Patent GB-1038611-A (GB)
Title: Thiophosphoric acid esters containing sulphonyl groups
Inventor: SARKAR ASIM KUMAR
IPC: C07C317/18
Filed: 1961-11-08
Abstract: The invention comprises compounds having the general formula S = P(OR1)(OR2)S.Z.SO2R3 wherein R1 and R2 are the same or different and each is a C1-C4 alkyl group, R3 is a phenyl group substituted by at least one substituent selected from halogen (e.g. Cl or Br), nitro and C1-C4 alkyl, and Z is a saturated straight or branched chain divalent aliphatic hydrocarbon group containing at least two carbon atoms and which may be interrupted by one or more oxygen or sulphur atoms.  They may be obtained by reacting a compound of the formula S = P(OR1)(OR2)S.Z.SO2R2 where M is alkali metal or ammonium with a compound of the formula Hal.Z.SO2R3 in which Hal is a halogen atom e.g. Cl or Br.  The reaction is suitably effected in an inert organic solvent e.g. an ester or ketone, at elevated temperature e.g. at or about the boiling point of the solvent.  The products have pesticidal properties (see Division A5).  The compounds Hal.Z.SO2R3 may be obtained by reacting HO.Z.SO2R3 with a halogenating agent e.g. PBr3 or thionyl chloride.  1 - nitro - 4 - (21 - hydroxyethyl) phenyl thioether is obtained by reacting ethylene chlorhydrin with p-nitrothiophenol and may be reacted with PBr3 to form 1 - nitro - 4 - (21-bromethyl) - phenyl thioether which may be oxidized to the corresponding sulphonyl compound by means of H2O2 and acetic acid. 1-Chloro - 4 (21 - hydroxypropylsulphonyl) benzene is obtained by reacting propylene oxide or propylene chlorhydrin with p-chlorobenzene sulphinic acid or by oxidation of the corresponding sulphide with H2O2 and acetic acid and may be reacted with PBr3 to form the corresponding 2-bromopropyl compound.  b -Chloro - ethoxyethyl - 4 - nitrophenyl sulphone is obtained by reacting di-(2-chloroethyl) ether with the sodium salt of p-nitrothiophenol. 1-Chloro - 4 - nitro - 2 - (21 - chloroethoxyethyl) sulphonyl benzene is obtained by reacting di(2-chloroethyl) ether on sodium 2-chloro-5-nitro-benzene sulphinate. 1-Methyl-4-(21-chloroethyl-sulphonyl) benzene is obtained by the action of SOCl2 in CHCL3 on the corresponding 21-hydroxy ethyl compound which may be obtained by the reaction of ethylene oxide or ethylene chlorhydrin on p-toluene sulphinic acid.  1-Chloro - 4 - (21 - bromoethylsulphonyl) - benzene is prepared by (a) reacting PBr3 with the corresponding 21 hydroxyethyl compound which is prepared by reacting ethylene oxide with p-chlorobenzene sulphinic acid; or (b) by the action of ethylene oxide on the sodium salt of 4-chlorobenzene sulphinic acid and then treating with PBr3. 1 - Bromo - 4 - (21 - bromoethyl-sulphonyl)-benzene may be obtained similarly by reacting ethylene oxide with sodium 4-bromobenzene sulphinate and then treating with PBr3.ALSO:A pesticidal composition comprises a carrier or solvent and a compound of the formula: S = P (OR1) (OR2) S. Z. SO2R3 wherein R1 and R2 are C1-C4 alkyl groups, R3 is a phenyl group substituted by at least one substituent selected from halogen (e.g. Cl or Br), nitro, and C1-C4 alkyl and Z is a saturated straight or branched chain divalent aliphatic hydrocarbon group containing at least 2 carbon atoms and which may be interrupted by one or more O or S atoms.  The carrier may be solid or liquid.