Patent GB-774886-A (GB)
Title: Process for the production of aromatic o-hydroxydiazo compounds, and the products
IPC: C09B41/00
Filed: 1954-07-16
Abstract: Aromatic o-hydroxydiazo compounds are made by adding stabilizers for them to a mineral acid solution of an unsulphonated diazonium compound of formula: <FORM:0774886/IV(b)/1> where R1 and R2 are non-salt-forming substituents which have an attracting influence on the pair of electrons linking the substituents to the residue of the diazonium compound and in which the benzene ring may be further substituted and raising the pH value of the medium, preferably to 6-11, by neutralization of the mineral acid so that R1 is replaced by a hydroxy group.  R1 may be a halogen atom or preferably a nitro group and R2 is e.g. a nitro, alkyl or aryl keto, cyano, sulphonamide or N-substituted sulphonamide, sulphonic acid aryl ester or an alkyl, cycloalkyl or aryl sulphone group.  The substituents may themselves be substituted, e.g. by halogen, alkyl, alkoxy or sulphonamide groups.  The products are used in the preparation of metallized dyestuffs and especially when R2 is a group -SO2-X, where X is a methyl, ethyl or chloromethyl group.  Starting compounds in which R1 is a nitro group may be made by nitrating an acylamino, alkoxy or halogen compound which is negatively substituted in the p-position followed by conversion of the acylamino, halogen or alkoxy group to an amino group and diazotization of the amino compound. o-Nitroamines may advantageously be diazotized in concentrated sulphuric acid with dry alkali nitrite or nitrosyl sulphuric acid. Conventional stabilizers may be used, preferably those not disadvantageous in the preparation of metallizable dyestuffs, particularly aromatic sulphonic acids and their alkali metal salts, e.g. p-toluene- and 1,2-dimethylbenzene-4-, tetrahydronaphthalene- and naphthalene-1-and 2-mono- and 2,7-di-sulphonic acids.  Other specified stabilizers are zinc chloride and fluoboric acid or soluble salts thereof.  Preferably an aquous solution of the diazo solution and stabilizer is added dropwise to a cold aqueous sodium carbonate solution.  In examples: (1) 3-nitro - 4 - aminobenzene - 1 - methyl sulphone; (2) 3 - nitro - 4 - aminobenzene - 1 - ethyl sulphone; (3) 2,4 - dinitraniline; and (4) 3-nitro - 4 - aminobenzene - 1 - chloromethyl sulphone are diazotized in mineral acid and neutralized with caustic soda or sodium carbonate to yield the corresponding diazoxide.  Other specified amines are 3-nitro-4-aminobenzene-vinyl and phenyl sulphones, 3-nitro-4-amino-benzo-and aceto-phenones and benzonitrile, 3-nitro-4-aminobenzene - 1 - sulphonic acid dimethylamide and sulphonic acid morpholide and 3-nitro - 4 - amino - 41 - methyl - diphenyl sulphone.  Specifications 774,884 and 774,885 are referred to.ALSO:Aromatic o - hydroxydiazo components made by adding stabilizers for them to a mineral acid solution of an unsulphonated diazonium compound of formula <FORM:0774886/IV(b)/1> where R1 and R2 are non-salt forming substituents which have an attracting influence on the pair of electrons linking them to the nucleus and in which the benzene ring may be further substituted and raising the pH value of the medium, preferably to 6-11, by neutralization of the mineral acid so that R1 is replaced by OH, yield diazoxides which may be coupled with azo components and metallized.  R1 may be a halogen atom or preferably a nitro group and R2 is e.g. a nitro, alkyl or aryl keto, cyano, sulphonamide, N - substituted sulphonamide, sulphonic acid aryl ester or an alkyl cycloalkyl or aryl sulphone group.  The substituents may themselves contain such groups as halogen, alkyl, alkoxy or sulphonamide groups. For the formation of metallized dyestuffs R2 is preferably -O2X where X is a methyl, ethyl or chloromethyl group.  In an example the diazoxide from 3 - nitro - 4 - aminobenzene - 1 - methyl sulphone is alkaline coupled with 1 - phenyl - 3 - methyl - 5 - pyrazolone. Specifications 774,884 and 774,885 [Group IV(a)] are referred to.