Patent GB-605466-A (GB)
Title: Manufacture of vat dyestuffs
IPC: C09B1/48
Filed: 1945-08-02
Abstract: Vat dyes are made by a process comprising heating a vattable amine with a carboxylic acid containing a sulphonamido group or a functional derivative of such an acid.  Amines specified are 1-aminoanthraquinone, 1.4- or 1.5-diaminoanthraquinone, 1-amino-4- or -5-, or -8-benzoyl-aminoanthraquinone, which may be further substituted by methoxy, chlorine, or bromine, aminodibenzanthrones, aminoanthraquinone - acridones, aminothiazole-anthrones, aminopyrazole-anthrones, aminoanthrapyrimidines, aminoanthrimide carbazoles, and amines containing two or more vattable residues, connected, e.g. by imino or carboxylic acid amide groups and non-vattable hydrocarbon residues, such as amino-di- and poly-anthrimides.  Acids specified are benzene-1-carboxylic acid-3 or 4-sulphonamide and benzene-1-carboxylic acid-3 or 4-(N-dimethyl, diethyl, methyl-phenyl, or phenyl)-sulphonamide.  Solvents for the reaction are chlorobenzene, o-dichlorobenzene, nitrobenzene, or naphthalene.  The dyes obtained are used for dyeing or printing wool, silk, cotton, linen, artificial silk, regenerated cellulose, and superpolyamide fibres, as such, or as their sulphuric acid leuco-esters.  The acylation may be an intermediate or final step in a sequence of steps comprising, for example, reduction of a nitro group, benzoylation of an amino group, acridone ring closure, reaction of amines or amides with halogen-aryl bodies or with mono- or dicarboxylic chlorides, phosgene, or cyanuric chloride, carbazolation, or formation of an azole ring.  The products dye wool, silk, cotton, linen, artificial silk, regenerated cellulose and nylon, and they may be converted to leucosulphuric esters by usual methods.  In examples: (1) 1 - amino - 4 - benzoylaminoanthraquinone is reacted with p-(N-dimethyl) sulphonamido benzoic acid chloride or with the corresponding 3-(N-dimethyl), 4 - N - phenyl, 4 - (N - methyl - phenyl), 4-N-methyl, 4-N-ethyl, 4-N-diethyl, or unsubstituted sulphonamido bodies; (2) 1 - amino - 5 - benzoylamino - anthraquinone, or 1 - amino-5-nitroanthraquinone, or 1-amino-5-chloroanthraquinone are each reacted with p - (N - dimethyl - sulphonamido) benzoic acid chloride, the nitro group being subsequently reduced and benzoylated, and the chlorine atom replaced by an amino group by reaction with p-toluene-sulphonamide and hydrolysis; alternative sulphonamido bodies are listed as under (1); (3) 1.4- or 1.5-diaminoanthraquinone is reacted with p-N-dimethyl-sulphonamido benzoic acid chloride or the corresponding N-methyl-phenyl body; (4) 4-aminoanthraquinone - 2 : 1 -(N) - 11 : 21 - (N) - benzacridone is reacted with p - (N - diethyl) - sulphonamido benzoic acid chloride or the corresponding N-dimethyl body; (5) 1-nitro-4-aminoanthraquinone is first reacted with p-(N-dimethyl or diethyl)-sulphonamido-benzoic acid chloride, the nitro group is reduced, and the amino body so obtained is reacted with the reaction product of 1-chloro-4-aminoanthraquinone and p-(N-diethyl)-sulphonamido-benzoic acid chloride to give an anthrimide, which is carbozolised; (6) 4 - [Bz - 4 -(N - diethyl or dimethyl or methyl - phenyl)-sulphonamido]-41-benzoylamino - 1.11-dianthrimide or similar di-anthrimides are carbazolised; (7) 1-amino-5-[Bz-4-(N-dimethyl)-sulphonamido - benzoylamino] - anthraquinone (2 mols.) is reacted with 2.6-dichloranthraquinone or with oxalyl chloride; (8) terephthalyl chloride is reacted with 1 mol. 1-amino-anthraquinone and 1 mol. 1-amino-5-[Bz.-4-(N-dimethyl) -sulphonamido-benzoylamino]-anthraquinone; (9) cotton is vat dyed with products obtained under (1) and (6) above.  The sulphonamido benzoic acids may be obtained by alkylation with a dialkyl sulphate of the unsubstituted sulphonamido benzoic acid or by reaction of the sulphochlorides with amines.