Patent GB-761162-A (GB)
Title: New organic thiophosphoric acid derivatives and compositions containing them
Inventor: METIVIER JEAN
IPC: C07F9/655
Filed: 1954-04-01
Abstract: The invention comprises as new products phosphorus derivatives of g -pyrone of the formula <FORM:0761162/IV(b)/1> in which X is an oxygen or sulphur atom, Y is a hydrogen or halogen atom, R1 is a hydrogen atom or an alkyl group containing not more than 4 carbon atoms and R2 and R3 are the same or different alkyl radicals each containing not more than four carbon atoms, e.g. methyl, ethyl, n-propyl and isopropyl.  The products may be obtained by reacting a salt of the formula (R2O)(R3O)P(X).SMe. (I) in which Me is an alkali metal, e.g. sodium or potassium, with a derivative of the formula <FORM:0761162/IV(b)/2> in which Z is a halogen atom or a reactive ester group such as a sulphate or sulphonate group.  The salts I in which X is an oxygen atom can be obtained in situ by the action of flowers of sulphur on an ester of phosphorous acid of the formula (R2O)(R3O)P.OH in the presence of an alkali metal derivative of ethyl alcohol.  The reaction for the preparation of the g -pyrone derivatives is preferably effected at 50-100 DEG  C. and in an organic solvent, e.g. an aliphatic alcohol or ketone. Examples are given for the production of (1) 2-(diethoxyphosphinothioylthiomethyl) - 5 - methoxy - g  - pyrone from 2-chloromethyl - 5 - methoxy - g  - pyrone and O,O diethyl potassium phosphorodithioate; (2) 2 - (diethoxyphosphinothioylthiomethyl)-5 - hydroxy - g  - pyrone from 2 - chloromethyl-5 - hydroxy - g  - pyrone and O,O - diethyl potassium phosphorodithioate; (3) 2 - (diethoxyphosphinylthiomethyl) - 5 - hydroxy - g -pyrone from O,O-diethyl potassium phosphorothioate and 2-chloromethyl-5-hydroxy-g -pyrone; (4) 2-(diethoxyphosphinothioylthiomethyl) - 5 - hydroxy - 6 - chloro - g - pyrone from 2 - chloromethyl - 5 - hydroxy - 6 - chloro - g -pyrone and O,O-diethyl potassium phosphoro dithioate; (5) 2 - (dimethoxyphosphinothioylthiomethyl) - 5 - methoxy - g  - pyrone from O,O - dimethyl potassium phosphorodithioate and 2 - chloromethyl - 5 - methoxy - g  - pyrone; (6) and (7) 2 - (di - n - propoxy (and - isopropoxy -) phosphinothioylthiomethyl) - 5 - methoxy - g  - pyrone from O,O - di - n - propyl (or - isopropyl -) - potassium phosphorodithioate and 2 - chloromethyl - 5 - methoxy - g  - pyrone; (8) and (9) 2 - (diethoxyphosphinylthio - methyl) - 5 - methoxy - g - pyrone from O,O - diethyl potassium phosphorothioate and 2-chloromethyl - 5 - methoxy - g  - pyrone, or by reacting the latter with the reaction mixture obtained by adding sodium ethylate and flowers of sulphur to a solution of diethyl hydrogen phosphite in ethanol; (10) and (11) 2-(di-isopropoxy-(and n - propoxy -)phosphinyl thiomethyl) - 5-methoxy - g - pyrone using a procedure as in (9) except that di-isopropyl and di-n-propyl hydrogen phosphites are used respectively; (12) 2 - (diethoxyphosphino thioylthiomethyl) - 5-ethoxy - g  - pyrone from 2 - chloro - methyl - 5-ethoxy - g  - pyrone and O,O - diethyl potassium phosphorodithioate; (13) 2 - (dimethoxyphosphinothioylthiomethyl) - 5 - ethoxy - g -pyrone by a procedure as in (12) except that the dimethoxy compound is used.  The 2-chloromethyl - 5 - ethoxy - g  - pyrone used in (12) may be obtained by the action of thionyl chloride on 2 - hydroxymethyl - 5 - ethoxy - g -pyrone.  The products are stated to be valuable pesticides (see Group VI) According to the second Provisional Specification the products in which R1 is C1-C4 alkyl and Y is H may also be obtained by reacting an acid chloride of the formula (R2O)(R3O)P(X)Cl with a kojic acid derivative of the formula <FORM:0761162/IV(b)/3> preferably in the presence of an acid binding agent or by alkylation by known methods of a phosphoric ester of the formula <FORM:0761162/IV(b)/4>ALSO:A pesticidal composition contains a diluent and as the active ingredient or as one of the active ingredients at least one compound of the formula:- <FORM:0761162/VI/1> p  wherein X is an oxygen or sulphur atom, Y is a hydrogen or halogen atom, R, is a hydrogen atom or an alkyl group containing not more than 4 carbon atoms and R2 and R3 are the same or different alkyl groups each containing not more than 4 carbon atoms (see Group IV(b)).  The compounds may be formulated as solid compositions using solid diluents such as talc or clay or as aerosols, emulsions, or solutions in an organic or aqueous organic medium and the solutions or emulsions may contain a wetting, dispersing or emulsifying agent of the ionic or non-ionic type. Other pesticides may also be present.  Specific compositions mentioned include self emulsifying concentrates containing 2 - (diethoxyphossions, or solutions in an organic or phinothioylthiomethyl) - 5 - methoxy - g  pyrone, acetone, dimethylacetonylcarbinol, and an emulsifier derived from 10 moles of ethylene oxide and 1 mole of octyl phenol and similar compositions in which the g  - pyrone derivative is 2 - (diethoxyphosphinylthiomethyl) - 5 - methoxy - g  - pyrone or 2 - ( - dimethoxyphosphinothioylthiomethyl) - 5 - methoxy - g  - pyrone.