Patent GB-603594-A (GB)
Title: Electrolytic recording
IPC: B41M5/20
Filed: 1945-10-11
Abstract: Diazoamino compounds of the general formul  <FORM:0603594/IV(b)/1> <FORM:0603594/IV(b)/2> (wherein R1, R2, R3 and R4 represent aliphatic radicals, e.g. ethyl, methyl, propyl, butyl, isopropyl, isobutyl, amyl, octyl, ethanol, propanol, butanol, hexanol, carboxyethyl, carboxymethyl, carboxypropyl, carboxybutyl, sulphomethyl, sulphoethyl, sulphopropyl or sulphobutyl, araliphatic radicals, e.g. benzyl, cycloaliphatic radicals, e.g. cyclopentyl, cyclohexyl, hydroxycyclohexyl, sulphocyclohexyl or carboxycyclohexyl, aromatic radicals, e.g. the residues of mono- or di-sulphobenzoic acids, or heterocyclic radicals, e.g. pyridyl, or R1 or R3 may also represent hydrogen, A and A1 represent aromatic residues, e.g. of the benzene, naphthalene, anthracene, diphenyl or diphenyl ether series, with or without nuclear substituents such as alkyl, e.g. ethyl, methyl or propyl, alkoxy, e.g. methoxy or ethoxy, halogen, e.g. chlorine or bromine, nitro, amino, acylamino, e.g. acetylamino, benzoylamino or naphthoylamine, carboxy, sulpho or carbamyl, e.g. benzene carbamyl or 8-hydroxy-3 : 6-disulphonaphthalenecarbamyl, Z represents the atoms necessary to complete a nitrogenous heterocyclic ring system, e.g. that of pyrroles such as a -carboxypyrrolidine, a 1 : a 2-dicarboxypyrrolidine or pyrrolidine-a -sulphonic acid, piperidines such as piperidine itself, a - or b -carboxypiperidine or piperidine-g -sulphonic acid, morpholine, carbazole, 1 : 2 : 3 : 4-tetrahydroquinoline or tetra- or hexa-hydrocarbazoles, and x is 1 or 2) are manufactured by the interaction in alkaline solution of a diazonium compound and an organic amine which does not easily couple to form an azo dye.  The stabilizing amine should be in excess, which may be up to 0.5 per cent for insoluble diazoamino compounds whilst for a soluble diazoamino compound there may be used up to 2.62 mols. of stabilizer to one of diazonium compound.  In examples: (1) dianisidine is tetrazotized and added to a solution of diethanolamine and soda ash; (3) sodium nitrate is added to a solution of sodium naphthionate in aqueous caustic soda, which is then added to hydrochloric acid and the diazonium compound is filtered off, slurried in water and added to a solution of diethanolamine; (6) 41 - diethanolamino - 4 - aminoazobenzene is treated as in (3); (7) the dianisidine in (1) is replaced by benzidine; (8) 1-naphthylamine-4 : 8-disulphonic acid is treated as in (3); (9) the diethanolamine in (1) is replaced by sarcosine; (10) anthranilic acid is treated as in (3); (11) the diethanolamine in (3) is replaced by 2 : 5-dihydroxydicyclohexylamine-31-carboxylic acid; (12) by p-hydroxycyclohexenylglycine; (13) by g -hydroxypiperidine; (14) by morpholine; (15) by cyclohexylamine; and (16) by 4-sulpho-2-aminobenzoic acid.  The following additional starting materials (and specific combinations of some of them) are listed: diazotizable amines: 1- and 2-naphthylamine-5-sulphonic and 3 : 6-disulphonic acids, benzidine-3 : 31 - disulphonic acid, 1 - aminodiphenylene oxide and sulphide, 1 - amino - 2 - methoxy - 5 - chlorobenzene, 1 - aminoanthracene, 4 - amino - diphenyl, 6 - amino - 3 - benzoylamino - 1 : 4 - di - ethoxybenzene and 4 : 41 - diamino - 3 : 31 - dimethyldiphenyl; stabilizing agents: monoethanolamine, di-isopropanolamine, methylglucamine, a -carboxy- and a 1 : a 2-dicarboxypyrrolidine, carboxypiperidines, loiponic acid, 1 : 2 : 3 : 4-tetrahydroquinoline, piperidine, carbazole, diglycolamino acid, benzylxylamine, dibenzylaminedisulphonic acids, taurine, cyclohexylaminoacetic acid, 2-methylamino-4-sulphobenzoic acid, methylmannamine, dimethylamine, diethylamine, dibutylamine, di-2-ethylhexylamine, a -hydroxypyrrolidine, ö-hydroxypiperidine and carbazole-2-sulphonic acid.