Patent GB-309102-A (GB)
Title: Process for the manufacture of condensation products of the benzo-diazine series
IPC: C09B1/467
Filed: 1927-12-31
Abstract: 309,102. Carpmael, A., (I. G. Farbenin dustrie Akt.-Ges.). Dec 31, 1927. Quinazoline derivatives are prepared by condensing a 2 : 4-dihalogenquinazoline successively with one molecular proportion of each of two dissimilar compounds containing a reactive hydrogen atom attached to nitrogen, oxygen or sulphur. Suitable compounds are ammonia, primary and secondary amines, mercaptans, thiophenols, sulphinic acids, sulphites, water, alcohols, or phenols. The process is carried out by allowing one molecular part of one compound to react with the dihalogen quinazoline at a low temperature, and then allowing one molecular. part of the second compound to react with the product at an elevated temperature. Further, 2 : 4-dihalogenquinazoline is condensed simultaneously or successively with two molecular parts of a compound containing a reactive hydrogen atom attached to nitrogen, oxygen or sulphur, but excepting ammonia, alkali hydrosulphide, water, or a monohydric aliphatic alcohol, In examples : (1) 2 : 4-Dichlorquinazoline is condensed with two molecular parts of H-acid; the product does not react with nitrous acid, and couples with two molecular parts of diazo-compounds; the use of aminonaphthol sulphonic acids, their N-monoalkyl and N-(aminobenzoyl) derivatives, in general. and of J, S, and y-acids, and N-maminobenzoyl-J-acid in particular, in place of H- acid, is mentioned. (2) 2 :-4-Dichlorquinazoline is condensed in two stages with two molecular parts of p nitraniline-3-sulphonic acid, and the product reduced to a diamino compound, which may be tetrazotized; the same diamino compound is obtained by using p-phenylenediaminesulphonic acid, and an isomeric one (which can also be tetrazotized) by using m-phenylenediamine-4-sulphonic acid. (3) 2 : 4-Dichlorquinazoline is condensed with two molecular parts of aaminoanthraquinone; the use of #-aminoanthraquinone, 1-amino-4 or 5-benzoylaminoanthraquinone, or other aminoanthraquinones or aminohydroxyanthraquinones in general is mentioned. (4) 2 : 4-Dichlorquinazoline is condensed with two molecular parts of aniline; the use of other amines, such as the toluidines, nitranilines, halogenanilines, naphthylamines, chloro and nitronaphthylamines, of aliphatic amines, as #-dimethylaminoethyl-ethylamine, or of aminoazo compounds is mentioned. (5) 2 : 4-Dichlorquinazoline is condensed with two molecular parts of p-phenylenediaminecarboxclic acid; the product can be tetrazotized. (6) 2 :-4-Dichlorquinaxoline is condensed with two molecular parts of 5- aminosalicylic acid. (7) 2 :4-Dichlorquinazoline is condensed with two molecular parts of salicylic-5- sulphinic acid. (8) 2:-4-Dichlorquinazoline is condensed with two molecular parts of phenol or of a-naphthol. (9) 2 : 4-Dichlorquinazoline is condensed with two molecular parts of y-thiocresol. Other examples deal with the introduction of two different substituents : (10) 2 : 4-Dichlorquinazoline is first condensed with one molecular part of H-acid, and then with one molecular part of J-acid; an isomeric, product is obtained by carrying out the condensations in the reverse order; the condensation of the same intermedate product with one molecular part of ammonia, methylalcohol (giving a product which couples with diazo compounds), benzyl alcohol, cyolohexanol. p-aminobenzene-5-azosalicylic acid. or phenol (giving a product which couples with diazo-compounds), or with one-half molecular part of dithioglycol is described, and its condensation with polyphenols, as resorcinol or 2 : 7-dihydroxynaphthalene, or with aminoazo compounds in general, and m-benzoic acid -5-azo-o-anisidine, aminoarylazopyrazolones, and aminoarylazoacetoaceturylides in particular is mentioned; the condensation of 2 : 4-dichlorquina,zoline with aminonaphtholsulphonic acids in general, and of the products so obtained with hydrazines, as phenylhydrazine, or with methylamine, benzylamine, eyclohexylamine, aniline and its homologues and substitution products, as m-nitraniline, N-alkylanilines, o.- and #-naphthylamines and their substitution products, 2.: 5-diamino-4-methyl-diphenylsulphone (in which only the 5-amino group resets), aminophenols (especially ortho), monoarylated phenylenediamines. aromatic aminosulphonic and aminocarboxylic acid, as metanilic, m-aminobenzoic acid, or m-phenylenediamine-4- sulphonic acid, the aminosalicylic, acids, aminoaryl pyrazolines, aminobenzoylaminonaphtholsulphonic acids, aminoazo compound, o-aminoalkylnaphthylamines, or ammonia or with phenols, as p-nitrophenol, naphthols, phenol or naphthol sulphonic or carboxylic acids, or with thiophenols or sulphinic acid salts, is also mentioned. (11) 2 : 4-Dichlorquinazoline is condensed with one molecular part of S-acid and the remaining halogen replaced by hydroxyl by boiling the product with alkali. (12) The intermediate product, containing