Patent GB-490744-A (GB)
Title: Improvements in the manufacture and production of dyestuffs
IPC: C09B47/067
Filed: 1937-01-26
Abstract: Dyestuffs are manufactured by heating with cuprous cyanide in the presence of an organic nitrogenous base a cyclic o-dichloro compound other than one in which the nucleus bearing the two chlorine atoms is substituted by the grouping -A-R, where A is a simple linkage or an atomic bridge and R is the radicle of a vattable compound.  Suitable starting materials are o-dichlorobenzene and its derivatives and o-dichloro compounds of the naphthalene, anthracene and anthraquinone series, of the pyrene and perylene series (e.g. the compounds obtainable by condensing pyrene or perylene with 3 : 4-dichlorobenzoyl chloride in the presence of a Friedel-Crafts catalyst), of the quinoline series (e.g. 2 : 3-or 6 : 7-dichloroquinoline), of the azaphenanthrene series (e.g. the compound obtainable from 1 : 3-dichloronaphthalene by nitration and reduction followed by the Skraup synthesis), and of the benzoxazine and benzthiazine series p  (e.g. the compounds obtainable by condensing o-aminophenol or o-aminothiophenol with 3 : 4-dichlorobenzoic acid), which compounds may contain additional chlorine or bromine, iodine or fluorine atoms or cyano, thiocyano, nitro, alkyl, aryl, acyl, amino, substituted amino, hydroxy, ether, ester, mercapto, thioether, 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 high boiling alkylamines, dialkylamines, hydroxyalkylamines, dihydroxyalkylamines, alkylarylamines and cyclic bases such as pyridines and quinolines, which compounds may advantageously be used together with finely divided copper salts such as cuprous chloride or bromide, which may be produced in situ, e.g. from o-dibromobenzene and cuprous cyanide.  The reaction may be carried out in the presence of diluents, e.g. the nitrogenous base itself, excess of the o-dichloro compound, or also benzene and its derivatives, e.g. alkylbenzenes, such as the xylenes and trimethylbenzenes, benzoic esters, alcohols of high molecular weight, phenols, nitrobenzene, diphenyl, benzophenone, phenol ethers, naphthalene, alkylnaphthalenes or anthracene.  The products may be used as pigments and for dyeing fibrous materials. In examples: (1) 1 : 2-dichloranthraquinone is heated with cuprous cyanide, pyridine and nitrobenzene; (2) a mixture of 3 : 4-dichloro- and dibromo-1-benzoic amide is heated with cuprous cyanide and pyridine; (3) commercial o-dichlorobenzene is heated with cuprous cyanide, cuprous bromide and quinoline; the o-dichlorobenzene may be replaced by its alkyl, alkoxy, amino or substituted amino derivatives; (4) commercial trichlorobenzene is similarly treated; (5) commercial o-dichlorobenzene is heated with cuprous cyanide, cuprous chloride and pyridine; (6) commercial o-dichlorobenzene is dropped into a heated mixture of quinoline, cuprous bromide, cuprous cyanide and commercial o-dichlorobenzene; (7) 3 : 4-dichloracetanilide, 5 : 6-dichloro-2-acetotoluidine or 1 : 2-dibenzoyldiamino-3 : 4-dichlorobenzene is heated with cuprous cyanide, cuprous bromide and pyridine; (8) 3 : 4-dichloro-41-methylor -21 : 51-dimethylbenzophenone, or 3 : 4-dichlorobenzophenone, or the methyldichlorobenzophenone obtained from 3 : 4-dichlorotoluene, benzoyl chloride and aluminium chloride, is heated with cuprous cyanide, cuprous bromide and quinoline; in succeeding examples, the following compounds are similarly treated: (9) 3 : 4-dichloranisol or -phenetol; (10) 3 : 4-dichlorotoluene; (11) 2 : 4 : 5 : 21 : 41 : 51 - hexachlorodiphenylmethane; (12) 3 : 4 - dichlorobenzoic - p - anisidide; (13) 6 : 7 - dichloroquinoline, 1 : 4 - diaza - 2 : 3-dichloronaphthalene or 5 : 6 : 7 : 8 - dibenzodichlorophenazine (obtainable from phenanthraquinone and 1 : 2-diamino-3 : 4-dichloro-benzene); (14) 3 : 4 : 31 : 41 - tetrachlorobenzophenone; (15) 3 : 4 - dichlorobenzenesulphonic acid amide, phenylamide or methylphenylamide; (16) 3 : 4 - dichlorobenzoic acid isobutyl, amyl, cyclohexyl or octodecyl ester; (17) benzoic acid 3 : 4-dichlorophenyl ester or 3 : 4 - dichlorobenzoic acid phenyl ester; (18) benzenesulphonyl - 3 : 4 - dichloraniline; (19) 3 : 4 - dichlorodiphenylsulphone, 3 : 4: 31 : 41 - tetrachlorodiphenylsulphoxide, or the methyldichlorodiphenylsulphone obtained from 3 : 4 - dichlorotoluene, benzenesulphochloride and aluminium chloride; (20) 3 : 4-dichlorobenzoic acid