyl derivatives are specified as starting materials and also 2:2<1>-dinaphthylamine-5 : 5<1>-dioxy-7: 71-disulphonic acid. In an example, diazotized sulphanilic acid is coupled with N-o<1>-carboxyphenyl-J acid in mineral acid and 2-sulpho-4-oxy-alpha : #-naphtho-8-carboxyphenazine is obtained by heating; a dihydroazine is obtained on reduction. The parent materials and properties of the following azines are tabulated : 2 - sulpho - 4 - oxy-alpha: #-naphtho-10-oxy-9(11)-carboxy-, 10-carboxy-, 10-ethoxy-, 8-methoxy, 8: 10- di-methyl-, and 9 (11)-chlorophenazines. N-substituted derivatives of 2: 5:7- and 2 : 8 :6-acids are made from 2 : 5-dioxynaphthalene-7-sulphonic acid or 2 : 8-dioxynaphthalene-6- sulphonic acid, or from 2 : 5 : 7- or 2 : 8 : 6-acid by heating with the appropriate primary amine in presence of a sulphite.