Patent GB-719670-A (GB)
Title: Manufacture of new anthraquinone vat dyestuffs
IPC: C09B5/44
Filed: 1952-07-23
Abstract: 2 - Halogenaryl - 4 - chloro - 6,7 - phthaloylquinazolenes are obtained by reacting a 2-halogenaroylamino anthraquinone-3-nitrile with phosphorus pentachloride.  Products specified are those in which the halogenaryl radical is o-chlorphenyl, m-bromophenyl, p-bromophenyl, 31 - chloro - 21 - naphthyl, 41 - bromodiphenyl.ALSO:The invention comprises dyes of the formula:- <FORM:0719670/IV(c)/1> and <FORM:0719670/IV(c)/2> in which R is an aromatic residue, to which in the right-hand formula -NH- and R1 are bound in adjacent positions. R1 is a vattable residue bound to NH by a ring carbon atom in a position vicinal to a ring carbon atom bound to hydrogen or vicinal to the carbon atom bound directly to R, and R2 is a cyclic residue containing at least one six-membered aromatic ring. They are made by condensing, in a high-boiling organic solvent in presence of an acid-binding agent and copper or a copper salt, (1) a vattable amine with a compound of the formula:- <FORM:0719670/IV(c)/3> (halogen being bound directly to a ring carbon atom) or (2) two mols of a vattable amine with one mol of a compound of one of the formulae:-  <FORM:0719670/IV(c)/4> or <FORM:0719670/IV(c)/5> In each case, the condensation may be followed by carbazolization. Compounds of formula 1 are made by condensing a 2-halogen-aryl-4-chloro-6, 7-phthaloyl-quinazoline with an amine of formula H2N-R2.  The products may be used as pigment dyestuffs, or to dye or print linen, cotton, artificial silk, or regenerated cellulose, and may be converted to leuco-sulphuric esters.  Examples describe the condensation of a compound of formula I wherein (1) R is o-chlorphenyl and R2 is the radical of 4-aminoanthraquinone-2, 1 (N)-benzacridone with 1-aminoanthraquinone or with 1-amino-4 or 5-benzoylamino-anthraquinone; (2) R is o-chlorphenyl and R2 is the radical of 1-aminoanthraquinone with 1 - amino - 4 - benzoylamino-anthraquinone; (3) R is o-chlorphenyl and R2 is the radical of 1 - amino - 5 - benzoylaminoanthraquinone with 1 - amino - 5 - benzoylaminoanthraquinone; (4) R is 31-chloro- 21-naphthyl, and R2 is the radical of 4-aminoanthraquinone-2.1 (N)-benzacridone with 1-amino-4-benzoylaminoanthraquinone; (5) R is 3-bromophenyl and R2 is the radical of 4 - aminoanthraquinone - 2 . 1 (N)-benzacridone (or its 31-phenoxy or 51-chloro derivatives) with 1-amino-4 or 5-benzoylaminoanthraquinone, 1-amino-4-methoxy-anthraquinone, 4-amino-1.9-isothiazoleanthrone, aminodibenzanthrone, 4-aminoanthraquinone-2.1 (N)-benzacridone and 4- or 5-amino-1.11-dianthrimide; (6) R is 3-bromophenyl and R2 is the radical of 1-amino-5-benzoylamino-anthraquinone, 2-aminoanthraquinone, 4-aminoanthraquinone-2.1 (N) - naphthacridone; 3-aminopyrene, aniline, or o-chloraniline, with 1-amino-4 or 5-benzoylaminoanthraquinone; (7) R is 4-bromophenyl and R2 is the radical of 4 - aminoanthraquinone - 2.1 (N) - benzacridone, with 1-amino-4-benzoylamino-anthraquinone, or with 4-aminoanthraquinone-2.1 (N)-benzacridone; (8) R is 41-bromodiphenyl and R2 is the radical of 4-amino-anthraquinone-2.1 (N)-benzacridone with 1 - amino - 4 or 5 - benzoylamino - anthraquinone.  Also in examples, (8) 1 mol of 2-(31-bromophenyl)-4-chloro-6.7-phthaloyl-quinazoline is reacted with 2 mols 4-amino-2.1 (N) - anthraquinone-benzacridone, and (9) the compound of formula I wherein R is 31-bromophenyl and R2 is the radical of 51-chloro-4-amino-anthraquinone - 2.1 (N) - benzacridone is reacted with 2 mols 1-amino-4-benzoylamino-anthraquinone.  In each example the product is carbazolized by means of an aluminium chloride-sodium chloride-sulphur dioxide mixture or with sulphuric acid.  2 - Halogenaroylamino-anthraquinone - 3 - nitriles are made by acylation of 2 - amino - 3 - halogen-anthraquinones and replacement of the halogen by cyano by reaction with cuprous cyanide.  Products specified are those in which the halogenaroyl radical is o-chlorbenzoyl-, m- or p-brombenzoyl-, 31-chloro-21-naphthoyl-, and the radical of 41-bromodiphenyl-4-carboxylic acid, and the 3- halogen atom is bromine.