Patent GB-819240-A (GB)
Title: Chlorinated and brominated polycyclic hydrocarbons, their preparation, and insecticidal compositions containing them
Inventor: WEBBER WILLIAM CYRIL
IPC: C07C23/38
Filed: 1958-05-20
Abstract: The invention comprises halogenated adamantanes containing at least 3 chlorine or bromine atoms in the molecule, and a process for preparing chlorinated or brominated polycyclic hydrocarbons or a mixture of such compounds by reacting adamantane (tricyclo (3 : 3 : 1 : 13 : 7) decane) <FORM:0819240/IV (b)/1> in an inert solvent, with a chlorination or bromination agent. The process of the invention may be carried out by reacting adamantane in solution, in an inert solvent, with chlorine or bromine, preferably at elevated temperature, e.g. by passing the gaseous halogen into the solution. A suitable solvent is carbon tetrachloride and halogenation catalysts such as ferric chloride, antimony pentachloride, cupric chloride and cerous chloride or actinic light may be present.  The amount of halogenating agent used may be controlled in order to produce the desired product. Other halogenating agents specified are phosphorus pentachloride, antimony pentachloride, sulphuryl chloride; generally the reagents are heated together.  When sulphuryl halide is used it is preferable to also use a catalyst such as benzoyl peroxide, which promotes its decomposition into sulphur dioxide and halogen. Examples are given of the preparation of 2 : 2 : 4 : 4 : 6 : 6 : 8 : 8 : 9 : 9 : 10 : 10-dodecachlorotricyclo (3.3.1.13 : 7) decane (containing 77.4 per cent chlorine) by passing chlorine into a solution of adamantane in carbon tetrachloride in which is suspended a mercury vapour lamp, also other compounds containing an average number of chlorine atoms per molecule of 2.1, 5.0, 8.2, 10.0, 10.4 and 12.0, and of the preparation 2 : 4 : 6 : 8 : 9 : 10-hexachlorotricyclo (3.3.1.1.3: 7) decane by reacting adamantane with sulphuryl chloride in the presence of benzoyl peroxide.  Compounds containing an average of 0.8, and 6.6 chlorine atoms per molecule are also prepared by this method.ALSO:The invention comprises pesticidal compositions containing chlorinated or brominated adamantanes.  Compounds specified are 2 : 2 : 4 : 4 : 6 : 6 : 8 : 8 : 9 : 9 : 10 : 10 dodecachlorotricyclo (3.3.1.13 : 7) decane, 2 : 4 : 6 : 8 : 9 : 10 hexachlorotricyclo (3.3.1.13 : 7) decane, also other compounds containing an average number of chlorine atoms per molecule of 0.8, 2.1, 5.0, 6.6, 8.2, 10.0 and 10.4.  The corresponding bromine compounds are also referred to.  The compounds may be incorporated in one or more finely divided solid carriers, or liquid carriers.  Surface-active agents such as the condensation products of ethylene oxide with oleyl alcohol, abietic acid or p-octyl phenol may also be used.  The compositions may contain the following specified materials, finely powdered talc, clay, silica, fuller's earth, kieselguhr, sodium phosphate, sodium polyphosphate, methyl cellulose, the sodium salt of cellulose glycollic acid, a petroleum spray oil boiling in the range 275-575 DEG  F. or 575 DEG -1000 DEG  F. and having an unsulphonatable residue of at least 75 per cent, or a mixture of these two types of oil, C1-C6 aliphatic alcohols and ketones, aromatic hydrocarbons, fertilizers and other pesticidal compounds.  The compositions may contain 10-95 per cent by weight of the chlorinated adamantanes.