Patent GB-810602-A (GB)
Title: Unsaturated polycyclic sulphites and a process for their manufacture
IPC: C07D327/10
Filed: 1955-04-18
Abstract: The invention comprises compounds of the general formula <FORM:0810602/IV (b)/1> wherein X represents a hydrogen or chlorine atom, at least 4 chlorine atoms being present, and Y represents a hydrogen atom or a methyl group, and derivatives thereof containing 2 hydrogen atoms in the 5:6 positions, and the preparation thereof by reacting a diol of the general formula <FORM:0810602/IV (b)/2> wherein X and Y have the above significance, or a 5:6-dihydro-derivative thereof, with thionyl chloride, if desired, in the presence of an inert solvent.  The reaction may be carried out by heating, or it may be necessary to cool the reaction mixture.  An agent capable of binding hydrochloric acid may or may not be present in the reaction mixture.  Suitable reaction solvents are carbon tetrachloride, chloroform, dichloromethane, benzene, toluene, xylene or petroleum ether.  In the examples: (1) hexachlorobicyclo - [2:2:1] heptadiene - (2:5) bishydroxyethylene-(5:6) sulphite (a product of the above general formula wherein each X is chlorine and each Y is a methyl group) is prepared by treating hexachlorobicyclo-[2:2:1] heptadiene - (2:5) bis - hydroxyethylene-(5:6) (a reactant of the above general formula where each X is chlorine and each Y2 is a methyl group) with thionyl chloride; (2) hexachlorobicyclo - [2:2:1] heptene - (2) - bis - hydroxymethylene - (5:6) sulphite and in the form of a mixture of isomers which may be separated (the 5,6-dihydro product of the above general formula wherein each X is chlorine and each Y is hydrogen) are prepared as in (1) using the corresponding 5:6-dihydro reactant; (3) a pentachlorobicyclo - [2:2:1] heptene - (2) - bishydroxymethylene - (5:6) sulphite having a boiling point of 180-181 DEG  C. at 2.6 mm. pressure is prepared by treating a pentachlorobicyclo - [2:2:1] heptene - (2) - bis - hydroxymethylene-(5:6) with thionyl chloride; (4) a tetrachlorobicyclo - [2:2:1] heptene - (2) bishydroxymethylene-(5:6) sulphite having a boiling point of 170-172 DEG  C. at 3.0 mm. pressure is prepared as in (3) from a tetrachlorobicyclo-[2:2:1] heptene - (2) bis - hydroxymethylene-(5:6).  Diols of the second general formula above and the corresponding derivatives having hydrogen atoms in the 5:6-positions, wherein X and Y have the above significance, are prepared by reacting a diester of the required unsaturated dihydric alcohol with a halogenated cyclopentadiene, e.g. hexachloro-cyclopentadiene, at an elevated temperature and, if desired, with the application of pressure, and converting the resulting addition product into the corresponding desired free diol, for example, by reaction in alcoholic solution in the presence of a substance serving as an acid catalyst such as a mineral acid.  In the examples: (1) a pentachlorobicyclo - [2:1:1] heptene - (2) bis - hydroxymethylene-(5:6) is prepared by heating a pentachlorocyclopentadiene with butene-(2) diol-(1:4) diacetate to form a pentachlorobicyclo-[2:2:1] heptene - (2) - bis - hydroxymethylene-(5:6) diacetate and hydrolysing this compound under acid conditions; and (2) a tetrachlorobicyclo - [2:2:1] heptene - (2) - bis - hydroxymethylene - (5:6) is prepared as in (1) starting from a tetrachlorocyclopentadiene.ALSO:Pesticidal preparations contain as the active ingredient a compound of the general formula <FORM:0810602/VI/1> wherein X represents hydrogen or chlorine atom at least four chlorine atoms being present, and Y represents hydrogen or a methyl group, or the corresponding 5 : 6-dihydro-compound.  A solid or liquid extender may be used for the preparation. Preparations are detailed comprising (1) emulsions suitable for spraying containing hexachlorobicyclo - [2 : 2 : 1] - heptene-(2) - bis - hydroxymethylene - 5 : 6) sulphite (a 5 : 6-dihydro-compound of the above general formula in which each X represents a chlorine atom and each Y a hydrogen atom) and an oxyethylated alkyl-phenol and dipentene, dioxane or cyclohexanone; (2) an emulsifiable preparation containing hexachlorobicyclo - [2 : 2 : 1]-heptadiene-(2 : 5)-bis-hydroxyethylene-(5 : 6)-sulphite (a compound of the above general formula in which each X represents a chlorine atom and each Y a hydrogen atom); (3) powders containing the active ingredient of (2) and cellulose pitch, oxyethylated alkyl-phenol and chalk, or talc.