Patent GB-310076-A (GB)
Abstract: 310,076. Carpmael, A., (I. G. Farbenindustrie Akt.-Ges.). Jan. 16, 1928. Addition to 309,102. Quinazolines.-The process of the parent Specification for the manufacture of condensation products of the benzodiazine series is modified by condensing a 2 or 4-monohalogen quinazoline, or a substitution product or derivative thereof, with ammonia, a substituted or unsubstituted primary or secondary amine, phenol, sulphinic acid, or an organic compound containing a reactive hydrogen atom attached to a sulphur atom. In examples, (1) 4-chlorquinazoline is condensed with H-acid; the product does not react with nitrous acid; the use of 6 or 8-methyl-4-chlorquinazoline or 2- phenyl-4-chlorquinazoline in place of 4-chlorquinazoline, and of other aminonaphtholsulphonic acids in place of H-acid is mentioned. (2) 6- methyl-4-chlorquinazoline is condensed with 1-paminophenyl-5-pyrazolone-3-carboxylic acid; the product couples with diazo compounds; it is also stated that the products from aminoaryl pyrazolones and 4-halogen quinazolines, in general, give nitroso derivatives with nitrous acid. (3) 4- chlorquinazoline is condensed with p-phenylenediamine sulphonic acid. (4) 6-nitro-4-chlorquinazoline is condensed with J-acid; the product does not react with nitrous acid; on reduction it yields a product which can be diazotized or coupled with diazo-compounds; the use of aminonaphthol sulphonic acids in general, of aminoarylpyrazolones, or aminosulphonic or aminocarboxylic acids of the benzene and naphthalene series in general, and of dehydrothiotoluidine sulphonic acid and 5-aminosalicylic acid (which gives a product which may be reduced to a diazotizable compound) in particular is mentioned. (5) 6-nitro-4-chlorquinazoline is condensed with #-naphthylamine; the use of aniline, monomethylaniline, p-toluidine, o-anisidine, oaminophenol, m-nitraniline, monoformyl-mphenylene diamine, 2-amino-5-naphthol, 1-amino- 7-naphthol, or aliphatic amines is mentioned; 2 : 6-dichlor-p-phenylenediamine gives a diazotizable product. (6) 6-nitro-4-chlorquinazoline is condensed with ammonia. (7) Two molecular parts of 6-nitro-4-chlorquinazoline are condensed with one molecular part of p-phenylenediamine; the product is reduced to a tetrazotizable diamino compound; the use of as-m-toluylenediamine, naphthylenediamine, or an aliphatic diamine is also mentioned. (8) Linear 4-chlornaphtho-1: 3- diazine is condensed with H-acid; the product couples with diazo-compounds; with diazotized aniline it gives a reddish-violet; the use of other amino or diamino-aryl sulphonic or carboxylic acids, or of unsulphonated amines, as aniline, or m-nitranilino is also mentioned. (9) 4 : 4'- dichlor-6 : 6<1>-diquinazolyl is condensed with two molecular parts of N-p-aminobenzoyl-H-acid; the use of two molecular parts of other similar or dissimilar amines is mentioned. (14) 4-chlorquinazoline is condensed with a-aminoanthraquinone; the use of other aminoanthraquinones, as 1- amino-5-benzoylaminoanthraquinone, or of onehalf molecular part of 1 : 5-diaminoanthraquinone, or of aminoanthraquinone sulphonic acids is also mentioned. (11) 2-chlorquinazoline is condensed with p-phenylenediamine sulphonic acid; the product can be diazotized the use of 6-methyl-4- phenyl-2-chlorquinazoline, and of other aminoaryl sulphonic or carboxylic acids, as m-phenylenediamine-4-sulphonic acid or benzidine-3-sulphonic acid, or of aminonaphthol sulphonic acids or aminoarylpyrazolones is also mentioned. (12) 6- Nitro-4-chlorquinazoline is condensed with salicylic-5-sulphinic acid (see Specification 245,865); the product is reduced; the amino compound so obtained can be diazotized. (13) 6-nitro-4-chlorquinazoline is condensed with 4-nitro-1-naphthol- 5-sulphonic acid; the use of phenols, naphthols, nitrophenols, and phenol sulphonic acids in general is mentioned. (14) Two molecular parts of 6-nitro-4-chlorquinazoline are condensed with one molecular part of dithioglycol. Halogen and hydroxy-quinazolines.-Linear 4- chlor-naphtho-1 : 3-diazine is prepared by heating 2-naphthylamine-3-carboxylic acid with formamide, and treating the hydroxy derivative so obtained with phosphorus chlorides. 4:4<1>- dichlor-6: 6<1>-diquinazolyl is similarly prepared, via the dihydroxy compound, from 4 : 4'-diamino- 3: 3<1>-diphenic acid. 2-Phenyl-4-chlorquinazoline is prepared by heating ethyl anthranilate with benzonitrile and sodium ethoxide and treating the 2-phenyl-4-oxyquinazoline thus obtained with phosphorus pentachloride. 6-Nitro-4-chloroquinazoline is made by treating 6-nitro-4-oxyquinazoline with phosphorus pentachloride.