Patent GB-813966-A (GB)
Title: Thiophosphoric acid esters
IPC: C07F9/165
Filed: 1957-06-14
Abstract: The invention comprises thiophosphoric acid esters of the formula <FORM:0813966/IV (b)/1> in which R1 and R2 are C1-C4 alkyl radicals, R is H or a C1-C4 alkyl radical, X is O or S, at least one X being sulphur, and n is a whole number of from 2 to 4.  They may be obtained by (a) reacting an appropriate nitroalkanol with an appropriate O,O-dialkylthionophosphoric acid halide in the presence of an acid binding agent, or (b) by reacting an appropriate nitroalkyl halide with an appropriate O,O-dialkylthiol or thionothiol phosphoric acid salt.  In a modification of the first type of reaction an appropriate O,O-dialkyl phosphite halide is first condensed with an appropriate nitroalkanol in the presence of an acid binding agent to form an intermediate nitroalkyl phosphite product which is then reacted with sulphur.  Method (a) and its modification are only applicable to the preparation of compounds in which the X atom adjacent to the <FORM:0813966/IV (b)/2> group is oxygen and the other X is sulphur and method (b) is applicable only to the production of compounds in which the X atom adjacent to the <FORM:0813966/IV (b)/3> group is sulphur and the other X is oxygen or sulphur.  Method (a) may be carried out at 0-100 DEG  C. and in the presence of an insert solvent such as benzene, toluene or a lower aliphatic liquid hydrocarbon.  Suitable acid binding agents are alkali metal hydroxides or alcoholates on tertiary amines such as pyridine or triethylamine.  Method (b) is preferably carried out at about 60 DEG  to 70 DEG  C. and in the presence of an inert organic solvent, e.g. an aliphatic alcohol or ketone, such as methanol, ethanol, acetone or methyl ethyl ketone.  The salts used are preferably the ammonium, sodium, or potassium salts.  Examples are given for the production of compounds of the general formul  (1) (C2H5O)2P(S)OCH2CH2NO2, (2) (CH3O)2 P(S)OCH2CH2NO2, (3) (C2H5O)2P(O)SCH2CH2 NO2, (4) (CH3O)2P(O)SCH2CH2NO2 (5) (n - C3H7O)2P(O)SCH2CH2NO2, (6) (C2H5O)2 P(S)SCH2CH2NO2, (7)) (CH3O)2P(S)SCH2 CH2NO2, and (8) (C2H5O)2P(S)OCH(CH3)CH2 NO2. The products are stated to be useful as contact and systemic insecticides (see Group VI).ALSO:A pesticidal composition having both contact and systemic activity comprises as active ingredient a thiophosphoric acid ester of the general formula <FORM:0813966/VI/1> in which R1 and R2 are C1-C4 alkyl radicals, R is hydrogen or a C1-C4 alkyl radical, X is oxygen or sulphur, at least one X being sulphur, and n is a whole number of from 2 to 4 and a solid or liquid carrier.  Other known pesticidal agents may also be present.  Specified carriers are chalk, talc, bentonite, water, alcohols, and liquid hydrocarbons. The compositions may be applied as sprays or dusts or as aerosols.  A suitable composition is prepared by adding an equal amount of acetone to O-(b -nitroethyl) - O,O - diethyl thionophosphate, then adding 50 per cent by weight of a commercial emulsifier based on benzyl-hydroxydiphenyl polyglycol ether and then diluting the mixture with water to give an aqueous solution of a concentration of 0.01 or 0.1 per cent active ingredient.  Other active ingredients of the above general formula which are specified are (1) (CH3O)2P(S)OCH2CH2NO2; (2) (C2H5O)2P(O)SCH2CH2NO2; (3) (CH3O)2P(O)SCH2CH2NO2; (4) (n-C3H7O)2P(O)SCH2CH2NO2; (5) (C2H5O)2P(S)SCH2CH2NO2; (6) (CH3O)2P(S)SCH2CH2NO2; and (7) (C2H5O)2P(S)OCH(CH3)CH2NO2.