diphenylamide, phenylamide, cyclohexylamide or dicyclohexylamide, or 3 : 4-dichlorobenzoyldehydrothiotoluidine; (21) 3 : 4 - dichlorobenzenesulphonic ethyl ester; (22) 3 : 4-dichlorobenzenesulphonic acid methylamide or dimethylamide; (23) 41-hydroxy - 3 : 4 - dichlorobenzophenone; (24) a mixture of 3 : 4-dichlorobenzenesulphomethylamide and benzoyl-3 : 4-dichloraniline; (25) 31 : 41 - dichlorophenylbenzimidazole; (26) the sodium salt of 3 : 4-dichlorobenzophenonesulphonic acid; (27) a mixture of benzoyl3 : 4-dichloraniline and 31 : 41-dichlorobenzoylaniline; (28) a mixture of 3 : 4-dichlorobenzoic methylamide, 3 : 4-dichlorobenzenesulphomethylamide or 31 : 41-dichlorobenzoylaniline with 3 : 4-dichlorobenzoic acid; (29) 2 : 3-dichlorotoluene; (30) 3 : 4-dichlorodiphenyl ether; (31) 2 : 3-dichlorobenzamide; (32) 3 : 4-dichlorobenzoic acid or 2 : 4 : 5-trichlorobenzoic acid; (33) 3 : 4- or 2 : 3-dichlorobenzotrifluoride, 3 : 4 - dichloro - 1 - trifluoromethylmercaptobenzene or 3 : 4-dichloronitrobenzene. Specification 466,194 is referred to.  6 : 7-Dichloroquinoline is obtainable by Skraup's synthesis from 3 : 4-dichloraniline, glycerine and sulphuric acid.  1 : 2 - Dibenzoyldiamino - 3 : 4 - dichlorobenzene is obtainable by reducing 3 - 4-dichloro2-nitraniline and reacting the product with benzoyl chloride.  3 : 4 - Dichloro - 41 - methyl- and -21 : 51-dimethylbenzophenone are obtainable by condensing 3 : 4-dichlorobenzoyl chloride with toluene and p-xylene respectively, in the presence of aluminium chloride.  3 : 4 - Dichlorphenetol is obtainable by reacting 3 : 4-dichlorphenol with diethyl sulphate.  2 : 4 : 5 : 21 : 41 : 51 - Hexachlorodiphenylmethane is obtainable by reacting trichlorobenzene with formaldehyde. 3 : 4 - Dichlorobenzoic acid p-anisidide, diphenylamide, phenylamide, cyclohexylamide, dicyclohexylamide and methylamide are obtainable by reacting 3 : 4-dichlorobenzoyl chloride with the appropriate amines.  3 : 4 : 31 : 41 - Tetrachlorobenzophenone is obtainable by reacting o-dichlorobenzene with phosgene by the Friedel-Crafts synthesis.  3 : 4 - Dichlorobenzenesulphonic acid phenylamide, methylphenylamide, and dimethylamide are obtainable by reacting 3 : 4-dichlorobenzenesulphochloride with aniline, methylaniline and dimethylamine respectively.  3 : 4 - Dichlorobenzoic acid isobutyl, amyl, cyclohexyl, octodecyl and phenyl esters are obtainable by condensing 3 : 4-dichlorobenzoyl chloride with the appropriate hydroxy compounds.  Benzoic acid 3 : 4 - dichlorophenyl ester is obtainable by condensing benzoyl chloride with 3 : 4-dichlorophenol. Benzenesulphonyl - 3 : 4 - dichloraniline is obtainable by reacting benzene sulphochloride with 3 : 4-dichloraniline.  3 : 4 - Dichlorodiphenylsulphone is obtainable by condensing 3 : 4-dichlorobenzenesulphochloride with benzene in the presence of aluminium chloride.  3 : 4 - Dichlorobenzoyldehydrothiotoluidine is obtainable by condensing 3 : 4-dibenzoyl chloride with dehydrothiotoluidine.  3 : 4 - Dichlorobenzenesulphonic ethyl ester is obtainable by reacting 3 : 4-dichlorobenzenesulphochloride with ethanol.  41 - Hydroxy - 3 : 4 - dichlorobenzophenone is obtainable from 3 : 4-dichlorobenzoyl chloride, phenol and aluminium chloride. Benzoyl-3 : 4 - dichloraniline is obtainable by reacting benzoyl chloride with 3 : 4-dichloraniline.  31 : 41 - Dichlorophenylbenzimidazole is obtainable by reacting 3 : 4-dichlorbenzoyl chloride with o-phenylenediamine.  3 : 4 - Dichlorobenzophenonesulphonic acid is obtainable from 3 : 4-dichlorobenzophenone and oleum.  3 : 4 - Dichlorodiphenyl ether is obtainable from 3 : 4-dichlorophenol, bromobenzene and caustic potash.  2 : 3 - Dichlorobenzamide is obtainable by reacting 2 : 3-dichlorobenzoyl chloride with ammonia.  3 : 4 - Dichlorobenzotrifluoride is obtainable by reducing 4-chloro-3-nitrobenzotrifluoride and replacing the amino group by chlorine by Sandmeyer's method.  2 : 3 - Dichlorobenzotrifluoride is obtainable by chlorinating 2 : 3-dichlorotoluene and heating the resulting 2 : 3-dichlorobenzotrichloride with hydrofluoric acid under elevated pressure.  3 : 4 - Dichloro - 1 - trifluoromethylmercaptobenzene is obtainable by reacting the sodium compound of 3 : 4-dichlorothiophenol with methyl iodide, chlorinating and treating the product with hydrofluoric acid.  Reference has been directed by the Comptroller to Specifications 470,499, 470,542, and 470,703.