Patent GB-726797-A (GB)
Title: Improvements in and relating to vat dyestuffs
IPC: C09B1/43
Filed: 1952-07-25
Abstract: The invention comprises vat dyestuffs of the general formula <FORM:0726797/IV (c)/1> wherein A and A1 represent either -CO-HN-in which the nitrogen atom is attached to the first or second carbon atom of the anthraquinone nucleus, the alternative carbon atom bearing halogen, hydrogen or a methyl or methylthio group, or <FORM:0726797/IV (c)/2> in which X (which represents O or S) and the nitrogen atom are respectively attached to the first and second carbon atoms of the anthraquinone nucleus, Z represents H, Cl, Br, methoxy, methylthio or SO3M (M being hydrogen or an alkali metal), R represents H, halogen, carboxyl, benzoylamino, methoxy or methylthio, R1 has the same meaning as Z or represents carboxyl, and R11 represents H, halogen or methylthio, and wherein the molecule contains at least one but not more than two SO3M groups and each anthraquinone nucleus contains not more than one SO3M group.  These compounds, which yield yellow tints on textiles by the usual vat dye processes, are prepared by condensing 4 : 41 - azobiphenyl - 411 : 4111 - dicarboxylic acid chloride with the same or different appropriately substituted aminoanthraquinones.  When it is desired to form an oxazole ring, a 1-chloro- or 1-bromo-2-aminoanthraquinone is employed and ring formation is subsequently effected at about 180-220 DEG  C. in the presence of a copper catalyst and an acid binding agent.  In examples, 1 mol. of 4 : 41-azobiphenyl-411 : 4111-dicarboxylic acid chloride is condensed with: (1) 1 mol. of 2-aminoanthraquinone-3-sulphonic acid sodium salt and 1 mol. of 1-aminoanthraquinone; (2) 1 mol. of 1-chloro-2-aminoanthraquinone and 1 mol. of 2-aminoanthraquinone-3-sulphonic acid sodium salt; (3) as in (2) with subsequent ring closure on one side to an oxazole by heating with sodium carbonate, potassium acetate, cupric acetate and cuprous chloride; (4) 1 mol. of 2-aminoanthraquinone-3-sulphonic acid sodium salt and 1 mol. of 1-bromo-2-aminoanthraquinone-3-sulphonic acid sodium salt, with ring closure as in (3); (5) 1 mol. of 1-amino-6-chloroanthraquinone and 1 mol. of 1 - bromo - 2 - aminoanthraquinone - 3 - sulphonic acid sodium salt, with ring closure as in (3); (6) 1 mol. of 2-aminoanthraquinone-3-sulphonic acid sodium salt and 1 mol. of 1-mercapto-2-aminoanthraquinone sodium salt, ring closure to a thiazole occurring on one side; (7) 2 mols. of 1-bromo-2-aminoanthraquinone-3-sulphonic acid sodium salt, with ring closure on both sides by treatment as in (3); (8) 1 mol. of 1-chloro-2-aminoanthraquinone and 1 mol. of 1-bromo-2-aminoanthraquinone-3-sulphonic acid potassium salt, with ring closure on both sides as in (7); (9) 2 mols. of 1 - mercapto - 2 - aminoanthraquinone-3-sulphonic acid disodium salt, ring closure to a thiazole occurring on both sides; (10) 1 mol. of 1-chloro-2-aminoanthraquinone and 1 mol. of 1-mercapto-2-aminoanthraquinone-3-sulphonic acid disodium salt, ring closure to a thiazole occurring on one side and ring closure to an oxazole being effected as in (3) on the other side; (11) 1 mol. of 1-bromo-2-aminoanthraquinone-3-sulphonic acid sodium salt and 1 mol. of 1-mercapto-2-aminoanthraquinone sodium salt, with ring closure as in (10).  Lists of alternative reactants are given.  Reference has been directed by the Comptroller to Specification 675,149.