Patent GB-490745-A (GB)
Title: Improvements in the manufacture and production of dyestuffs
IPC: C09B47/067
Filed: 1937-02-15
Abstract: Dyestuffs are manufactured by heating with cuprous cyanide in the presence of an organic nitrogenous base a compound of the general formula <PICT:0490745/IV/1> where X is another halogen atom, Y is a monovalent atom or atomic group or an attached ring but not the grouping -A-R, where A is a simple linkage or an atomic bridge and R is a radicle of a vattable compound, and n is a whole number. Suitable starting materials are derivatives of o-chlorobromobenzene, and o-chlorobromo-compounds of the naphthalene, anthracene and anthraquinone series (obtainable from the corresponding chloroamino-compounds by Sandmeyer's method), of the pyrene and perylene series (e.g. the compounds obtainable by condensing pyrene or perylene with 4-chloro-3-bromobenzoyl chloride in the presence of a Friedel-Crafts catalyst), of the quinoline series (e.g. 6 : 7 - chlorobromoquinoline), of the azaphenanthrene series (e.g. the compound obtainable from 1-chloro-2-bromonaphthalene by nitration and reduction followed by the Skraup synthesis), and of the benzoxazine and benzthiazine series (e.g. the compounds obtainable by condensing o-aminophenol or o-aminothiophenol with 3-bromo-4-chlorobenzoic acid), which compounds may also contain cyano, thiocyano, nitro, alkyl, aryl, acyl, amino, substituted amino, hydroxy, ether, ester, mercapto, thioether, -CH2CN, -CH2.halogen, -CF3, -CH2OH, -CH2COOH, carboxylic acid, ester or amide, sulphonic acid, sulphonic acid amide, alkylamide or arylamide, or azo groups.  The cuprous cyanide may be produced in situ, e.g. from alkali metal cyanides and copper salts.  Suitable nitrogenous bases are those specified in Specification 490,744, and the reaction may be performed in the presence of the diluents and other additional substances specified therein.  The products may be used as body dyestuffs and for dyeing fibrous materials.  In examples: (1) 3-chloro-4-bromaniline is heated with cuprous cyanide and pyridine; (2) 1-benzoylamino-3-bromo-4-chlorobenzene is heated with cuprous cyanide, cuprous bromide and quinoline; (3) 4-chloro-3-bromobenzoic acid or 3-chloro-4-bromophthalimide is heated with cuprous cyanide and quinoline; (4) 1-chloro-2-bromoanthraquinone is heated with cuprous cyanide, pyridine and nitrobenzene; (5) 1-chloro-2-bromonaphthalene is heated with cuprous cyanide, cuprous bromide and quinoline; (6) 4-chloro-3-bromo-41-methylbenzophenone, 4-chloro-3-bromobenzophenone or 4-chloro-3-bromo-21 : 41 dimethylbenzophenone is similarly treated; (7) 4-chloro-3-bromo-1-trifluoromethylbenzene is similarly treated; (8) 4-chloro-3-bromobenzoyldehydrothiotoluidine is similarly treated; (9) 4-chloro-3-iodobenzoic acid is heated with cuprous cyanide and quinoline; (10) 2 : 4-dichloro-5-bromobenzoic acid is heated with cuprous cyanide, cuprous bromide and quinoline; (11) 41-chloro-31-bromobenzoylaniline is similarly treated.  6 : 7-Chlorobromoquinoline is obtainable by Skraup's synthesis from 3-chloro-4-bromaniline.  1 - Benzoylamino - 3 - bromo - 4 - chlorobenzene is obtainable by reacting 3-bromo-4-chloraniline with benzoyl chloride.  3 - Chloro - 4 - bromophthalimide is obtainable by replacing the amino group in 3-nitro-4-amino-1 : 2-dimethylbenzene by bromine by Sandmeyer's method, reducing the nitro group, replacing the amino group by chlorine, oxidizing the methyl groups, converting the 4-bromo-3-chlorophthalic acid to its anhydride and reacting this with ammonia.  4 - Chloro - 3 - bromobenzophenone and its 41-methyl and 21 : 41-dimethyl derivatives are obtainable by condensing 4-chloro-3-bromobenzoyl chloride with benzene, toluene and m-xylene respectively by the Friedel-Crafts process.  4 - Chloro - 3 - bromo - 1 - trifluoromethylbenzene is obtainable by replacing the amino group in 4-chloro-3-amino-1-trifluoromethylbenzene by bromine by Sandmeyer's method.  4 - Chloro - 3 - bromobenzoyldehydrothiotoluidine is obtainable by condensing 4-chloro-3-bromobenzoyl chloride with dehydrothiotoluidine.  4 - Chloro - 3 - iodobenzoic acid is obtainable by replacing the amino group in 4-chloro-3-aminobenzoic acid by iodine by Sandmeyer's method.  2 : 4 - Dichloro - 5 - bromobenzoic acid is obtainable by replacing the amino group in 4 : 6 - dichloro - 3 - bromaniline by a cyano group by Sandmeyer's method and saponifying the resulting nitrile.  41 - Chloro - 31 - bromobenzoylaniline is obtainable by condensing 4-chloro-3-bromobenzoyl chloride with aniline.  Reference has been directed by the Comptroller to Specifications 470,499, 470,542, and 470,703.