Patent GB-525794-A (GB)
Title: Manufacture of vat dyestuffs
IPC: C09B1/32
Filed: 1939-03-01
Abstract: 525,794. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. March 1, 1939, Nos. 6690 and 6691. Convention dates, March 2, 1938, and Feb. 1, 1939. [Classes 2 (iii) and 15 (ii)] Vat dyes are made by treating with a condensing agent a compound of the general formula (R-NH)n-R 1  where R is the residue of a compound capable of being vatted containing at least two cyclic bound carbonyl groups and at most 8 condensed hexacarbon rings, R 1  is a phenanthrene nucleus, and n is the number 1 or a greater number. The products may be treated with a halogenating agent. The parent materials are made by causing a phenanthrene substituted by one or more halogen atoms or amino groups to react, preferably in the presence of a copper catalyst and an acid binding agent, with a compound containing the residue R and at least one amino group or halogen atom. The compounds containing the residue R include anthraquinone derivatives and compounds containing fused-on carbocyclic or heterocyclic rings, e.g., acridone rings. Specified compounds are 1- and 2-aminoanthraquinone, 1-amino-4-methoxyanthraquinone, 1 - amino - 4 - or 5 - benzoylaminoanthraquinone, 1-amino-5-benzoylamino- 8-methoxyanthraquinone, 1 - amino - 5 : 8 - dibenzoylaminoanthaquinone, also halogen-or amino-acylaminoanthraquinones, in which the residue of the benzoic acid has been replaced by the residue of an aliphatic or heterocyclic or another aromatic carboxyline acid, e.g., p-chlorobenzoic acid, cinnamic acid, anthraquinone - 2 - carboxylic acid or acetic acid, aminopyranthrones, or 4-amino-1: 2-anthraquinoneacridane. The phenanthrane derivatives may contain further substituents, e.g., alkoxy groups, or alkyl groups with branched or straight chains, in addition to the halogen atoms-or amino groups. The condensing agents may be acid or alkaline, e.g., concentrated sulphuric acid, chlorsulphonic acid, aluminium chloride or concentrated caustic alkali ; the condensation products probably contain carbazole or similar rings. It is advantageous to treat the products with an oxidizing agent, e.g., alkali nitrite, perborate or hypochlorite, preferably in an acid medium. The products, insofar as they contain a substituent such as halogen suitable for reaction, may be caused to react with an amine containing the residue of a compound capable of being vatted, and the products obtained further treated with a condensing agent, if desired. The dyes obtained dye and print animal and cellulosic fibres, including staple fibres, in fast tints of very varied shades. In examples (1) 4- or -5 benzoylamino - 1<SP>1</SP> - anthraquinonyl - 10 - aminophenanthrene, di- ( 4 or 51-benzoylamino-11- anthraquinonyl) - 6 : 10 - diaminophenanthrene, 5<SP>1</SP> - acetylamino - 1<SP>1</SP> anthraquinonyl - 6: 10 - diaminophenanthrene, and the corresponding p-chlorbenzoylamino, cinnamoylamino and (2)-anthraquinonylamino derivatives, are condensed in concentrated sulphuric acid, (2) the product of the reaction of 6 : 10-dibromphenanthrane (1 mol.) with 4-aminoanthraquinone-1 (N)-2-benzacridone (2 mols.) is condensed by means of aluminium chloride, concentrated sulphuric acid, or alcoholic caustic alkali, (3) the product of the reaction of 6 : 10- dibromphenanthrene (1 mol.) with 1-amino-5- benzoylaminoanthraquinone (1 mol.) is condensed in sulphuric acid, and the product is reacted with 1-amino-5-benzoylaminoanthraquinone (1 mol.) and further condensed in sulphuric acid, (4) the product from 6: 10- dibromphenanthrene (1 mol.) and 1-amino-5- benzoylaminoanthraquinone (1 mol.) is further reacted with 1-amino-4-benzoylamino-anthraquinone (1 mol.) and then condensed in sulphuric acid, (5) di-(5<SP>1</SP>-benzoylamino-1<SP>1</SP>-anthraquinonyl)-8 : 10-diaminophenanthrene is condensed in sulphuric acid, (6) the product of the reaction of a mixture of different dibromphenanthrenes, obtained by brominating phenanthrene in nitrobenzene, and 1-amino-5- benzoylaminoanthraquinone is condensed in sulphuric acid, (7) di-(5<SP>1</SP>-benzoylamino-1<SP>1</SP>-anthraquinonyl) - diamino - 1 - methyl 7 - isopropylphenanthrene (from dibrom - 1 - methyl-7-isopropylphenanthrene)is condensed in sulphuric acid, (8) di-(4<SP>1</SP>- or 5<SP>1</SP>-benzoylamino-1<SP>1</SP>- anthraquinone-3 : 6-diamino-9 : 10-dimethoxyphenanthrene (from 3 :6-dibrom-9: 10-dimethoxyphenanthrene) is condensed in sulphuric acid, and (9) tetra-(5<SP>1</SP>-benzoylamino-1<SP>1</SP>- anthraquinonyl) - tetraaminoanthraquinone (from tetrabromphenanthrene) is condensed in sulphuric acid. Phenanthrene derivatives.-8 : 10 - Dibromphenanthrene is produced, together with the 6: 10 - isomer, by brominating 10-bromphenanthrene in carbon tetrachloride. Dibrom - 1 - methyl - 7 - isopropylphenanthrene is obtained by brominating retene in carbon tetrachloride. 3:6- Dibrom - 9 : 10 - dimethoxyphenanthrene is made by reducing 3 : 6 - dibromphenanthrenequinone with sodium hydrosulphite, and alkylating the product with dimethylsulphate. Tetrabromphenanthrene is made by heating phenanthrene with bromine in a sealed tube.