Patent GB-476599-A (GB)
Title: Process for the manufacture of condensation products of the anthraquinone series
IPC: C09B5/24
Filed: 1936-06-12
Abstract: Dyes are made by reacting amines containing at least one replaceable hydrogen atom attached to nitrogen with phthaloylquinazolines containing in the heterocyclic nucleus at least one halogen atom linked to a carbon atom.  The phthaloyl residue may be linked to the quinazoline residue in 5.6-, 6.7- or 7.8-position.  The reaction may be carried out at temperatures of 40--200 DEG  C. if desired in indifferent diluents such as nitrobenzene, trichlorbenzene or phenol. Amines specified are aliphatic, hydroaromatic and aromatic amines and amines of the anthraquinone, benzanthrone, dibenzpyrenequinone, anthanthrone or dibenzanthrone series.  In examples: (1) 2 - phenyl - 4 - chloro - 7.8 - phthaloylquinazoline is condensed with 1-amino-5-benzoylamino anthraquinone (orange shades on cotton); (2) 2.4 - dichloro - 7.8 - phthaloylquinazoline is condensed with 1-aminoanthraquinone (orange); (3) 2 - phenyl - 4 - chloro - 6.7 - phthaloylquinazoline is reacted with 4-aminoanthraquinone - 2.1 (N) - 1<1>.2<1>-(N) - benzacridone or its 4<1> - chlor, 5<1> - chlor, 6<1>-chlor, or 3<1>.5<1>-dichlor derivatives or with 4 - aminoanthraquinone - 2.1 (N) - 1<1>.2<1> (N) - naphthacridone (green), or with dimethylamine or with dehydrothiotoluidine (greenish-yellow); (4) 2 - (2<1>.5<1> - dichlorphenyl) - 4 - chlor - 6.7 - phthaloylquinazoline is reacted with b -aminoanthraquinone (greenish-yellow); (5) 2-(p-methoxyphenyl) - 4 - chloro - 6.7 - phthaloylquinazoline is reacted with 1-amino-5-benzoylaminoanthraquinone (orange-red); (6) the acid chloride of 2 - (p - carboxyphenyl) - 4 - chlor - 6.7 - phthaloylquinazoline is reacted with 1-aminoanthraquinone (reddish-yellow); (7) 2-chloro-4-phenyl-6.7-phthaloylquinazoline is reacted with 4-aminoanthraquinone-2.1(N) - 1<1>.2<1>(N) - 5<1>-chloro benzacridone (green); (8) 2-phenyl-4-chloro-5.6 - phthaloylquinazoline is reacted with 4-amino - 3<1>.5<1> - dichloranthraquinone - 2.1(N)-1<1>.2<1>(N)-benzacridone or the corresponding 4<1>-or 5<1>- or 6<1>-chlor compounds. Halogenphthaloylquinazolines are made from anthraquinones containing an acylamino group and a carbonamide group in o-position to each other by treatment with alkaline agents, and conversion of the hydroxy bodies so obtained to the corresponding chlor-bodies or in many cases by use of phosphorus pentachloride or thionyl chloride in one stage; e.g. 2-phenyl-4-chlor-7.8-phthaloylquinazoline is obtained from 1-benzoylaminoanthraquinone-2-carboxylic acid amide, 2-phenyl-4-chlor-6.7-phthaloylquinazoline from 2-benzoylaminoanthraquinone-3-carboxylic acid amide and p 2-phenyl-4-chlor-5.6-phthaloylquinazoline from 2 - benzoylaminoanthraquinone 1-carboxylic acid amide; 2-(2<1>.5<1> - dichlorphenyl)-, 2-(p-methoxyphenyl)-, and 2-(p-toluyl)-4-chlor-6.7-phthaloylquinazoline are obtained similarly; the last-mentioned may be oxidized to 2-(p-carboxyphenyl)-4-chlor-6.7-phthaloylquinazoline, which may be converted to the acid chloride.  2.4 - Dioxy - 7.8 - phthaloylquinazoline is obtained by reacting excess oxalyl chloride with 1 - aminoanthraquinone - 2 - carboxylic acid amide, and may be converted to the corresponding dichlor compound.  2 - Hydroxy - 4 - phenyl - 6.7 - phthaloylquinazoline is obtained by heating 2-amino-3-benzoylanthraquinone in urethane in presence of zinc chloride, and may be converted to the 2-chlor compound by phosphorus pentachloride.  2-Benzoyl (or p-toluyl) aminoanthraquinone-3-carboxylic acid amide is made by heating 2-aminoanthraquinone-3-carboxylic acid with benzoyl or p-toluyl chloride in nitrobenzene and heating the anhydride so obtained with ammonia.