Patent GB-745886-A (GB)
Title: Improvements in or relating to processes for the photo-mechanical production of planographic printing plates and light-sensitive material therefor
IPC: C07C311/44
Filed: 1954-05-26
Abstract: Aromatic azido compounds substituted in the azido-containing nucleus by a sulphonic acid group amidated with a primary aromatic amine or by a primary amine group substituted with the sulphonyl residue of an aromatic sulphonic acid are made by (1) reaction of chlorides of nitrosulphonic acids with bases, reduction of the nitro group to the amino group, diazotization and conversion of the diazo compound to the azide; (2) conversion of sulphonic acids which already have an azido group in the molecule into sulphonyl chlorides and reaction of the latter with bases; (3) reaction of aromatic nitroamines with sulphonyl chlorides and conversion of the nitro group to the azido group as in (1).  Particular compounds are  4.41 - Diazidostilbene - 2,2 - disulphonanilide, made by condensing 4.41-dinitrostilbene 2.21-disulphonylchloride with excess of aniline in dioxane or benzene, reducing the anilide formed with Raney nickel in dimethyl formamide, diazotization of the resulting amine and reaction of the product with sodium azide; or by chlorination of 4.41-diazidostilbene-2,21-disulphonic acid and reaction of the disulphonylchloride so obtained with aniline. The corresponding substituted anilides may be made by replacing the aniline with para-toluidine, 2-amino - 1,4 - dimethylbenzene, para - aminophenolglycolether, para - anisidine, paraaminophenol, para-aminobenzoic acid or paraaminobenzophenone.  4 - Azido - 1 - phenylaminobenzene - 2 - sulphon - a  - naphthylamide, made by condensing 1 - chloro - 4 - nitrobenzene - 2 - sulphonylchloride with a -naphthylamine, boiling the product with aniline to replace the chlorine by a phenylamine group, and reducing the nitro group, diazotizing and reacting with sodium azide as above.  The corresponding 2-sulphonanilide may be made by replacing the a -napthylamine with aniline.  4 - Azido - 2 - p - toluenesulphonamido - 1-phenylaminobenzene, made by combining 1-chloro-2.4-dinitrobenzene with aniline in boiling alcohol, partially reducing the product with sodium disulphide to 4-nitro-2-amino-1-phenylaminobenzene, combining this with paratoluenesulphonylchloride, reducing the nitro group, diazotizing and reacting with sodium azide as above.  1,4 - Bis - (41 azido - 11 phenylaminobenzene-21 sulphonamido) - benzene, made by condensing 2 mols. of 1-chloro-4-nitrobenzene-2-sulphonylchloride with para-phenylenediamine, boiling with excess aniline to replace the chlorines with phenylamino groups, reducing the nitro groups, diazotizing and reacting with sodium azide as above.  The corresponding 1,4-bis - benzophenone and 1,4 - bis - 11,51 naphthalene compounds may be made similarly by replacing the para-phenylene diamine with 4,41-diaminobenzophenone and 1,5-diaminonaphthalene respectively.  4 - Azido - 1 - (paratoluenesulphonamido)-naphthalene, made by reacting para-toluensulphonylchloride with 4-nitro-1-naphthalene and reducing, diazotizing and reacting the product with sodium azide as above.  2 - Azido - 1,4 - naphthalenedibenzene-sulphonamide, made by oxidizing 1,4-naphthalenedibenzenesulphonamide with lead tetraacetate in glacial acetic acid solution to the corresponding naphthoquinone-di-sulphonimide and treating this with sodium azide to add hydrazoic acid.  2,3 - Diazido - 1,4 - naphthalenedibenzene-sulphonamide, made by oxidizing similarly and then again adding hydrazoic acid to the 2-azido compound.  2 - Azido - 4 - (para - toluenesulphonamido)-1,8 - naphthosultam, made by condensing paratoluenesulphonylchloride with 4 - amino - 1,8-naphthosultam, oxidizing the product similarly to the corresponding di-imide and adding hydrazoic acid to this.  2 - Azido - 1,4 - benzenedibenzenesulphonamide, made by oxidizing, similarly 1,4 - benzenedibenzenesulphonamide to 1.4-benzoquinonedibenzenesulphonimide and adding hydrazoic acid to this.  The tetraazido compound 2.21 - bis - (paraazidobenzeneaminosulphonyl) - 4,41 - diazidostilbene is made by condensing 4.41-dinitrostilbene - 2,21 - disulphonylchloride with 2 mols. of paranitroaniline, reducing the product to the tetra amino compound, fully diazotizing this and treating with sodium azide.  3 - Azido - 4.41 - bis(benzenesulphonamido)-benzidine, made by oxidizing 4.41-benzidinedibenzenesulphonamide to the corresponding diphenoquinone imide and reacting this with sodium azide.  1,3 - Bis - (41 - azido - 21,51 - diethoxybenzeneamidosulphonyl) - benzene, made by condensing 1,3 - benzenedisulphonylchloride with 2 mols. of aminohydroquinonediethylether, nitrating, reducing and diazotizing the product to the bisdiazonium chloride and reacting this with sodium azide.  4.41 - Bis - (411 - azido - 211.511 - diethoxybenzeneamidosulphonyl - 3111 - phenylene - carbonamido) - diphenylmethane, made by condensing benzoic acid-3-sulphonylchloride with aminohydroquinone-diethylether, nitrating the product, treating with PCl5 to form the acid chloride, condensing this with 4,41-diaminodiphenylmethane, and reducing, diazotizing and treating with sodium azide.  1.4 - Bis - (51 - azidonaphthalenesulphonylamido) - benzene, made by condensing paraphenylenediamine with 2 mols. of 5-nitro-1-naphthalenesulphonylchloride, reducing the nitro groups to amino, diazotizing and treating with sodium azide.  1.3 - Bis - (41 - azido - 21 - 51 - diethoxysulphonylamido) - benzene, made similarly from the condensate of metaphenylene diamine with 2 mols. of 4-nitro-2.5-diethoxybenzene-1-sulphonylchloride.