title: Nucleophilic reactions of phorate and terbufos with reduced sulfur species under anoxic conditions.
abstract: The reactions of phorate and terbufos with bisulfide (HS-), polysulfide (Sn2-), thiosulfate (S2O32-), and thiophenolate (PhS-) were examined in well-defined aqueous solution under anoxic conditions to investigate their role in the degradations of phorate and terbufos. Reactions were monitored at various concentrations of reduced sulfur species to obtain the second-order rate constants. The reactivity of the reduced sulfur species decreased in the order Sn2- > PhS- > HS- > S2O32-. Hydrolysis products, formaldehyde and diethyl disulfide/di-tert-butyl disulfide, indicated that OH-/H2O attacked the carbon atom between the two sulfur atoms, the so-called thioacetal carbon, which is very reactive due to the presence of the two neighboring sulfur atoms. The reaction of phorate and terbufos with PhS- was investigated to study the transformation products in the reactions with reduced sulfur species. The transformation products demonstrated that the observed increase in rate constants in the reaction with reduced sulfur species compared to hydrolysis could result from the nucleophilic attack of reduced sulfur species at the alpha-carbon of the ethoxy group and at the thioacetal carbon atom. The temperature dependence of measured second-order rate constants of the reaction of phorate and terbufos with HS- over 25-50 degrees C was investigated to explore activation parameters, which are not significantly different for phorate and terbufos. All of the observations may imply similar pathways in the degradation of phorate and terbufos in the presence of reduced sulfur species. Slightly higher hydrolysis rates of terbufos and second-order reaction rate constants for the reactions with sulfur species of terbufos compared with those for phorate are observed, which could be attributed to the slightly different substituents.
authors.affiliation: Chemistry Department, The City College of New York, 138th Street and Convent Avenue, New York, New York 10031, USA.
authors.forename: Qiu
authors.initials: Q
authors.lastname: Gan
authors.forename: Urs
authors.initials: U
authors.lastname: Jans
mesh_terms: D006868:Hydrolysis; D007306:Insecticides / Q000737:chemistry*; D007700:Kinetics; D009946:Organothiophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000032:analysis*; D010702:Phorate / Q000737:chemistry*; D012996:Solutions; D013457:Sulfur Compounds / Q000737:chemistry*
chemical_list: D007306:Insecticides; D009946:Organothiophosphorus Compounds; D012996:Solutions; D013457:Sulfur Compounds; D010702:Phorate; C012568:terbufos; D010100:Oxygen