Manufacture of 3.5-diaminopyrazine-2.6-dicarboxylic acid derivatives and their use as optical brightening agents

摘要

3,5-Diaminopyrazine-2,6-dicarboxylic acid amide optical brightening agents of the formula wherein R1, R2 and R3 each represent an aliphatic, araliphatic or cycloaliphatic group which may contain chlorine, alkoxy or hydroxy substituents, and X represents a primary amino group, an aliphatic, araliphatic, cycloaliphatic, mononuclear-aromatic, or heterocyclic-substituted secondary or tertiary amino group (each of which may contain optional chlorine, hydroxy, alkoxy, phenoxy, carboxylic, sulphonic and sulphonamide substituents), a cyclic tertiary amino group, a ureido group, or a residue of a di-primary or di-secondary aliphatic or araliphatic diamine in which one nitrogen atom is attached to the 6-carbonyl group of the above formula and the other nitrogen atom is attached to a similar 3,5-diamino-pyrazine-2-carboxylic acid amide-6-carbonyl residue, are incorporated with fats and waxes, and with sodium, potassium and alkanolamine soaps, as well as with synthetic anionic or non-ionic detergents such as alkyl sulphates, fatty acid mono-glyceride sulphates, sulphated ethers of fatty alcohols, alkylphenols, fatty alkanolamide sulphates, alkyl, alkylbenzene and alkylnaphthol sulphonates, sulphonated alkyl derivatives of N-phenyl-1:3:5-triazines, alkylsulphosuccinates, isethionates, taurine and taurides; and ethylene oxide condensates with fatty alcohols, acids and alkanolamides. Alkali metal or ammonium salts of sulphuric, hydrochloric, carbonic, boric, silicic, phosphoric, perboric, percarbonic and persulphuric acids, magnesium metasilicate, cellulose methyl and ethyl ethers and alkali metal salts of carboxymethyl cellulose and polyamine polyacetic acids may also be included. Specification 674,847 is referred to.ALSO:3,5-Diaminopyrazine-2,6-dicarboxylic acid amide optical brightening agents of the formula wherein R1, R2 and R3 each represent an aliphatic, araliphatic or cycloaliphatic group which may contain chlorine, alkoxy or hydroxy substituents, and X represents a primary amino group, an aliphatic, araliphatic, cycloaliphatic, mononuclear-aromatic or heterocyclic-substituted secondary or tertiary amino group (each of which may contain optional chlorine, hydroxy, alkoxy, phenoxy, carboxylic, sulphonic and sulphonamide substituents), a cyclic tertiary amino group, a ureido group, or a residue of a di-primary or disecondary alipahtic or araliphatic diamine in which one nitrogen atom is attached to the 6 carbonyl group of the above formula and the other nitrogen atom is attached to a similar 3,5-diamino-pyrazine-2-carboxylic acid amide-6-carbonyl residue, are incorporated with cellulose nitrate varnishes; acetyl cellulose admixed with diethyl phthalate and optional titanium dioxide in acetone, which is then cast into films; acetyl cellulose in acetone, which is then formed into fibres by dry spinning; powdered and moulded polystyrene; granulated and tubular polyethylene; polyvinyl chloride foils containing additionally dioctyl phthalate, di-n-butoxy tin dilaurate, and sodium penta-octyl tripolyphosphate and optionally titanium dioxide; monomeric methyl methacrylate, which is then polymerized in moulds with lauroyl peroxide. Specification 674,847 is referred to.ALSO:3.5 - Diaminopyrazine - 2,6 - dicarboxylic acid amide optical brightening agents of the formula wherein R1, R2 and R3 each represent an aliphatic, araliphatic of cycloaliphatic group which may contain chlorine, alkoxy or hydroxy substituents, and X represents a primary amino group, an aliphatic, araliphatic, cycloaliphatic, mononuclear - aromatic, or heterocyclic-substituted secondary or tertiary amino group (each of which may contain optional chlorine, hydroxy, alkoxy, phenoxy, carboxylic, sulphonic and sulphonamide substituents), a cyclic tertiary amino group, a ureido group, or a residue of a di-primary or di-secondary aliphatic or araliphatic diamine in which one nitrogen atom is attached to the 6-carbonyl group of the above formula and the other nitrogen atom is attached to a similar 3.5-diamino-pyrazine -2-carboxylic acid amide-6-carbonyl residue, are prepared by condensing a 4-amino-uracil