Patent GB-769003-A (GB)
Title: New dibenzothiophene dioxide derivatives and their manufacture and use
IPC: C07D333/76
Filed: 1953-10-29
Abstract: Dibenzothiophene dioxide derivatives of the formula <FORM:0769003/IV(a)/1> are applied to films or threads, for brightening purposes, in the course of their manufacture, e.g. they may be added to spinning solutions of viscose or acetyl cellulose or to synthetic polyamides.  In the formula x and y are amino, substituted amino or an organic residue attached via O or S, v and w are halogen, hydroxy or groups as specified for x and y, and Z1 and Z2 are hydrogen, halogen, alkyl, alkoxy or sulphonic acid, the last-named being meta to the -NH- group; v, w, x and y do not contain any group imparting colour.  Suitable compounds are mentioned.ALSO:The invention comprises dibenzothiophene dioxide derivatives of the formula <FORM:0769003/IV(b)/1> where x and y are amino, substituted amino or an organic residue attached via O or S, v and w are halogen, hydroxy or groups as specified for x and y, and Z1 and Z2 are hydrogen, halogen, alkyl, alkoxy or sulphonic acid, the last-named being meta to the -NH- group; v,w,x and y do not contain any group imparting colour.  Preferred compounds are (a) Z1=H, Z2=alkyl and v, w, x and y are residues of aliphatic amines; (b) Z1=H, Z2=alkyl ortho to the -NH- group, v and w are residues of a sulphonated aromatic amine and x and y are residues of a non-aromatic amine; and (c) Z1=H, Z2=sulphonic acid meta to the -NH-group and v, w, x and y are residues of nonaromatic amines.  Sulphonic acid groups are preferably converted into their alkali metal, ammonium or amine salts.  The compounds are made by reacting in any order (a) benzidine optionally substituted by Z1 and Z2, (b) an agent yielding SO3, (c) 2 mols. of cyanuric chloride, and (d) 2-4 mols. of ammonia, a primary or secondary amine, a hydroxyl compound or a mercaptan; any remaining chlorine atoms can then be converted to hydroxyl.  The agent yielding SO3 may be oleum or an organic solvent solution of sulphur trioxide. Thus benzidene or an unsulphonated derivative thereof may be ring-closed with oleum (at low temperatures) to the dibenzothiophene dioxide, the latter condensed with two mols. of cyanuric chloride (preferably in the presence of glacial acetic acid) and the chlorine atoms then replaced as necessary, e.g. by reaction with amines; water-solubilizing groups may be present in the amine (e.g. diethanolamine) or when ammonia or a primary amine is used such groups may be introduced by reaction with aldehyde-bisulphite compounds, sulphonated alkyl or aralkyl halides, or sultones. Alternatively benzidine or an unsulphonated derivative thereof is condensed with two mols of cyanuric chloride, the chlorine atoms replaced as necessary and the cyclic sulphone group finally introduced by reaction with oleum; the latter treatment may effect sulphonation of the nuclei of arylamine residues attached to the triazine ring.  Both the above methods may be modified by replacing the spare chlorine atoms in the cyanuric chloride before instead of after condensation.  In another method benzidine-2 : 21-disulphonic acid or a derivative thereof is condensed with two mols. of cyanuric chloride and the product ring-closed with oleum, the extra chlorine atoms being replaced as necessary.  In the examples: (1) cyanuric chloride is condensed with one-half mol. of benzidine-2 : 21-disulphonic acid and two mols. of ethylamine, and the product ring-closed with oleum to 3 : 7-bis-[(2 : 4-diethylamino-6-triazinyl) - amino] - dibenzothiophenedioxide - 1 : 9-disulphonic acid (isolated as di-sodium salt); (2) cyanuric chloride is condensed with one-half mol. of o-tolidine, one mol. of aniline and one mol. of ethylamine; the product is treated with oleum to give 3 : 7-bis-[(2-sulphoanilino - 4 - ethylamino - 6 - triazinyl) - amino] - dimethyl-dibenzothiophene dioxide (isolated as di-sodium salt); (3) N : N1-bis-(2 : 4-diethylamino - 6 - triazinyl) - o - tolidine prepared similarly is ring-closed with oleum to the corresponding dibenzothiophene dioxide; (4) cyanuric chloride is condensed with one-half mol. of the cyclic sulphone of o-tolidine, one mol. of ethylamine and one mol. of sulphanilic acid; the product is isolated as its di-sodium salt; (5) cyanuric chloride is condensed with one-half mol. of benzidine sulphone, one mol. of phenol and one mol. of sulphanilic acid.  