Patent GB-738839-A (GB)
Title: New basic esters of phosphorus-containing acids
Inventor: GHOSH RANAJIT
IPC: C07F9/165
Filed: 1952-11-19
Abstract: The invention comprises as new compounds basic esters of thiophosphoric acid of the general formula S = P(OR1)(OR2)-O-LX and basic esters of phosphorothiolic acid of the general formula O = P(OR1)(OR2)-S-LX in which R1 and R2 are like or unlike alkyl radicals, L is a saturated straight- or branched-chain aliphatic hydrocarbon radical or such a radical in which the carbon atoms are interrupted by an oxygen or sulphur atom or by a nitrogen atom carrying an alkyl substituent, and X stands for a secondary aliphatic or heterocyclic amine attached to L through the amino nitrogen atom. The preferred esters are those in which the hydrocarbon radicals present do not contain more than 4 carbon atoms.  The thiophosphoric acid esters may be made by interacting without heating a halide of a thiophosphoric acid of the formula S = P(OR1)(OR2)-Y in which Y is a halogen atom and R1 and R2 are like or unlike alkyl radicals either with an amino alcohol of the formula HOLX in which L and X are as defined above in the presence of an acid-absorbing agent or with a metal derivative of the formula MeOLX in which Me is a metal and L and X are as defined above.  The thiophosphoric acid esters may also be obtained by interacting without heating a metal salt of a thiophosphoric acid of the formula S = P(OR1)(OR2)-OMe in which R1 and R2 are as defined above and Me is a metal with an aminoalkyl halide of the formula YLX in which Y, L and X are as defined above. The phosphorothiolic acid esters are obtained by the same three processes defined above except that the reactants are heated in each case.  In examples b -diethylaminoethanol, sodium and benzene are heated under reflux until all the sodium is dissolved and, after cooling, diethylchlorothionophosphonate is added and the mixture heated under reflux to yield the compound <FORM:0738839/IV (b)/1> (2) diethylchlorothionophosphonate, b  - diethylaminoethanol, anhydrous sodium carbonate, xylene, and a small amount of copper bronze powder are heated at 90 DEG  C. for 5 hours to yield the same product as in (1); (3) to (10) and (12) as in (1) except that b -dimethylaminoethanol, 1 - diethylaminopropan - 2 - ol, g  - diethylaminopropanol, 2 - (11 - piperidyl) ethanol, b  - (N) - morpholinoethanol, 1 - diethylamino - 3 - ethyl - mercaptopropan - 2 - ol, 1,3 - bis - diethylamino - propan - 2 - ol, 1 - diethylamino - 3 - methoxy - propan - 2 - ol, and g  - di - n - butylaminopropanol, respectively, are used as the amino alcohol, the corresponding phosphorothiolates being obtained; (11) as in (1) except that methylethylchlorothionophosphonate is used to form the corresponding phosphorothiolate; (13) as in (1) except that b  - di - n - butylaminoethanol is used, the corresponding phosphorothiolate being obtained; (14) sodium O : O1-diethyl phosphorothioate is suspended in benzene and treated with b -diethylaminoethyl chloride, the mixture being refluxed in an atmosphere of nitrogen to yield O : O1 - diethyl S - (b  - diethylamino)ethyl phosphorothiolate; (15) a solution of sodium O : O1 - diethyl phosphoro thioate is prepared from diethyl phosphite, sodium, ethanol and sulphur and is refluxed with b -diethylaminoethyl chloride in an atmosphere of nitrogen for 7 hours to yield O : O1-diethyl S-(b -diethylamino)ethyl phosphoro thiolate; (16) sodium is dissolved in a mixture of b -diethylaminoethanol and benzene, the mixture cooled to 10-15 DEG  C. under nitrogen and diethylchlorothionophosphonate added cautiously and reaction effected at 20-25 DEG  C. under nitrogen to yield O : O1-diethyl O11-(b )-diethylaminoethyl thionophosphate; (17) and (18) as in (16) except that 1-diethylamino - propan - 2 - ol and 2 - di - (n)-propylaminoethanol respectively are used to give the corresponding thionophosphates.  The ester products are stated to have outstanding pesticidal properties.