Patent GB-384311-A (GB)
Title: Improvements in the manufacture and production of vat dyestuffs
IPC: C09B49/12
Filed: 1931-04-29
Abstract: Oxazole and thiazole dyes are obtained by condensing an anthraquinone acridone- or thioxanthone-carboxylic acid or substitution product thereof with an aromatic amine substituted in the o-position to the amino group by an OH, SH or NO2 group or halogen, whereby compounds of the general formula:  <FORM:0384311/IV/1> In which A, B and R are mono- or polynuclear aromatic radicals of which at least A or B is an anthraquinone radical, X is an imino group or a sulphur atom, and Y is a sulphur or oxygen atom, are obtained, either directly or by the action of condensing agents on the acylamines intermediately produced; the reaction is effected in solution or suspension in presence of condensing agents.  The thioxanthone- or acridone-carboxylic acids may be employed in the form of their chlorides, anhydrides or esters and other substituting groups, e.g. halogen, alkyl, alkoxy, amino and amino groups substituted by alkyl, aryl or acyl radicals may be present both in the anthraquinone nucleus and in the amines employed. When employing o-halogenamines initially, agents supplying sulphur may be employed in the conversion of the intermediate product to a thiazole.  According to examples, the preparation of condensation products from 1-mercapto-2-aminoanthraquinone and 1 : 2 (S)-anthraquinonethioxanthone-Bz-4-carboxylic acid chloride (obtainable by condensing 2 - bromanthraquinone - 1 carboxylic acid with p-mercaptobenzoic acid followed by ring-closure and conversion to acid chloride), 1 : 2(S)-anthraquinonethioxanthoneBz-2-carboxylic acid chloride (obtainable by condensation thioxanthone ring-closure and conversion to chloride from 1-cyan-2-bromanthraquinone and thiosalicylic acid), 2 : 1-(S) anthraquinonethioxanthone-Bz4-and - Bz-2-carboxylic chlorides, 3 : 2-(S)-anthraquinonethioxanthone-Bz,2-carboxylic chloride, and the corresponding Bz3- and Bz4 - carboxylic chlorides, 2 : 1-(S)-anthraquinonethioxanthone-6-carboxylic chloride, (the 3 : 2-(S)-thioxanthones being obtained by condensing the requisite o-, m- or p-mercaptobenzoic acid with 2-chloranthraquinone - 3 - carboxylic acid ring closure and conversion to acid chloride) is described.  The condensation products from 1-amino-2-hydroxyanthraquinone and 2 : 1-(S)-anthraquinonethioxanthone - Bz2 - carboxylic chloride (obtainable by condensing 1-chloranthraquinone - 2 - carboxylic acid with thiosalicylic acid &c.), the corresponding Bz4, and -6-, carboxylic acids, referred to in Specification 357,195, 1 : 2-(S)-anthraquinonethioxanthone Bz2 - Bz4 - carboxylic chlorides (Specification 357,195) from 2-amino-3-hydroxyanthraquinone and 2 : 1 (S)-anthraquinonethioxanthrone-Bz4-carboxylic chloride and 3 : 2-(S)-anthraquinonethioxanthone - Bz2 - and Bz,4 - carboxylic chloride, from 1-chloro - 2 - aminoanthraquinone, and 1 : 2-(S)-anthraquinonethioxanthone-Bz2-carboxylic chloride followed by sulphurization, from o-aminomercaptobenzene and 3 : 2 (S)-anthraquinonethioxanthone Bz2-carboxylic chloride, and from 1 - amino - 2 - mercapto-anthraquinone and 3 : 2 - (S)-anthraquinonethioxanthone¦-Bz,4 - carboxylic chloride, are similarly described, all the above products being anthraquinone-thioxanthoneoxazoles or thiazoles. Anthraquinone-acridone oxazoles obtained by condensing 2 : 1-(N)-anthraquinone-1<1> : 2<1>-(N)-naphthacridone-3<1>-carboxylic chlorid (obtainable from 1 - chloranthraquinone-2-carboxylic acid and 2-amino-3-naphthoic acid by condensation &c.) with 2-amino - 3 - hydroxyanthraquinone, and anthraquinone 2 : 1-(N)-benzacridone-Bz4-carboxylic chloride (Specification 357,195) with 1-amino - 2 - hydroxyanthraquinone, 1-chlor-2-aminoanthraquinone, and 1 - nitro - 2-amino -anthraquinone, followed by ring closure where necessary, are also described.  The products are vat-dyes.