Patent GB-882541-A (GB)
Title: New unsaturated thiophosphoric acid esters
IPC: A01N57/12
Filed: 1959-09-18
Abstract: The invention comprises phosphorus esters of the formula: (RO)2PX-S-CH2-CR1 : CR2-CO-NR3 R4 wherein R is a C1-C4 alkyl group, X represents oxygen or sulphur and R1, R2, R3 and R4 ar the same or different and represent bydrogen or C1-C4 alkyl groups.  They may be obtained by condensing a salt of a phosphoric or thiophosphoric acid of the formula:  (RO)2P(X1)X2H with a compound of the formula: Y.CH2.CR1 : CR2.CO.NR3R4 wherein Y is a reactive ester residue such as a halogen atom or a sulphuric or sulphonic ester residue, R, R1, R2, R3 and R4 are as defined above, and one of X1 and X2 is sulphur and the other is oxygen or sulphur.  Suitable salts are alkali metal or ammonium salts or salts with a tertiary organic base, e.g. pyridine.  The reaction is preferably effected in an organic solvent medium, e.g. an alcohol, ketone, ester, nitrile or aromatic hydrocarbon, and at between room temperature and 120 DEG C. When X1 in the starting material is a sulphur atom and X2 is an oxygen atom the product obtained is in the thiolo form, i.e. X in the product is an oxygen atom.  Examples are given for the production of 4-0,0-diethyl-thiolo-phosphoryl crotonamide and the corresponding N-methyl, N,N-diethyl, N,N-dimethyl and N-isopropyl compound; 4-0,0-diethyl-thiolo-phosphoryl crotonamide and the corresponding N-methyl, N,N-dimethyl, and N-ethyl compounds; and N-alkyl-4,0,0-dimethylthiolophosphoryl crotonamide.  The products have pesticidal properties (see Group VI).  N-methyl-, N,N-diethyl-, N,N-dimethyl-, N-isopropyl-, and N-ethyl-4-chloro-crotonamide are obtained by reacting methylamine, diethylamine, dimethylamine, monoisopropylamine and monoethylamine respectively with 4-chlorocrotonyl chloride.ALSO:A pesticidal composition comprises a thiophosphoric ester of the general formula <FORM:0882541/VI/1> wherein R is a C1-C4 alkyl group, X is oxygen or sulphur, and R1, R2, R3 and R4 are the same or different and represent hydrogen atoms or C1-C4 alkyl groups (see Group IV (b)) in association with one or more diluents compatible therewith.  Specified diluents are solid diluents e.g. talc, magnesia, kieselguhr, tri-calcium phosphate, cork powder, absorbent charcoal, kaolin and bentonite, and liquid diluents, e.g. an organic or aqueous-organic medium such as an aromatic hydrocarbon, e.g. toluene or xylene, a mineral or vegetable oil, or a mixture of such diluents, and the composition may be in the form of an aerosol, suspension, emulsion or solution in such liquid diluents.  Ionic or non-ionic wetting, dispersing or emulsifying agents may be present. Other pesticides may also be present.  In examples: (1) to a solution of N - methyl - 4 - O,O - diethylthiolophosphoryl in xylene is added a condensation product of 10 molecular proportions of ethylene oxide and one molecular proportion of octyl phenol, xylene is added, and the solution diluted with water; (2) the wetting agent used in (1) is added to a solution of N-ethyl-4-O,O-diethylthiolophosphoryl crotonamide in acetone and the solution diluted with water; (3) to a solution of 4-O,O-diethyldithiophosphoryl-crotonamide in xylene is added sodium dioctylsuccinate sulphonate, xylene is added and the solution dispersed in water to form an emulsion.