one molecule of J-acid. is treated with sodium hydrosulphide, whereby the remaining halogen is replaced by the mercapto group. (13) 2: 4-Dichlorquinazoline is condensed with one molecular part of K-acid and then with one molecular part of p-toluene sulphinie acid. (14) Two molecular parts of 2: 4-dichlorquinazoline are condensed with one molecular part of p-phenylene diamine; one molecular part of the intermediate product so obtained is condensed with two molecular parts of H-acid; the product does not react with nitrous acid, and couples with two molecular parts of diazo compounds. The same intermediate product may also be condensed with two molecular parts of p-phenylenediamine sulphonic acid or m-phenylenediamine-4-sulphonic acid, with benzidine-3-sulphonic acid, giving a, tetrazotizable compound, with ammonia, or aliphatic amines, with phenols or sulphinic acids, with aminoarylpyrazolones, with the aminobenzoyl-J- acids, or with p-aminophenyl-5-hydroxy-2- naphthylurea-7-sulphonic acid. (15) 2 : 4-Dichlorquinazoline is condensed with one molecular part of sulphanilic acid and the product (which can not he diazotized) is condensed with one molecular part of J-acid. (15a) 2 : 4-Dichloroquinazoline is condensed with phenol and the product condensed with p-sulphanilic acid. (16) 2: 4-Dichlorquinazoline is condensed with one molecular part of m-phenylenediamine-4-sulphonic acid, giving an intermediate product which may be diazotized, and this is condensed with one molecular part of J-acid. to give a product which may be diazotized and also couples with diazo-compounds: the same intermediate product may be condensed with monoformyl-m-phenylenediamine. and the product so obtained saponified by alkali, giving a tetrazotizable product. (17) 2: 4-Dichlorquinazoline is condensed with p-aminoacetanilide-2-sulphonic acid, and the product condensed with 5-aminosalicylic acid; an isomer of this product is obtained by carrying out the condensations in reverse order. (18) 2:4-Dichlorquinazoline is first condensed with 4-m-nitrobenzoylaminometanilic acid and the product condensed with 6-m-nitrobenzoyl-o-toluidine- 4-sulphonic acid, and the product reduced; an isomer is obtained by carrying out the condensations in reverse order. (19) Two molecular parts of 2 : 4-di-chlorquinazoline are condensed with one molecular part of p : p<1>-diaminodiphenylamine-o-sulphonic acid or p : p<1>-diaminostilbeneo : o'-disulphonic acid, and the product condensed with two molecular parts of suitable phenols or amines, as p-phenylenediamine sulphonic acid or 2 : 6-dichlor-p-phenylenediamine. (20) 2 : 4-Dichlorqninazoline is condensed with one molecular part of p-nitraniline- 3-sulphonic acid, and then with one molecular part of dimethylamine, diethylaminoethyl-methylamine, s-di-#-aminoethyl-ethylenediamine (triethytenetetramine) or other aliphatic amines, of with cyclohexylamine, benzylamine or p-nitro. benzylamine, or with aromatic amines, as o-anisidine. aniline, monoformyl-m-phenylenediamine. 2-amino-5-naphthol, y-acid, or aminophenyl pyrazolones. (21) 2: 4-Diohlorquinazoline is condensed with one molecular part of 4-nitro-1- naphthylamine-6-sulphonic acid and the product condensed with one molecular part of glycol: from this body an ethereal sulphate is formed on the remaining hydroxyl of the glycol, and the product so obtained is reduced to an amino-compound. (22) 2 : 4-Dichlorquinazoline is condensed with one molecular part of acetyl-1 : 4- naphythlenediamine-6-sulphonic acid and the product treated with excess of ammonia, whereby the acetyl group is hydrolysed off, and the remaining chlorine atom replaced by an amino group: this product can be diazotized; the condensation of 2: 4-dichlorquinazoline with one molecular part of naphthylenediamine sulphonic acid, in particular 1: 8-naphthylenediamine-4- sulphonic acid, and further condensation of the product with a phenol or naphthol, a substitution product, as p-nitrophenol or a phenol or naphthol sulphonic or carboxylic acid, or with a thiophenol, or a sulphonic acid salt are also mentioned. (23) 2 : 9-Dichlorquinazoline is condensed with one molecular part of m - (p - aminophenylurea - 1 - benzoylamino-8- naphthol-4: 6-disulPhonic acid, and the remaining halogen in the condensation, product replaced by a sulphonic acid group by treatment witli neutral sodium sulphite. (24) 2: 4-Dichlorquinazoline is condensed with one molecular part of salicylic-5-sulphinic acid. and the product further condensed with one molecular part of H- acid, or of X-ethyl-H-acid. N-methyl- or N- cyclohlexyl - J - acid, or 1-m-aminophenyl-5- pyrazolone-3-carboxylic acid; if the last component be m-phenylenediamine-4-sulphonic acid or p-phenylenediamine sulphonic acid, diazotizable products result. (25) The condensation of 2 : 4-dichlorquinazoline with two dissimlar aminoanthraquinones. with an aminoanthraquinone and another component, with aniline or naphthylamine or the like and another unsulphonated aromat