Patent GB-909053-A (GB)
Title: Rotenone derivatives, their preparation and insecticidal compositions
IPC: C07D493/04
Filed: 1960-03-16
Abstract: The invention comprises nordihydrorotenone having the formula: <FORM:0909053/IV (b)/1> and nordihydro-dehydro-rotenone and nordihydro-rotenol, represented, respectively, by the formulae <FORM:0909053/IV (b)/2> and <FORM:0909053/IV (b)/3> Nordihydro-rotenone may be made by the steps of reacting 2-ethyl-4-hydroxy-coumarane and an alkyl ester of 2-cyanomethyl-4,5-dimethoxy-phenoxyacetic acid, containing 1 to 5 carbon atoms in the alkyl group, by the Hoesch's reaction in absolute ether in the presence of zinc chloride and hydrochloric acid gas or aluminium chloride at room temperature to form an ester which is hydrolysed, e.g. with alcoholic potash, to form a new compound, nordihydro-derris acid:  <FORM:0909053/IV (b)/4> which is heated in acetic anhydride in the presence of sodium acetate or pyridine, or in a mixed solution of acetic anhydride and acetic acid in the presence of acetamide, to effect dehydrative ring closure to give nordihydro-dehydro-rotenone, reducing this product with alkali metal borohydride to form nordihydro-rotenol and finally oxidizing the latter to form nordihydro - rotenone by the Oppenauer's oxidation method with a ketone, such as acetone, cyclohexanone and diphenyl ketone, and an aluminium alkoxide in an inert solvent. 2-ethyl-4-hydroxy-coumarane may be made from 2-acetyl-4-hydroxy-5-carbalkoxycoumarone by hydrogenation and hydrolysis to 2-ethyl-4-hydroxy-5-carboxy-coumarane followed by decarboxylation, or by successive hydrogenations via 2 - ethyl - 4 - hydroxy - 5 - carboxy-coumarone and the corresponding coumarane followed by decarboxylation, a combination of hydrogenation, hydrolysis and decarboxylation steps being possible in any order. 2 - acetyl - 4 - hydroxy-5-carbomethoxycoumarone is obtained by adding 3-formyl-b -resorcylic acid methyl ester in methanol to sodium hydroxide, adding to the precipitated sodium compound chloroacetone, refluxing for 5 hours and filtering the precipitated crystal of the desired product.ALSO:An insecticidal composition comprises nordihydro-rotenone <FORM:0909053/VI/1> (for preparation see Group IV (b)), as an active ingredient, and an inert carrier therefor. Suitable solvents are alcohol, benzene, acetone and chloroform.  The compound may be used in the form of an oil with xylene or kerosene; in the form of an emulsifiable liquid using sulphated oil, cresol soap and soapless detergent; in the form of an emulsion using an emulsifier such as an anionic or non-ionic surface-active agent; in the form of a powder using a neutral carrier, such as starch, diatomaceous earth or pilophilite; may be admixed into a common aerosol composition or formed as a semi-solid type of composition. The compound may be mixed with conventional agricultural chemicals in any proportion, provided that alkaline agents are excluded.  In examples, dl-nordihydrorotenone is mixed with a non-ionic surface-active agent containing alkyl allyl polyether alcohol and solvent naphtha to give a uniform emulsion, with the same emulsifier and talc to give a water-miscible type of powder, with kerosene to give an oil composition, with pyrethrin, an anionic surface-active agent and benzene to give a uniform emulsion; further examples describe comparative tests of dl-nordihydrorotenone and rotenone in aqueous acetone solution, in emulsions using chloroform and an alkyl allyl polyether alcohol surface-active agent, and as a water spray using the same surface-active agent.