Patent GB-618432-A (GB)
Title: Improvements in or relating to method of forming halogenated organic compounds and the products resulting therefrom
IPC: C07C23/18
Filed: 1946-03-19
Abstract: Halogenated Diels-Alder adducts of a hexahalocyclopentadiene with a conjugated diene are prepared by halogenating the hexahalocyclopentadiene adduct, to give addition halogenation or substitution of halogen for hydrogen or for another halogen atom. The products are useful as insecticides.  In examples: (1) chlorine is passed into a solution of the adduct of hexachlorocyclopentadiene and cyclopentadiene in carbon tetrachloride, giving octachlorodicyclopentadiene-dihydride; the same product may also be obtained by chlorination under pressure; (2) the adduct starting material of (1) is brominated in carbon tetrachloride in the absence of light and oxygen, in the presence of diphenylamine to give the expected dibromo compound; the addition of a small quantity of aluminium bromide to the reaction mixture causes the bromine to substitute to give hexachloromonobromodicyclopentadiene; (3) the starting material of (1) is treated with liquid anhydrous hydrogen fluoride and lead peroxide in chloroform solution in a steel bomb to produce the difluoride; (4) the Diels-Alder adduct of hexabromocyclopentadiene and cyclopentadiene is chlorinated in carbon tetrachloride to give the dichloro-addition product; (5) a solution of the starting material of (1) in carbon tetrachloride is treated with bromine in the presence of lauryl peroxide giving 1-bromohexachlorodicyclopentadiene; (6) the starting material of (1) is chlorinated with sulphuryl chloride in carbon tetrachloride in the presence of benzoyl peroxide to give a chloro-derivative C10H5Cl7; (7) the product of (5) is treated with sodium iodide in acetone, replacing the bromine atom with an iodine atom; (8) the product of (5) is treated with silver chloride gel, replacing the bromine atom with a chlorine atom; (9) chlorine is passed into a solution of the product of (5) in carbon tetrachloride to give a mixture of 1-chloro- and 1-bromo-octachlorodicyclopentadiene-dihydride; (10) the product of (5) is treated with chlorine and antimony pentachloride in carbon tetrachloride giving the 1-bromo-2,3-dichloro-hexachlorodicyclopentadienedihydride; (11) the adduct of hexachlorocyclopentadiene and methylcyclopentadiene is chlorinated to give a mixture of chloromethyland methyl - octachlorodicyclopentadiene - di - hydride, and (12) the adduct of hexachlorocyclopentadiene and isoprene (1,4,5,6,7,7-hexachloro-3-isopropenyl D 5-bicycloheptene-(1,2,2)) is chlorinated to give the dichloro-addition product. Specification 614,931 is referred to. p ALSO:Insecticides contain as the active ingredient a halogenated Diels-Alder adduct of a hexahalocyclopentadiene with a conjugated diolefine.  The insecticides may be used as dusts, oil sprays, aerosols and water emulsions.  In examples insecticides are prepared comprising a hydrocarbon oil base containing 1 per cent of an organic thiocyanate and, as the lethal constituent, (1) octacheorodicyclopentadiene dihydride; (2) and (5) a monobromo derivative of the hexachlorocyclopentadiene-cyclopentadiene adduct; (9) a mixture of 1-chloro-and 1-bromo octachlorocyclopentadiene dihydride; (11) a mixture of chloromethyl and methyl-octachlorodicyclopentadiene dihydride, and (12) the dichloride of the adduct of hexachloro-cyclopentadiene and isoprene.  Specification 614,931 is referred to.