Patent GB-706879-A (GB)
Title: Improvements in materials and processes for photomechanical reproduction
IPC: G03F7/022
Filed: 1952-01-11
Abstract: Intermediates for water-insoluble azo dyes (see Group IV (c)) used as light-sensitive photographic reproduction material (see Group XX) comprise:-  71 - Hydroxynaphtho - 11 : 21 : 4 : 5 - imidazol substituted on the nitrogen by a 2-diazonaphthol (1)-5-sulphonyl residue, which is made by heating the imidazole with the corresponding sulphochloride in dioxane and precipitating the intermediate with hydrochloric acid.  Benzoxazolone - 5 - (N - p - aminophenyl)-sulphonamide hydrochloride, made by heating benzoxazolone-5-sulphonic acid with phosphorus pentachloride in dioxane and condensing the resulting sulphochloride with 4-nitraniline, purifying and reducing the product with Raney nickel. (Benzoxazolone - 5 - sulphonyl) - 41 : 411-diaminodiphenyl hydrochloride, made by treating benzoxazolone-5-sulphochloride with 4 : 41-diaminodiphenyl in dioxane, evaporating off the latter and treating the residue with caustic soda solution and then hydrochloric acid.  N1 - (3 - amino - 4 - hydroxybenzyl) - 41 - amino-2 : 51 - diethoxyaniline, made by condensing p-hydroxybenzoic acid and aminohydroquinone diethyl ether in toluene in the presence of phosphorus trichloride, nitrating and then reducing the product.ALSO:Water-insoluble azo dyes used as light-sensitive material in photographic or photomechanical reproduction contain in the molecule at least one residue of an orthoquinone diazide and in addition to the azo group at least one auxochromic group.  The dyes are derived from a sulphonic or carboxylic acid of an ortho-quinone diazide and the azo dye residue thereof is coupled in ester-like or amide-like manner to the sulphonic or carboxylic group.  In preparation (a) amino azo or hydroxyazo dyestuffs are reacted with the chlorides of diazo-naphthol or diazo-phenol sulphonic or carboxylic acids (b) the compounds obtained by condensation of benzoxazolone sulphochlorides with aromatic nitroamines are reduced to amino compounds and the latter diazotized, coupled, treated with dilute alkali to split off the oxazolone groups and diazotized again (c) poly-amino, -hydroxy or -aminohydroxy compounds are reacted as in (a) to produce several diazo naphthol or diazo phenol residues in the molecule and coupled with azo components.  In examples dyes are made (1) by treating the azo dye from diazotized 4-amino-4\sv-hydroxydiphenyl and b -naphthol with 2-diazo naphthol-(1)-5-sulphochloride p  (naphthoquinone-(1: 2)-diazide-(2)-5-sulphonic acid chloride) in dioxane; (2) by coupling b  naphthol with the condensation product from 2-diazonaphthol-(1)-5-sulphochloride and 2:7-naphthylene diamine; (3) by heating 7\sv-hydroxynaphtho-1\sv:2\sv:4:5-imidazole and 2-diazonaphthol-(1)-5-sulphochloride in dioxane, filtering off deposited hydrochloride of the former and pouring the solution into dilute hydrochloric acid to precipitate 7\sv-hydroxynaphtho-1\sv:2\sv:4:5-imidazole substituted on the nitrogen by the 2-diazonaphthol-(1)-5-sulphonyl residue, dissolving this as in monomethyl glycol ether, adding sodium carbonate solution and coupling with a diazo solution from aminohydroquinone diethyl ether.  A similar dye is obtained by coupling the first mentioned imidazole derivative with diazotized aniline to make the 8\sv phenyl-azo-substitution product thereof and reacting this in dioxane with 2-diazo-naphthol-(1)-5 sulphochloride by addition of sodium carbonate solution; (4) by heating 1-(p-hydroxyphenylazo)-2-hydroxy-naphthalene with benzoquinone (1:2)-diazide-(2)-4-sulphochloride in dioxane; (5) by coupling diazotized benzoxazolone-5-(N-p-aminophenyl)-sulphonamide hydrochloride with b -naphthol and hydrolysing and then diazotizing the product; (6) the hydrochloride of N-(benzoxazolone-5-sulphonyl)-4\sv-4\sM-diaminodiphenyl is diazotized in dioxane, coupled with 2:3-hydroxynaphthoic acid anilide, treated to split the oxazolone ring and diazotized (7) 2:3-hydroxynaphthoic acid replaces the b -naphthol of Example 5; (8) N:N\sv-bis-(2:3-hydroxynaphthoyl)-ethylene diamide is used instead of the coupler of Examples (5) and (7) (9) benzoxazolone-5-sulphochloride is condensed with benzidine, hydrolysed, diazotized and coupled with b -naphthylamine; (10) an ortho-carboxylic acid derivative of the dye of Example (5) is made by an analogous procedure; (11) N\sv-(3-amino-4-hydroxybenzoyl) -4\sv-amino-2\sv:5\sv-diethoxyaniline is partially diazotized and coupled with b -naphthol in dilute alkali, precipitated with hydrochloric acid, dissolved in the calculated quantity of caustic soda solution, treated with the calculated quantity of sodium nitrite and acidified for re-diazotization.