substituted in the 1- and 3-positions by an aliphatic, araliphatic or cycloaliphatic group with a 4-amino-5-nitrosouracil substituted in the 1- and 3-positions by an aliphatic, araliphatic or cycloaliphatic group in an acidic medium at elevated temperature while splitting of water and ammonia to form a corresponding 3,2 : 5,6 - bis - [(21,41 - diketo - 11,21,31,41 - tetrahydro) - 11,41 - pyrimidino]-pyrazine and hydrolysing this compound direct in aqueous or organic-aqueous medium with a strong base to form a compound of the above formula in which X is an aliphatic, araliphatic or cycloaliphatic secondary amino group, or hydrolysing this compound in steps first by aminolysis at a raised temperature with an aliphatic, araliphatic or cycloaliphatic primary amine and then by hydrolysis in aqueous or organic-aqueous medium with alkalies, to form a 3,5 - diamino - pyrazine - 2,6 - dicarboxylic acid amide of the above formula in which X is an aliphatic, araliphatic or cycloaliphatic secondary amino group, or hydrolysing this compound with an alcoholic solution of an alkali hydroxide at the boil to form a 3,5-diamino-pyrazine-2-carboxylic acid amide-6-carboxylic acid corresponding to X=OH in the above formula and treating said carboxylic acid with thionyl chloride, phosphorus trichloride or phosphorus tribromide, to form the corresponding carboxylic acid halide and either subsequently or simultaneously (in the presence of a tertiary nitrogenous base) treating said acid halide with ammonia, a primary or secondary aliphatic, araliphatic, cycloaliphatic, mononuclear-aromatic or heterocyclic-substituted amine, a cyclic secondary amine, a di-primary or disecondary aliphatic or araliphatic diamine or a urea having at least one hydrogen atom on one of the two nitrogen atoms to form a compound of the above formula in which X is as defined for such formula. Specification 674,847 is referred to.ALSO:3, 5 - Diaminopyrazine - 2, 6 - dicarboxylic acid amide optical brightening agents of the formula wherein R1, R2 and R3 each represent an aliphatic, araliphatic or cycloaliphatic group which may contain chlorine, alkoxy or hydroxy substituents, and X represents a primary amino group, an aliphatic, araliphatic, cycloaliphatic, mononuclear-aromatic, or heterocyclic-substituted secondary or tertiary amino group (each of which may contain optional chlorine, hydroxy, alkoxy, phenoxy, carboxylic, sulphonic and sulphonamide substituents), a cyclic tertiary amino group, a ureido group, or a residue of a di-primary or di-secondary aliphatic or araliphatic diamine in which one nitrogen atom is attached to the 6-carbonyl group of the above formula and the other nitrogen atom is attached to a similar 3,5-diamino-pyrazine-2-carboxylic acid amide-6-carbonyl residue, are incorporated with fibres of wool, silk, nylon, polyurethane, acetate silk and cellulose acetate to triacetate, in presence of water, sulphate or sulphonate washing agents, formic acid, sodium hydrosulphite, sodium pyrophosphate, tetrapyrophosphate or tripolyphosphate, soap, sodium sulphate, carboxymethyl cellulose, magnesium metasilicate, sodium carbonate, water glass or perborate. Specification 674,847 is referred to.ALSO:3,5 - Diaminopyrazine - 2,6 - dicarboxylic acid amide optical brightening agents of the formula wherein R1, R2 and R3 each represent an aliphatic, araliphatic or cycloaliphatic group which may contain chlorine, alkoxy or hydroxy substituents, and X represents a primary amino group, an aliphatic, araliphatic, cycloaliphatic, mononuclear-aromatic, or heterocyclic-substituted secondary or tertiary amino group (each of which may contain optional chlorine, hydroxy, alkoxy, phenoxy, carboxylic, sulphonic and sulphonamide substituents), a cyclic tertiary amino group, a ureido group, or a residue of a di-primary or di-secondary aliphatic or araliphatic diamine in which one nitrogen atom is attached to the 6-carbonyl group of the above formula and the other nitrogen atom is attached to a similar 3,5-diamino-pyrazine-2-carboxylic acid amide-6-carbonyl residue, are incorporated with cosmetic preparations such as lipsticks and creams prepared from cetyl alcohol, paraffin oil, beeswax and wool fat. Specification 674,847 is referred to.