Patent GB-595246-A (GB)
Title: N-nitroaryl haloarylsulphonamides
Filed: 1944-05-09
Abstract: Halogenated arylsulphonamidonitroaryl compounds, having insecticidal properties, of the general formula XnArSO2NHAr(NO2)m wherein X represents a halogen, Ar represents an aryl nucleus which (where there are positions available therefor) may contain further neutral substituents, n represents an integer from 2 to 5 inclusive and m represents an integer from 1 to 3 inclusive, and wherein the nitro group (or one of the nitro groups) is in the p-position, are manufactured by reacting a halogenated arylsulphonyl halide XnArSO2X with the appropriate nitroarylamine, if desired in the presence of an organic solvent, e.g. benzene or pyridine (preferably the latter, which acts also as a basic reagent), or in the presence of aqueous alkali, e.g. sodium or potassium hydroxide solution (which may alternatively be added after the initial condensation), or of a quaternary ammonium hydroxide, e.g. benzyl trimethyl ammonium hydroxide.  In an example, 3 : 4-dichlorobenzenesulphonyl chloride is stirred with p-nitraniline in pyridine to produce 3 : 4 - dichlorobenzenesulpho - 41 - nitranilide.  There may similarly be prepared 3 : 4-dibromobenzenesulpho-41-nitranilide and compounds containing naphthyl, phenanthryl or anthryl groups.  Other starting materials specified are, on the one hand, 2 : 4- and 2 : 5-dichloro-, 3 : 4-dibromo-, tetrachloro- and pentachlorobenzenesulphonyl chloride, 3-chloro-5-bromobenzenesulphonyl bromide, and sulphonyl halides containing further neutral substituents such as alkyl or other aliphatic hydrocarbon groups (e.g ethyl, propyl, n- or tert.-butyl, n- or iso-octyl, a  : a  : g  - g -tetramethylbutyl, undecenyl or allyl), aryl (e.g. phenyl), aralkyl (e.g. benzyl, methylbenzyl or butylbenzyl), cycloaliphatic (e.g. cyclohexyl or methylcyclohenyl), alkoxy (e.g. methoxy or ethoxy), aryloxy (e.g. phenoxy), acyl (e.g. acetyl or propionyl) or nitro groups, and, on the other hand, di- and tri-nitroanilines in which one of the nitro groups occupies the p-position, p-nitranilines containing other neutral substituents such as methyl, ethyl, propyl, butyl, amyl, phenyl benzyl, acetyl, chlorine or bromine, and polynuclear nitroarylamines such as the 4-nitro-1-naphthylamines.  2 : 5-Dichloro- and tetrachloro-benzenesulphonyl chlorides are obtainable by the action of chlorosulphonic acid on p-dichlorobenzene and tetrachlorobenzene respectively.  Pentachlorobenzenesulphonyl chloride is obtainable similarly, or by perchlorination of a di-, tri- or tetra-chlorobenzenesulphonyl chloride. 2-Chloro-5-bromobenzenesulphonyl bromide is obtainable by successive chlorination and bromination of benzenesulphonyl chloride (the bromination simultaneously effecting a transformation of the sulphochloride group into a sulphobromide group).  The Specification as open to inspection under Sect. 91 comprises also an alternative process in which the halogenated arylsulphonyl halide is condensed with an arylamine, e.g. aniline, a naphthylamine or other polynuclear arylamine, and the product is subsequently nitrated.  This subject-matter does not appear in the Specification as accepted.ALSO:Insecticides comprise a halogenated arylsulphonamidonitroaryl compound of the general formula XnArSO2NHA(NO2)m (wherein X represents a halogen, Ar represents an aryl nucleus which, when there are positions available, may contain further neutral substituents, n represents an integer from 2 to 5 inclusive and m an integer from 1-3 inclusive, and wherein the nitro group (or one of the nitro groups) is in the p-position), in admixture with a solid inert diluent (e.g. clay, talc, chalk, magnesium carbonate, walnut shell flour or wood flour) or a liquid inert diluent such as an organic solvent or water, with or without a spreader (e.g. soap or synthetic detergent such as octylphenoxyethyl sodium sulphate or cetyldimethylbenzylammonium chloride), other toxic agents (e.g. rotenone, pyrethrins, nicotine, arsenates, oils from tars or petroleum or of animal or vegetable origin or organic thiocyanates) or fungicides (e.g. basic copper sulphate, cuprous oxide, copper oxychloride, dithiocarbamates or thiuram sulphides). When using a solid diluent, this may be coated or impregnated with a solution of the toxicant in an organic solvent and the latter evaporated.  Such a solution may also be used to apply the toxicant as an emulsion or aerosol therefrom.  In an example, 3 : 4-dichlorobenzenesulpho-41-nitroanilide is mixed with magnesium carbonate, and the mixture may be added to water.  In another composition, the toxicant is mixed with alum sludge, lime and soya bean oil.