Patent GB-994216-A (GB)
Title: New vat dyestuffs of the benzanthrone series
IPC: B66C9/14
Filed: 1961-09-06
Abstract: The invention comprises vat dyes of formula <FORM:0994216/C4-C5/1> wherein R1 is an amino group or substituted amino group the substituent of which may be connected with the 3- position of the benzanthrone nucleus to form a benz-pyridone residue, a carbonamide group, a thioether group or a sulphone group, R2 is a hydrogen atom or an amino group which may be substituted, R3 is a hydrogen atom or a sulphonamide group and R4 is a hydrogen or chlorine atom.  The dyes are prepared by treating a corresponding Bz - 1 - benzanthronyl - (1 - anthraquinonyl)-amine with a condensation agent to affect ring-closure.  Specified condensation agents are an alcoholic potassium hydroxide melt, a pyridine-aluminium chloride mixture, an aniline-sodium anilide mixture, an ethanolamine-potassium hydroxide mixture, sulphuric acid and a mixture of aluminium chloride, sulphur dioxide and sodium chloride.  The dyes give green shades on cotton. The preparation of intermediates is described as follows:-1,5-dichloroanthraquinone is converted via the anthrone into 4,8-dichlorobenzanthrone which is brominated in nitrobenzene to give Bz-1,4 - dibromo - 8 - chloro - benzanthrone (I); bromination in a mixture of hydrochloric and chloracetic acids yields Bz-1-bromo-4,8-dichlorobenzanthrone; I is reacted with p-toluene-sulphonamido-8-chlorobenzanthrone (II) which is treated with sulphuric acid to give Bz-1-bromo - 4 - amino - 8 - chloro - benzanthrone (III) which may also be obtained by treating I with ammonia in nitrobenzene; I is heated with cuprous cyanide in dimethyl formamide to give Bz - 1 - bromo - 4 - cyano - 8 - chloro - benzanthrone (IV) which is hydrolysed with sulphuric acid to yield Bz - 1 - bromo - 4 - carboxy - 8 - chloro - benzanthrone (V); V is treated with thionyl chloride to give the acid chloride (VI) which is condensed with 1-amino-anthraquinone to form the corresponding amide (VII); I is reacted with aniline to give Bz - 1 - bromo - 4 - anilino - 8 - chloro - benzanthrone (VIII); I is reacted with 1-amino-anthraquinone to give Bz - 1 - bromo - 8 -chlorobenzanthronyl - 4,11 - anthraquinonylimide (IX); I is reacted with methylanthranilate to replace the 4-bromo-substituent by an o - methoxycarbonyl - anilino - substituent and the ester obtained is cyclized with polyphosphoric acid to give Bz-1-bromo-4,3-benzacridone-8-chlorobenzanthrone (X).  In Example (1) the anthrimide IX is condensed with 1-amino-anthraquinone and the anthrimide so obtained is cyclized with an ethanolamine-potassium hydroxide mixture to yield a dye of the above formula wherein R1 is anthraquinonyl-1-amino-, R2 and R3 are hydrogen and R4 is hydrogen or chlorine (some dehalogenation occurs in the process).  In the following examples the process of (1) is carried out using the intermediates described above:-(2) VIII, (4) X, (6) IV (the -CN group is hydrolysed to -CONH2), (10) II and (ll) III. Examples (3) and (5) describe the dyes wherein the anthrimide is formed using 1-amino-5-benzoylamino-anthraquinone and the intermediates VIII and X respectively.  In Example (7) III is treated with benzoyl chloride, to give Bz - 1 - bromo - 4 - benzoylamino - 8 - chlorobenzanthrone (XI) which is reacted with 1-aminoanthraquinone and condensed using sodium anilide to give a dye wherein R1 is benzoylamino, R2 and R3 are hydrogen and R4 is hydrogen or chlorine.  Similar processes wherein the benzoyl chloride is replaced by p - methoxy - benzoyl chloride or isophthaloylchloride are mentioned. Example (17) describes the chlorosulphonation of the dye obtained in (7) followed by reaction with dimethylamine to give the dye wherein R3 is dimethylsulphamyl.  In Examples (8) and (9) XI is condensed with 1-amino-5- or -4-benzoylamino-anthraquinone and the resultant anthrimides cyclized.  In Example (13) XI is condensed with 1,5-diamino-anthraquinone and the anthrimide cyclized to give a dye wherein R1 is benzoylamino, R2 is -NH2 and R3 and R4 are hydrogen. In Example (14) the product of (13) is reacted with 1-nitro-anthraquinone-2-carboxylic acid chloride and the acylamino derivative is treated with ammonia in o-dichlorobenzene to replace the nitro group by amino.  In Example (12) III is condensed with 2-phenyl-4-chloro-6,7-phthaloylquinazoline the product reacted with 1-aminoanthraquinone and the anthrimide treated as in (7). In Example (15) I is reacted with p-chlorothiophenol to give Bz - 1 - bromo - 4 - (p - chlorophenylmercapto) - 8 - chlorobenzanthrone which is further reacted as in (1). In Example (16) I is reacted with sodium 4-chlorobenzenesulphinate to give Bz - 1 - bromo - 4 - (p-chlorophenylsulphonyl) - 8 - chlorobenzanthrone which is further reacted as in (1). Specifications 339,396 and 844,781 are referred to.