Patent GB-917924-A (GB)
Title: Improvements in or relating to organophosphorus insecticides
Inventor: PIANKA MAX
IPC: C07F9/09
Filed: 1959-04-16
Abstract: The invention comprises compounds of formula <FORM:0917924/IV (b)/1> where X and Y are oxygen or sulphur, at least one being sulphur; R and R1 are C1-4 alkyl; R2 and R3 are hydrogen or unsubstituted or substituted alkyl; Z is one of the following groups:- (i) a hydroxyl group when R2 or R3 is alkyl or substituted alkyl and X and Y are different; (ii) the group OR4, where R4 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkyl interrupted in the chain by, e.g. an oxygen or sulphur atom or a carbonyl group, aryl, substituted aryl, aralkyl, substituted aralkyl, an alicyclic group, a heterocyclic or substituted heterocyclic group, or an acyl group; (iii) a dithiocarbamoyl or substituted dithiocarbamoyl group; or (iv) the group NR5R6 where R5 is hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl or an alicyclic group and R6 is alkyl, substituted alkyl, aralkyl, substituted aralkyl or an alicyclic group or NR5R6 together form the residue of a heterocyclic ring together with acid addition and quaternary ammonium salts thereof.  Specified substituents include halogen, alkoxy and alkylmercapto groups.  They may be prepared by reacting a compound of formula <FORM:0917924/IV (b)/2> where M is hydrogen, alkali metal or ammonium in the presence of an inert solvent with a compound A-CHR2.CONH.CHR3.Z where A is chlorine, bromine or iodine, an acid binding agent being used when M is hydrogen.  Alternatively a compound <FORM:0917924/IV (b)/3> may be treated by known methods to replace OH by Z.  The products are pesticides (see Group VI).  Compounds of the formula <FORM:0917924/IV (b)/4> are stabilized by admixture with an acid binding agent and/or an alkanol.  Specified acid binding agents include aqueous ammonia, epichlorhydrin, epoxidised fatty acids, glycidyl ethers, and organic bases.  The following are prepared as starting materials: (C2H5O)2P(S)SCH2CONHCH2OH and (C2H5O)2P(S)OCH2CONHCH2OH by reacting ClCH2CONHCH2OH with (C2H5O)P (S)SK and (C2H5O)2P(S)OK respectively; compounds ClCH2CONHCH2OR1 where R1 is methyl, ethyl, isopropyl, n-butyl, allyl, cyclohexyl, benzyl, chloroethyl and p-chlorophenyl by reacting R1OH with ClCH2CONHCH2OH in the presence of HCl; ClCH2CONHCH2 OCH2CH2OCH2CH3, ClCH2CONHCH2O-tetrahydrofurfuryl, ClCH2CONHCH2OCH2CH2N (C2H5)2, ClCH2CONHCH2OCOC6H5, ClCH2 CONHCH2SC(S)N(CH3)2, ClCH2CONHCH2N (C2H5)2.HCl, ClCH2CONHCH2N(CH3)2.HCl, ClCH2CONHCH2NHC2H5.HCl, ClCH2CONH CH2NHCH3.HCl, ClCH2CONHCH2NH.CH2 C6H5.HCl, ClCH2CONHCH2NHC6H11.HCl and ClCH2CONHCH2-morpholinyl.HCl are prepared by reacting ClCH2CONHCH2Cl with C2H5OCH2CH2OH, tetrahydrofurfuryl alcohol, (C2H5)2NCH2CH2OH, sodium benzoate, NaSC (S)N(CH3)2 and the appropriate amine respectively; N - (chloracetamidomethyl)pyridinium chloride from ClCH2CONHCH2Cl and pyridine; ClCH2CONHCH[SC(S)N(CH3)2]CCl3 from ClCH2CONHCHClCCl3 and NaSC(S)N(CH3)2; CH3CHClCONHCH2OH by the action of HCHO on CH3CHClCONH2; CH3CHClCONH CH2OCH3 and CH3CHClCONHCH2OC2H5\t by reacting CH3CHClCONHCH2OH with CH3OH and C2H5OH respectively in the presence of HCl; ClCH2CONHCH2Cl and ClCH2CONH CHClCCl3 from thionyl chloride and ClCH2 CONHCH2OH and ClCH2CONHCHOHCCl3 respectively; ClCH2CONHCH(OCH3)CCl3 from ClCH2CONHCHOHCCl3 and sodium methoxide; ClCH2CONHCHOHCCl3 from chloral and ClCH2CONH2.  The Provisional Specification refers also to compounds in which Z is SR4, -S.C(S)OC2H5 or -S.C(O)OC2H5 and in which Z is hydroxyl when R2 and R3 are alkyl or substituted alkyl.  Exemplified compounds are: (C2H5O)2P(S)SCH2 CONHCH2SC2H5; (C2H5O)2P(S)SCH2CONH CH2S-C6H4-p-Cl; and (C2H5O)2P(S)OCH2 CONHCH2SC2H5.ALSO:Pesticidal compositions comprise compounds of formula <FORM:0917924/VI/1> where X and Y are oxygen or sulphur, at least one being sulphur; R and R1 are C1-4 alkyl; R2 and R3 are hydrogen or unsubstituted or substituted alkyl; Z is one of the following groups: (i) a hydroxyl group when R2 or R3 is alkyl or substituted alkyl and X and Y are different; (ii) the group OR41, where R4 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkyl interrupted in the chain by e.g. an oxygen or sulphur-atom or a carbonyl group, aryl, substituted aryl, aralkyl, substituted aralkyl, an alicyclic group, a heterocyclic or substituted heterocyclic group, or an acyl group; (iii) a dithiocarbamoyl or substituted dithiocarbamoyl group; or (iv) the group NR5R6, where R5 is hydrogen, alkyl, substituted alkyl, aralkyl, substituted aralkyl or an alicyclic group and R6 is alkyl substituted alkyl, aralkyl, substituted aralkyl or an alicyclic group or NR5R6 together form the residue of a heterocyclic ring together with acid addition and quaternary ammonium salts thereof, together with a carrier e.g. as emulsions, aerosols, dusts, wettable powders, granulates, pellets or pastes. Specified substituents include halogen, alkoxy and alkylmercapto groups.  Additives include surface active agents and adhesives. The invention also comprises pesticidal compositions of improved stability comprising a compound of formula <FORM:0917924/VI/2> in admixture with an acid binding agent, e.g. aqueous ammonia, an organic base or an epoxy compound such as epichlorhydrin, phenyl glycidyl ether or epoxidised fatty acids, pyridine or ethylene diamine, preferably dissolved in an alkanol.