Patent GB-828671-A (GB)
Title: Thiophosphoric acid esters and a process for their production
IPC: G01N21/64
Filed: 1957-12-13
Abstract: The invention comprises thiophosphoric acid esters of the general formula <FORM:0828671/IV (b)/1> in which R is a C1-C4 alkyl radical, R1, R2 and R3 are organic groups forming a quaternary ammonium salt, X is oxygen or sulphur and n is 2 or 3.  They may be obtained by reacting appropriate S-bromoalkyl-O,O-dialkyl-thiol or -thiolthiono-phosphoric acids with tertiary amines of the formula N(R1)(R2)(R3).  The radicals R1, R2 and R3 may be aliphatic radicals, e.g. alkyl, cycloalkyl radicals, e.g. cyclopentyl, alkylated cyclopentyl, cyclohexyl and alkylated cyclohexyl, or aryl- and cycloalkyl-substituted aliphatic radicals, e.g. phenyl- and alkylphenyl-substituted alkyl radicals and substituted aliphatic and cycloaliphatic radicals, e.g. alkoxy-substituted alkyl radicals or carbalkoxy alkyl radicals of the formula R1OOCR11-wherein R1 is C1-C4 alkyl and R11 is C1-C4 alkylene, cyano alkyl, aroxy substituted alkyl radicals, aromatic radicals including phenyl, xylyl, hydroxy-phenyl, acetyl phenyl and naphthyl or R1, R2 and R3 together with the N atom may form a heterocyclic nucleus of aromatic character, e.g. pyridine, quinoline, picoline, lutidine, chloropyridine and chloroquinoline. R1 and R3 together with the N atom may also form a saturated heterocyclic radical e.g. piperidine, piperazine, morpholine or thiomorpholine.  The reaction may be carried out in the presence of an inert solvent.  Examples are given for the production of: (1) (CH3)3N(Br) CH2CH2SP(O)(OC2H5)2 and the corresponding thiolothiono compound; (2) <FORM:0828671/IV (b)/2> and the corresponding thiolothiono compound; (3) (CH3)3N(Br)CH2CH2CH2SP(O) (OC2H5)2 and the corresponding thiolothiono compound; (4) (NC.CH2)(CH3)2N(Br) CH2CH2SP(O)(OC2H5)2; and (5) <FORM:0828671/IV (b)/3> and the corresponding thiolthiono compound. The products are useful as insecticides (see Group VI) and some of the compounds are strong cholinesterase inhibitors.ALSO:An insecticidal composition comprising as active ingredient at least one thiophosphoric acid ester of the general formula <FORM:0828671/VI/1> in which R is a C1-C4 alkyl radical, R1, R2 and R3 are organic groups forming a quaternary ammonium salt, X is oxygen or sulphur and n is 2 or 3 and a solid or liquid diluent or carrier.  The radicals R1, R2 and R3 may be the same or different and may be aliphatic, substituted aliphatic, cycloalkyl, aralkyl or aryl or may be groups which together with the N atom form a heterocyclic radical of aromatic character, e.g. pyridine, quinoline, picoline, butidine, chloropyridine or chloroquinoline or R1 and R2 together with the N atom form a saturated heterocyclic radical, e.g. piperidine, piperazine, morpholine or thiamorpholine.  Specified carriers or diluents are talc, chalk, bentonite, clay, water (if necessary with an emulsifier), an alcohol, ketone or a liquid hydrocarbon.  A known insecticide or fertilizer may also be present.  Typical dithiophosphate products are the compounds of the formul  : (1) (CH3)3 N(Br)CH2CH2SP(O)(OC2H5)2; (2) (CNCH2) (CH3)(CH3)N(Br)CH2CH2SP(O) (OC2H5)2; and <FORM:0828671/VI/2> and the dithiophosphate analogues of (1) and (2).