Patent GB-819424-A (GB)
Title: Production of bicyclo heterocyclic phosphorus compounds
IPC: C07F9/6571
Filed: 1956-01-11
Abstract: The invention comprises bicyclo heterocyclic phosphorus compounds having the structure <FORM:0819424/IV (b)/1> wherein R and R1 to R9 designate a hydrogen atom or an alkyl radical having from 1 to 20 carbon atoms, X designates a chlorine, bromine, or fluorine atom or a mercapto radical, and n is 0 or 1.  The compounds in which X is chlorine, bromine or fluorine can be obtained by reacting a thiophosphoryl chloride, bromide, or fluoride with a 2-(1-hydroxyalkyl) cycloalkanol having 5 or 6 carbon atoms in the cycloalkanol ring and 1 to 21 carbon atoms in the alkyl radical of the hydroxyalkyl group or a corresponding 2-(1-hydroxy-alkyl) cycloalkanol substituted in at least one carbon atom of the cycloalkanol ring with at least one C1-C20 alkyl radical and the compounds in which X is a mercapto radical are obtained by a similar reaction using phosphorus penta-sulphide instead of thiophosphoryl chloride, bromide or fluoride.  In the preparation of the thionohalide products the cycloalkane diol is generally added dropwise to an equimolar quantity of the thiophosphoryl halide dissolved in an inert volatile organic solvent, e.g. benzene, containing 2 mols. of a tertiary amine such as pyridine for each mol. of the diol. Alternatively, the thiophosphoryl halide can be added to the diol dissolved in benzene containing the tertiary amine.  An excess of either reactant may be used.  Suitable reaction temperatures are from 25 DEG  to 60 DEG  C., preferably about 40 DEG C.  In the preparation of products in which X is a mercapto group the diol may be added to an agitated suspension of phosphorus pentasulphide in an inert volatile organic diluent such as ethylene dichloride, heptane, benzene, toluene or xylene and suitable reaction temperatures are from 10 DEG  to 125 DEG  C., e.g. 50 DEG  to 70 DEG C.  The phosphorus pentasulphide and diol can be used in the molar ratio between 0.25 to 1 and 1 : 1.  The mercapto product may be purified by preparing an aqueous solution of its alkali metal salt by treatment with an aqueous solution of an alkali metal hydroxide or carbonate, filtering the solution or extracting it from the diluent and then adding a mineral acid such as hydrochloric acid to the filtrate or extract to regenerate the product.  Examples are given for the production of (1) P - chloro - 5,7 - dimethyl - 2,4 - dioxa - P - thiono - 3 - phospha - bicyclo [4.3.0] nonane; (2) 2,4 - dioxa - P - mercapto - 5 - methyl - P - thiono - 3 - phosphabicyclo [4.3.0] nonane; (3) P - chloro - 2,4 - dioxa - 5,7,7,9 - tetramethyl - P - thiono - 3 - phosphabicyclo [4.4.0] decane and/or P - chloro - 2,4 - dioxa - 5,7,9,9-tetramethyl - P - thiono - 3 - phosphabicyclo [4.4.0] decane; (4) 2,4 - dioxa - P - mercapto - 5,7,7,9 - tetramethyl - P - thiono - 3 - phosphabicyclo [4.4.0] decane and/or the corresponding - 5,7,9,9 - tetramethyl isomer; (5) P - chloro-2,4 - dioxa - 5 - methyl - P - thiono - 3 - phosphabicyclo [4.4.0] decane; and (6) 2,4 - dioxa-P - mercapto - 5 - methyl - P - thiono - 3 - phosphabicyclo [4.4.0] decane.  The products in which X is a mercapto group may be reacted with chlorine in the molar of 2 : 3 to form the products in which X is chlorine.  Products in which X is chlorine, bromine or fluorine may be reacted with amines, ammonia, and alkali metal salts of alcohols and phenols to give the corresponding amides or esters which have utility as plasticizers, pesticides, and oil additives. The main products are stated to be effective insecticides.  The cycloalkane-1,3-diols used as starting materials can be obtained by reacting acid anhydrides, acid chlorides, an enol ester of a ketone, ketene, or a ketene homologue CHR:C:O wherein R is hydrogen or a C1-C20 alkyl group with cyclopentanone, cyclohexanone or a ring carbon C1-C20 alkyl substituted cyclopentanone or cyclohexanone having an alpha-hydrogen atom followed by rearrangement and subsequent hydrogenation of the resulting diketone at 100-125 DEG  C. in the presence of a Raney nickel catalyst.  Several cycloalkanediols which may be used as starting materials are specified.