Patent GB-221843-A (GB)
Title: Manufacture of intermediate products for making azo-dyestuffs
Filed: 1923-05-17
Abstract: Cyanuric compounds suitable as diazo or coupling components for azo dye manufacture are obtained by the condensation of a cyanuric halide with one, two, or three molecules of an aromatic compound which contains on the one hand a group having a reactive hydrogen atom (amino, alkyl- or aryl-amino, hydroxy, or thio) and on the other hand an amino, alkyl- or aryl-amino, hydroxy, or active methylene group, or a group convertible into one of these. In place of one or two molecules of these aromatic compounds there may be employed water, ammonia, or any aliphatic or aromatic compound which will react with the halogen of the cyanuric halide. The following known compounds are excluded:-the condensation products of cyanuric chloride with one, two, or three molecules of m-toluylenediamine, the condensation products of cyanuric bromide with three molecules of p-phenylenediamine or benzidine, and the condensation product of cyanuric bromide with two molecules of p-aminophenol. According to examples:-(1) Cyanuric chloride is condensed with one molecule of H-acid; the product is a white powder, more soluble than H-acid itself, and showing no fluorescence in alkaline solution; either or both of the chlorine atoms in its molecule may be replaced by hydroxyl or amino groups by means of caustic soda or ammonia respectively, or they may be replaced successively by one and two aniline residues. In place of aniline there may be employed p-aminoacetanilide, m-aminobenzoic acid, p- or o-aminosalicylic acid, 4-chlor-6-aminosalicylic acid, 4-sulpho-6-aminosalicylic acid, amino-3 : 5-isophthalic acid, acetamide, or diethylamine. (2) Cyanuric chloride is condensed with one molecule of 2 : 5 : 7-aminonaphthol sulphonic acid: treatment of this product with hot mineral acid replaces one or both of the chlorine atoms by hydroxyl; treatment with aniline in the cold replaces one chlorine atom, and the remaining chlorine atom may be replaced by the hydroxyl or amino group, or another aniline residue; or the p dichlorinated condensation product may react with one molecule of m-nitraniline, and this product may be further treated with ammonia; the dichlorinated product may also be condensed with one or two molecules of m-aminoformanilide.  Cyanuric chloride is condensed with one molecule of sodium sulphanilate, and the two chlorine atoms in the product are replaced successively by 2 : 5 : 7-acid and aniline. Cyanuric chloride is condensed with two molecules of ammonia and the product further condensed with 2 : 5 : 7-acid.  (3) Cyanuric chloride is condensed first with one and then with a second molecule of H-acid.  The chlorine atom remaining may be replaced by treatment with water, ammonia, aniline, aminosalicylic acid, aminosulphosalicylic acid, m-aminobenzoic acid, or other amino, hydroxy, or thio compounds. In place of two molecules of H-acid, there may be employed two molecules of 1 : 8 : 4-aminonaphthol sulphonic acid, or one molecule of H-acid and one molecule of 2 : 5 : 7-acid, and these products may be further condensed, for example, with aminosalicylic acid.  (4) The condensation product from cyanuric chloride and two molecules of 2 : 5 : 7-acid is prepared, and may be further condensed with water, ammonia, aniline, m-aminoformanilide, p-aminoacetanilide, b -naphthol, etc.; one or both molecules of 2 : 5 : 7-acid may be replaced by 2 : 8 : 6-acid. (5) The condensation product from one molecule each of cyanuric chloride and H-acid is further condensed with one molecule of m-aminobenzoyl-2 : 5 : 7-acid, and the remaining chlorine atom then replaced by aniline; cyanuric chloride is condensed with two molecules of m-aminobenzoyl-m-aminobenzoyl-H-acid, and the product further condensed with aniline; two molecules of the condensation product from one molecule each of cyanuric chloride and 2 : 5 : 7-acid are condensed with one molecule of p-phenylenediamine giving a dichlorinated product containing two cyanuric groups united by the p-phenylenediamine residue; other diamines of the aliphatic or aromatic series may be used similarly.  (6) The product from cyanuric chloride and two molecules of H-acid described under (3) is condensed with a third molecule of H-acid; similar products are obtained from 2 : 5 : 7- or 2 : 8 : 6-acid or from unsulphonated aminonaphthols, e.g. 2 : 7-aminonaphthol.  (7) Cyanuric chloride is condensed with one molecule of 2 : 5 : 7-acid, then with one molecule of m-phenylenediamine, and the third chlorine atom replaced by treatment with ammonia; the same product is obtained by boiling with ammonia solution the compound from one molecule each of cyanuric chloride, 2 : 5 : 7-acid, and m-aminoformanilide described under (2), or by reducing the product from one molecule each of cyanuric chloride, 2 : 5 : 7-acid, m-nitraniline, and ammonia.  (8) Cyanuric chloride is condensed successively with one molecule each of 1 : 3-phenylenediamine-4-sulphonic acid, 2 : 5 : 7-acid, and ammonia. (9) Cyanuric chloride is condensed with one molecule of 2 : 8 : 6-acid, and then with two molecules of m-aminophenol; similar products are obtained by the reaction of phenylene-, toluylene-, or naphthylene-diamines upon the product from one molecule each of cyanuric chloride, 2 : 5 : 7-acid, and m-phenylenediamine described under (7), or by reduction or saponification of the corresponding products from a nitrated amine or monoacyl-diamine; saponification of the product from cyanuric chloride, 2 : 5 : 7-acid, and two molecules of m-aminoformanilide described under (2), gives a body of this type. (10) Cyanuric chloride is condensed with two molecules of 2 : 5 : 7-acid and then with one molecule of m-toluylenediamine or p-phenylenediamine; the latter product is identical with that obtained by saponifying the corresponding product from p-aminoacetanilide mentioned under (4).  (11) Cyanuric chloride is condensed with one molecule of 1 : 3-phenylenediamine-4-sulphonic acid; this product may be further condensed first with one and then with a second molecule of m-aminoformanilide.  In place of 1 : 3-phenylenediamine-4-sulphonic acid there may be used 1 : 4-phenylenediamine-3-sulphonic acid or other sulphonated or non-sulphonated diamines of the benzene or naphthalene series, aminophenols, aminophenylpyrazolones, &c., while in place of the m-aminoformanilide residue there may be introduced the residues of water, ammonia, phenols, alcohols, aliphatic or aromatic amines, or the amino or hydroxyl derivatives of salicylic or cresotinic acid; thus cyanuric chloride may be condensed with one molecule of m-aminophenol, and the two chlorine atoms of the product then replaced as described above.  (12) The product from cyanuric chloride and two molecules of ammonia is condensed with one molecule of 1 : 3-phenylenediamine-4-sulphonic acid.  (13) Cyanuric chloride is condensed successively with one molecule each of 1-amino-4-acetylaminobenzene-3-sulphonic acid, p-aminosalicylic acid, and sulphanilic acid, and the acetyl group is split off by dilute caustic sode lye.  (14) Cyanuric chloride is condensed with two molecules of 1 : 4-phenylenediamine-3-sulphonic acid or 1 : 3-phenylenediamine-4-sulphonic acid and one molecule of m-aminoformanilide.  (15) Cyanuric chloride is condensed with two molecules of sodium 1 : 4-acetnaphthylenediamine-6-sulphonate; the acetyl group is removed and the chlorine atom replaced by hydroxyl by means of caustic soda, or the chlorine atom is replaced by an amino group by heating with excess of ammonia and the acetyl group then removed by caustic soda.  (16) Cyanuric chloride is condensed with two molecules of m-aminoformanilide, the formyl groups are saponified and the chlorine atom replaced by the amino group by autoclaving with aqueous ammonia; a product whose alkali salts have marked affinity for cotton is obtained by condensing cyanuric chloride with two molecules of m-aminobenzoyl-m-phenylenediamine-p-sulphonic acid, and replacing the chlorine atom by the aniline residue.  Two molecules of the condensation product from one molecule each of cyanuric chloride and 1 : 3-phenylenediamine-4-sulphonic acid are condensed with one molecule of p-phenylenediamine and the two chlorine atoms of the dicyanuric product so formed are then replaced by aniline residues. (17) Cyanuric chloride is condensed with two molecules of 1-(31-amino) phenyl-5-pyrazolone-3-carboxylic acid; the last chlorine atom may be suitably replaced; analogous products are obtained from other aminoarylpyrazolones.  (18) The condensation product from one molecule of cyanuric chloride, two molecules of 1 : 3-phenylenediamine-4-sulphonic acid, and one molecule of m-aminoformanilide, is saponified by caustic soda; similar products are obtained by saponifying the condensation products from one molecule of 1 : 3-phenylenediamine-4-sulphonic acid and two molecules of m-aminoformanilide; in place of 1 : 3-phenylenediamine - 4-sulphonic acid 1 : 4-phenylenediamine-3-sulphonic acid may be used, and m-aminoformanilide may be replaced by m-nitraniline and the resulting products reduced.  Specifications 3615/00 and 205,525 are referred to.