Patent GB-363647-A (GB)
Title: Improvements in and relating to dyestuffs and intermediates of the anthraquinone series
Filed: 1930-06-13
Abstract: Anthraquinone and anthraquinoneacridone derivatives.--Dicarboxy derivatives of arylaminoanthraquinones are prepared by condensing a 1-halogenanthraquinone-2-carboxylic acid with a primary aminoaryl-carboxylic acid, other than an aminodiaryl-ketone-o-carboxylic acid, in an alkaline medium in the presence of a condensation catalyst, such as a copper salt, preferably cupric chloride or copper sulphate.  Suitable for the condensation are an amino-carboxylic acid derivative of a phenyl or naphthalene residue.  The products are converted to the dicarboxylic acid chloride derivatives, for example by treatment with phosphorus pentachloride, thionyl chloride or benzotrichloride in an inert solvent such as nitrobenzene or solvent naphtha, during which conversion ring-closure may also take place to the corresponding Bz-carbonyl chloride derivative of anthraquinone - 2 : 1 - arylacridone.  In examples (1) 1-chloroanthraquinone-2-carboxylic acid is condensed with p-aminobenzoic acid in aqueous alkaline solution and in presence of sodium or potassium carbonate and cupric chloride (or alternatively copper powder or cuprous chloride); instead of p-aminobenzoic acid may be used o- and m-aminobenzoic acids, o-, m-, and p-aminosalicylic acids or other aminohydroxybenzoic acids, and aminonaphthoic acids.  The use of 1-halogen-anthraquinone-2-carboxylic acids and of aminoarylcarboxylic acids containing substituent groups such as halogen is also referred to: (2) the 1-(p-carboxyphenylamino)-anthraquinone-2-carboxylic acid of (1) is treated with phosphorus pentachloride in nitrobenzene or solvent naphtha, or with thionyl-chloride in solvent naphtha and the Bz3-carbonyl chloride of anthraquinone - 2 : 1 - benzacridone obtained; similarly the Bz4- and Bz5-carbonyl chlorides may be derived from the 1-(m- and o-carboxyphenylamino)-anthraquinone-2-carboxylic acids respectively; the use of dichlorobenzene, toluene or xylene instead of nitrobenzene is also mentioned.  Anthraquinone-2 : 1-arylacridone dyestuffs are obtained by condensing these anthraquinone-2 : 1-arylacridone-Bz-carbonyl chloride derivatives with primary aliphatic or aromatic amines. The products passes greater covering power and freedom from tendency to bleeding than the known dyes of this class and dye cotton and rayon in yellowish-pink to light violet-red when simple aliphatic or aromatic amines are employed, and dye cotton red-orange to brown shades when aminoanthraquinones are employed. Condensation is preferably effected in an inert solvent such as nitrobenzene, dichlorbenzene or solvent naphtha.  In examples anthraquinone-2 : 1-benzacridone-Bz3-carbonyl chloride is condensed 1 : 5-monobenzoyldiaminoanthraquinone (one mol.), 1 : 5-diaminoanthraquinone (\ba1/2\be mol.), 1- or 2-aminoanthraquinone, 1 : 8- or -1 : 4-diaminoanthraquinone, 2 : 6- or 2 : 7-diaminoanthraquinone, 1-amino-2-methylanthraquinone, 1 : 6- or 1 : 5-aminochloranthraquinone, aniline, p-toluidine, a -naphthylamine, ethylamine, ethanolamine, and cyclohexylamine. Similar products are obtained by using the anthraquinone-2 : 1 - benzacridone-Bz4- and Bz5-carbonyl chlorides, and the use of methyl-, butyl-, and propylamines, methanolamine, o-toluidine, p-aminophenol, p-phenylenediamine, benzidine, naphthylamines, and of amines substituted by nitro-, methoxy and sulphonic acid groups is also mentioned.  Specifications 12653/09, 13907/09, and 894/11, [all in Class 2 (iii), Dyes &c.], are referred to.  Reference has been directed by the Comptroller to Specification 894/11.