Tables are given of other products in which the groups v, w, x and y are in addition methylamino, dimethylamino, diethylamino, piperidino, ethanolamino, diethanolamino, morpholino, amino, hydroxy, sulpho-anilino, sulpho-toluidino, sulpho - chloranilino, b  - diethylamino - ethylamino and phenylthio.  Other specified reactants for introducing these radicals are various alkanols, halo-alcohols, oxycarboxylic and oxysulphonic acids, allyl alcohol and mercaptan, isethionic acid, amyl mercaptan, thioglycollic acid, thioglycol, polyglycols, cresols, chloro- and bromo-phenols and cresols, naphthols, p-t-butylphenol, oxybenzoic acids, phenolsulphonic acids, thymol, guaiacol, benzyl alcohol, p - tolylcarbinol, tetrahydronaphthylcarbinols, 2-mercapto - thiazoline, 2 - oxybenzthiazole, 2 - mercapto-benzthiazole, various alkylamines and substituted alkylamines, allylamine, taurine, chloranilines, anisidines, naphthylamines, a -pipecoline, pyrrolidine, imidazole, benzimidazole, 2-aminothiazole, 5-amino-tetrazole and tetrahydroquinoline.ALSO:Dibenzothiophene dioxide derivatives of the formula <FORM:0769003/IV(b)/1> are used as fluorescent brightening agents for textile materials, fibres and films, which may be undyed, dyed or printed; in the formula x and y are amino, substituted amino or an organic residue attached via O or S, v and w are halogen, hydroxy or groups as specified for x and y, and Z1 and Z2 are hydrogen, halogen, alkyl, alkoxy or sulphonic acid, the lastnamed being meta to the -NH- group; v, w, x and y do not contain any group imparting colour.  The compounds are applied in aqueous or organic solution, or dispersed with the aid of soaps, polyglycol ethers, sulphite cellulose waste liquor or alkyl-aryl sulphonic acids.  They may be applied to materials at any stage in the manufacture, e.g. in washing baths, in anti-creasing liquors or for after-treating discharge prints.  Suitable washing agents with which they may be used are soaps, sulphonated higher alkyl benzimidazoles, sulphophthalic ester salts, fatty alcohol sulphonates, polyglycol ethers and amines, and condensation products of higher fatty acids with oxy- and aminosulphonic acids.  There may also be present alkali phosphates, and condensed phosphates, silicates, percarbonates, perborates and other brightening agents.  Materials treated may be wool, silk, polyamides, natural and regenerated cellulose or synthetic polymers.  In examples, (1) undyed cotton yarn is treated with the disodium salt of 3:7-di-[(2-sulphonanilino-4 - ethylamino - 6 - triazinyl) - amino] - dimethyl-dibenzothiophene dioxide; (2) undyed textile goods are washed with the product of (1) and the disodium salt of heptadecyl-N-benzyl-benzimidazole disulphonic acid; (3) undyed cotton yarn is treated with the disodium salt of 3:7-di-[(2:4-diethylamino -6- triazinyl)-amino]-dibenzothiophene dioxide-1:9-disulphonic acid and the disodium salt of 4:41-bisphenylureido-stilbene-2 : 21 - disulphonic acid; (4) undyed polyacrylonitrile yarn is treated with the dibenzothiophene dioxide compound of (3) and formic acid; (5) wool is treated with the compound of (1) and formic acid.  Other suitable compounds are mentioned.ALSO:Dibenzothiophene dioxide derivatives of the formula <FORM:0769003/III/1> are incorporated into washing agents, for brightening purposes, by mixing, grinding or fusing the components together.  In the formula x and y are amino, substituted amino or an organic residue attached via O or S, v and w are halogen, hydroxy or groups as specified for x and y, and Z1 and Z2 are hydrogen, halogen, alkyl, alkoxy or sulphonic acid, the last-named being meta to the -NH- group; v, w, x and y do not contain any group imparting colour. The washing agents may be soaps, sulphonated higher alkyl benzimidazoles, sulphophthalic ester salts, fatty alcohol sulphonates, polyglycol ethers and amines, and condensation products of higher fatty acids with oxy- and amino-sulphonic acids.  The usual additives such as alkali phosphates and condensed phosphates, silicates, percarbonates and perborates may be present, and the washing compositions may consist wholly or predominantly of inorganic cleansing agents and the dibenzothiophene derivatives.  Other brightening agents may also be present.  Suitable dibenzothiophene derivatives are mentioned.