Patent GB-708834-A (GB)
Title: Improvements relating to processes and materials for use in printing, with the application of diazo compounds
IPC: G03F7/022
Filed: 1951-07-31
Abstract: The invention comprises diazo-phenols which in their tautomeric quinone-diazide form have the structure <FORM:0708834/IV (b)/1> where X is -SO2OAr, -COOAr, -SO2NYAr or -CONHAr, Ar being an aromatic residue and Y being hydrogen or an aliphatic or aromatic residue. The benzene nucleus may be further substituted, e.g. by hydrocarbon residues.  Preferred compounds for use in light-sensitive printing plates (see Group XX) are those in which X is a sulphonamide group para to the oxygen atom. The sulphonamides are made from o - aminophenol - sulphonic acids by successive conversion into benzoxazolone-sulphonic acids, benzoxazolone-sulphochlorides, benzoxazolone - sulphonamides and aminophenol - sulphonamides, and diazotization of the latter, preferably in the presence of a water-miscible solvent such as dioxane.  The sulphonic esters are prepared from o-nitrophenolsulphonic acids by conversion into sulphochlorides, esterification with phenols in the presence of zinc dust, catalytic reduction of the nitro group and diazotization. Alternatively compounds of the above formula, where X is a sulphonic acid group, are converted into sulphochlorides and then esterified in alkaline solution.  The carboxylic amides are obtained from hydroxybenzoic acids by reaction with aromatic amines (in the presence of phosphorus chlorides and an inert solvent) to give hydroxybenzarylides, nitration of the latter, catalytic reduction and diazotization.  The carboxylic esters are made by esterifying o-nitrophenolcarboxylic acids in the presence of dehydrating agents (e.g. phosphorus chlorides), catalytic reduction of the esters and diazotization.  Examples show the production of (1) benzoxazolone-5-sulphonic acid, benzoxazolone-5-sulphochloride, benzoxazolone - 5 - (N : N - di-phenylsulphonamide), 2 - aminophenol - 4 - (N : N - diphenylsulphonamide) and its diazo compound; (2) benzoxazolone-5-(N-ethyl-N-21-naphthylsulphonamide), 2 - aminophenol - 5 - (N - ethyl - N - 21 - naphthylsulphonamide) and its diazo compound; (3) N : N1-di-(benzoxazolone - 5 - sulphonyl) - benzidine, N : N1 - di - (2 - aminophenol - 4 - sulphonyl) - benzidine and its bis-diazo compound; (4) 4 : 41-di-(benzoxazolone - 5 - sulphonamido) - benzophenone, 4 : 41 - di - (211 - aminophenol - 411 - sulphonamido) - benzophenone and its bis-diazo compound; (5) N : N1 - di - (benzoxazolone - 5 - sulphonyl) - N : N1 - dimethyl - p - phenylene diamine and the bis-diazo compound of N : N1-di-(2-aminophenol - 4 - sulphonyl) - N : N1 - dimethyl - p - phenylene diamine; (6) the N : N1 - dimethyl derivatives of (3); (7) as in (1) with a 5-methyl group in the aminophenol nucleus; (8) 6-methylbenzoxazolone - 5 - (N - methyl - N - p - tolyl - sulphonamide) as sodium derivative, 5-methyl-2 - aminophenol - 4 - (N - methyl - N - p - tolylsulphonamide) and its diazo compound; (9) as in (1) with a 6-methyl group in the aminophenol nucleus; (10) 7 - methylbenzoxazolone - 5 - (N - methyl - N - p - tolylsulphonamide), 6 - methyl - 2 - aminophenol - 4 - (N - methyl - N - p-tolylsulphonamide) and its diazo compound; (11) 5-chlorobenzoxazolone - 7 - sulphonic acid, 5 - chlorobenzoxazolone - 7 - sulphochloride, 5 - chlorobenzoxazolone - 7 - (N - phenylsulphonamide), 4 - chloro - 2 - aminophenol - 6 - (N - phenylsulphonamide) and its diazo compound; 5 - chlorobenzoxazolone - 7 - (N - 21 - naphthylsulphonamide) and the diazo compound of 4 - chloro - 2 - aminophenol - 6 - (N - 21 - naphthylsulphonamide); 5 - chlorobenzoxazolone - 7 - (N - ethyl - N - phenylsulphonamide), 4 - chloro - 2 - aminophenol - 6 - (N - ethyl - N - phenylsulphonamide) as sodium salt and its diazo compound; (12) phenol - 4 - carboxylic 21 : 41 - dichloranilide, 2 - nitrophenol - 4 - carboxylic 21 : 41-dichloranilide, 2-aminophenol-4-carboxylic 21 : 41-dichloranilide and its diazo compound; (13) phenol-4-carboxylic 21-naphthylamide, 2-nitrophenol-4-carboxylic 21-naphthylamide, 2 - aminophenol - 4 - carboxylic 21-naphthylamide and its diazo compound; (14) 3 - nitro - 4 - hydroxybenzoic phenyl ester, 3 - amino - 4 - hydroxybenzoic phenyl ester and its diazo compound; (15) 3-nitrosalicylic 2-naphthyl ester, 3-aminosalicylic 2-naphthyl ester and its diazo compound; (16) 2 - nitrophenol - 4 - sulphochloride, 2 - nitrophenol - 4 - sulphonic phenyl ester, 2 - aminophenol-4-sulphonic phenyl ester and its diazo compound; analogous 2-naphthyl esters; 2-diazophenol - 4 - sulphochloride and 4 : 41 - di - (2 - diazophenol - 4 - sulphonyloxy) - diphenyl; (17) 4 : 41 - di - (benzoxazolone - 5 - sulphonamido) - 2 : 21 : 5 : 51 - tetramethyl - triphenylmethane, 4 : 41 - di - (2 - aminophenol - 4 - sulphonamido) - 2 : 21 : 5 : 51 - tetramethyl - triphenylmethane and its bis-diazo compound; (18) benzoxazolone - 5 - (N - 21 - fluorenyl - sulphonamide), 2 - aminophenol - 4 - (N - 21 - fluorenyl-sulphonamide) and its diazo compound; (19) 1 : 1 - di - (41 - (benzoxazolone - 511 - sulphonamido) - phenyl) - cyclohexane, 1 : 1 - di - (41 - (211 - aminophenol - 411 - sulphonamido)-phenyl)-cyclohexane and its bis-diazo compound. Specifications 699,412 and 706,028 are referred to.