Patent GB-847550-A (GB)
Title: Phosphonic acid esters
IPC: C07F9/40
Filed: 1958-06-23
Abstract: The invention comprises phosphonic acid esters of the general formula:  <FORM:0847550/IV(b)/1> wherein R is a cycloalkyl, vinyl substituted by a C1-C6 alkyl radical, phenyl substituted vinyl, or phenyl radical, R is a C1-C6 alkyl radical, R11 and R111 are C1-C6 alkyl radicals or phenyl radicals or may, together with the N atoms, form a heterocyclic ring, e.g., piperidyl or morpholyl, Alk is an alkylene radical and X and Y are sulphur or oxygen atoms at least one of them being a sulphur atom.  The compound in which Y is sulphur may be activated by reacting the corresponding phosphonic or thiophosphonic ester chloride (R.P.(X) (OR1)Cl) with an appropriately substituted amino alkyl mercapton of the formula HS. Alk. (N (R11) (R111) preferably in the presence of an acid binding agent, e.g., an alkali metal alcoholate, and of an inert organic solvent.  Compounds in which Y is oxygen may be obtained by reacting the above mentioned thiophosphonic acid ester chlorides with the appropriate substituted amino alkyl alcohol, preferably in the presence of an acid binding agent, or by first forming the corresponding substituted amino alkyl alcoholates (e.g. with metallic sodium) and then reacting these with the thiophosphonic acid ester chlorides, preferably in the presence of an inert organic solvent.  Compounds in which X is oxygen and Y is sulphur may be prepared by reacting the appropriate thiophosphonic acid alkyl ester chlorides first with 2 molecular proportions of alkali metal hydroxide to form the corresponding thionophosphonic alkyl ester acids of the formula R.P.(S) (OR1) (OH) which react in their tautomeric form RP(O) (OR1) (SH) with appropriately substituted amino alkyl halides in the presence of the excess alkali metal hydroxide to form the products of the formula R P(O) (OR1) (S.Alky .N.R11,R111).  Several examples are given examples for specified R- groups in the products being cyclohexyl, phenyl, styryl, isobutenyl and diisobutenyl respectively.  The products have insecticidal properties (see Group VI).  Isobutenyl phosphonic acid ethyl ester chloride (CH3)2C = CH.P(O) (OC2H5) Cl used as starting material is obtained by heating isobutenyl phosphonic acid diethyl ester to about 60 DEG -65 DEG C., and then reacting with phosgene at 65 DEG  to 70 DEG C.  Phenyl thionophosphonic acid ethyl ester potassium salt is obtained by dissolving the corresponding ester chloride in acetonitrile, adding water and then an aqueous solution of potassium hydroxide, allowing the temperature to rise to about 70 DEG C. and maintaining it for one hour.ALSO:An insecticidal composition comprises as active ingredient one or more phosphoric acid esters of the general formula:  <FORM:0847550/VI/1> wherein R is a cycloalkyl, vinyl substituted by an alkyl radical containing 1 to 6 carbon atoms, phenyl substituted vinyl, or phenyl radical, R1 is an alkyl radical containing 1 to 6 carbon atoms, R11 and R111 are alkyl radicals containing 1 to 6 carbon atoms or phenyl radicals or may, together with the nitrogen atom form a heterocyclic ring e.g., piperidyl or morpholyl, Alk is an alkylene radical and X and Y are sulphur or oxygen atoms, at least one being a sulphur atom (see Group IV(b)) and a solid or liquid diluent or carrier.  Specified carriers are talc, chalk, bentonite, clay, water (if necessary with an emulsifier), alcohols, ketones and liquid hydrocarbons. The active ingredient may be used in conjunction with one or more known insecticides and/or fertilizers.  Suitable compositions are obtained by mixing the compounds:  <FORM:0847550/VI/2> and <FORM:0847550/VI/3> with acetone, adding benzyl hydroxy diphenyl polyglycol ether as emulsifier and then diluting with water.