Patent GB-1017440-A (GB)
Title: Phosphorylimino dithiocarbonic acid esters
IPC: C07F9/24
Filed: 1964-10-15
Abstract: The invention comprises phosphorylimino dithiocarbonic acid esters of the general formula <FORM:1017440/C2/1> wherein R1, R2, R3 and R4, which may be the same or different, are substituted or unsubstituted alkyl, cycloalkyl, aryl or aralkyl radicals and R3 and/or R4 may also be heterocyclic radicals, and X, X1 and X11 are oxygen or sulphur atoms.  They are prepared by reacting a phosphoryl isocyanide dichloride of the general formula <FORM:1017440/C2/2> in which R1, R2, X, X1 and X11 have the same meanings as above with a mercaptan of the general formula R3-SH and/or R4-SH, in which R3 and R4 have the same meanings as above, the mercaptan being used as such in the presence of an acid-binding agent or in the form of a salt. The reaction is preferably carried out in the presence of an inert organic solvent at temperatures of - 20 DEG  C. to 100 DEG  C. Suitable solvents are optionally chlorinated hydrocarbons and ethers, whilst suitable acid-binding agents are organic nitrogen bases or alkali metal hydroxides, carbonates or bicarbonates. Numerous examples are given of the radicals R1, R2, R3 and R4 which may be substituted, e.g. by halogen atoms, nitro, amino, alkylamino, arylamino, keto, carboxyl, carbalkoxy, hydroxy, thio, mercapto or alkoxy radicals.  The term alkyl includes saturated and unsaturated carbon chains preferably containing 1 to 12 carbon atoms.  The term cycloalkyl includes saturated and unsaturated cyclic carbon chains such as chains containing 3 to 8 carbon atoms, the term aralkyl includes saturated and unsaturated aryl substituted carbon chains and the term " heterocyclic " includes saturated or unsaturated carbon rings containing nuclear members such as oxygen, nitrogen and sulphur.  The esters may be used as the active ingredient in insecticidal and fasciolidical compositions (see Division A5).  The phosphoryl or thiophosphoryl isocyanide dichlorides used as starting materials may be produced by the reaction of the corresponding isothiocyanates of the general formula <FORM:1017440/C2/3> with elementary chlorine, optionally in the presence of inert organic solvents and catalysts at - 50 DEG  C. to + 50 DEG  C.  Preferred solvents are chlorinated hydrocarbons such as chlorobenzene or carbon tetrachloride.ALSO:Insecticidal and fasciolicidal compositions contain a phosphorylimino dithiocarbonic acid ester of the general formula:  <FORM:1017440/A5-A6/1> wherein R1, R2, R3 and R4, which may be the same or different, are unsubstituted or substituted alkyl including alkenyl, cycloalkyl including cycloalkenyl aryl or aralkyl radicals and R3 and/or R4 may also represent heterocyclic radicals, and X, X1 abd X11 are oxygen or sulphur atoms and a solid or liquid diluent or carrier.  Numerous examples are given of the radicals R1, R2, R3 and R4, which may be substituted with substituents such as halogen atoms, alkyl and alkoxy radicals and nitro groups, amino groups which may be substituted by alkyl acyl or aryl radicals, and also calbalkoxy keto, carboxyl, hydroxy, thio, mercapto or alkoxy groups.  Suitable carriers or diluents are talc, chalk, bentonite, clay, water (if necessary with commercial emulsifiers), alcohols, ketones and liquid hydrocarbons.  A preferred composition is prepared by mixing the ester with dimethyl formamide as auxiliary solvent, adding as emulsifier a benzyl hydroxy diphenyl polyglycol ether containing about 10 to 15 glycol units and diluting this premixture with water.