Phosphorodithioic Acid Research Articles

Monitoring Great Horned Owls for Pesticide Exposure in Southcentral Iowa

Organophosphorus pesticide (OP) residues occur in mice (Peromyscus spp.) inhabiting Iowa cornfields, suggesting a possible route of OP exposure to mouse predators. In 1988 and 1989 we livetrapped and radiotagged great horned owls (Bubo virginianus), common predators of mice, near cornfields in Iowa before and after OP applications of COUNTER 15G® (active ingredient terbufos, phosphorodithioic acid S-[[(1,1-dimethylethyl)thio]methyl] O,O-diethyl ester) and LORSBAN 15C® (active ingredient chlorpyrifos, phosphorothioic acid O-(3,5,6-trichloro-2-pyridinyl) O,O-diethyl ester). We captured 32 owls over the 2-year period and radiomonitored 7 owls in 1988 and 15 owls in 1989. We analyzed blood plasma from livetrapped owls for depression and reactivation of cholinesterase (ChE) activities and fecal-urate samples for excretory metabolites to determine if owls were exposed to OPs before capture. Plasma ChE activities from 3 owls captured post-application in 1989 were >2 standard deviations of the control mean, indicating OP exposure. However, no reactivation in enzyme activities occurred in plasma ChEs incubated in the presence of 2-PAM (pyridine-2-aldoxime methochloride), and alkyl phosphate residues were below quantification limits in fecal-urate samples. Most habitats within the home ranges of radiotagged owls were nontreated, and home range size estimates (min. convex polygon and 50% harmonic mean activity areas) and percent-use of treated areas did not differ (P > 0.05) between pre- and post-pesticide application periods. No radiotagged owls died during the 2-year study. We conclude that the relatively large proportion of nontreated habitats within home ranges and the diversity of prey consumed limited OP exposure in the great horned owls monitored.

S-methylation of O,O-dialkyl phosphorodithioic acids: O,O,S-trimethyl phosphorodithioate and phosphorothiolate as metabolites of dimethoate in mice.

O,O,S-Trimethyl phosphorodithioate and phosphorothiolate [(MeO)2P(S)SMe and (MeO)2P-(O)SMe, respectively are known from earlier studies to be impurities, delayed toxicants, and detoxication inhibitors in several major O,O-dimethyl phosphorodithioate insecticides. Our recent studies show extensive S-methylation of mono- and dithiocarbamic acids in mice, suggesting the possibility that phosphorodithioic acids such as (MeO)2P(S)SH might also undergo S-methylation. This possibility was examined in ip-treated mice with emphasis on the metabolites of dimethoate [(MeO)2P(S)SCH2C(O)NHMe], one of the most important organophosphorus insecticides. The urinary metabolites of dimethoate, which contains no P-SMe substituent, were found to include four compounds with P-SMe moieties identified by 31P NMR spectroscopy as MeO(HS)P(O)SMe, MeO(HO)P(O)SMe, (MeO)2P(S)SMe, and (MeO)2P-(O)SMe; the latter two compounds are also established by GC-MS as dimethoate metabolites in mouse urine, liver, kidney, and lung. Several approaches verified unequivocally that the previously unknown P-SMe metabolites in urine and tissues are due to in vivo S-methylation rather than to impurities. Studies with other O,O-dimethyl and O,O-diethyl phosphorodithioate insecticides established the analogous S-methylation pathway for ethion, malathion, phenthoate, phosalone, and phosmet in mice. Thus, metabolism of O,O-dialkyl phosphorodithioate insecticides in mammals is shown here for the first time to yield S-methyl phosphorodithioates and phosphorothiolates from in vivo S-methylation of the intermediate O,O-dialkyl phosphorodithioic acids.

In Vivo and in Vitro Inhibition of Nicosulfuron Metabolism by Terbufos Metabolites in Maize

Reduced maize tolerance to nicosulfuron [2-(((((4,6-dimethyoxy-2-pyrimidinyl)amino)carbonyl)amino)sulfonyl)-N,N-dimethyl-3-pyridinecarboxamide], a sulfonylurea herbicide, occurred when the herbicide was applied following terbufos (S-[[(1,1-dimethylethyl)thio]methyl]O,O-diethyl phosphorodithioate) insecticide. To determine the mechanism of this interaction, the effect of terbufos on the metabolism of nicosulfuron was studied in whole plants and in an in vitro microsomal system from maize. Terbufos applied in the nutrient solution of hydroponically grown maize 36 hr prior to herbicide application increased nicosulfuron uptake 4% 48 hr after treatment. Nicosulfuron metabolism decreased by 10 and 15%, respectively, for the 0.45 and 4.5 μM terbufos treatments 24 hr after application. Plants grown in the presence of the terbufos oxidative metabolites, terbufos-sulfoxide (phosphorodithioic acid S-[(tert-butylsulfinyl)methyl]O,O-diethyl ester) and terbufos-sulfone (phosphorodithioic acid S-[[(1,1-dimethylethyl)sulfonyl]methyl]O,O-diethyl ester), had 22 and 55% reductions in nicosulfuron metabolism, respectively, at 24 hr after herbicide application. In microsomal preparations, terbufos-SO and terbufos-SF severely inhibited cytochrome P450 mediated hydroxylation of nicosulfuron while terbufos had a lesser effect. Terbufos-SF was more inhibitory in vitro than terbufos-SO. Terbufos-SO and terbufos-SF reduced nicosulfuron tolerance in maize by inhibiting the cytochrome P450 monooxygenases involved in nicosulfuron hydroxylation.

Synthesis and performance evaluation of O, O-dialkylphosphorodithioic disulphides as potential antiwear, extreme-pressure and antioxidant additives

The ashless antiwear/EP additives based on phosphorodithioic acids are preferred to their heavy metal complexes, due to operational problems and enviromental restrictions being enforced in many countries. Four O, O-dialkylphosphorodithioic disulphides with varying alkyl chain length from C5 to C10 have been synthesized and their antiwear, EP and antioxidant performance examined vis-à-vis a commercial ZDDP in a mineral base oil. The synthesized products have been found to exhibit appreciable antiwear and antioxidant properties and mild EP performance, which are comparable to that of commercial ZDDP.

Synthesis and bioactivity of new phosphorodithioates derived from N-substituted maleamic esters

1. A new series of organophosphorus compounds derived from N-substituted maleamic esters by reaction with dimethyl and diethyl phosphorodithioic acid was synthesized. 2. Two isomers, with chemical structures analogous to malathion were obtained for each maleamic ester assayed. 3. They were characterized, and their toxicity against a resistant strain of Musca domestica (strain G), a susceptible one (strain RAC) and Triatoma infestans (vector of Chagas' disease) were measured. 4. The structural chemical modification introduced by replacing a carboxyester group for a N-substituted amido one, reverted the resistance obtained for malathion. 5. Replacement of methyl by ethyl dithiophosphoric acid did not introduce significative differences. 6. In the case of Triatoma infestans, the synthesized compounds were less active than malathion.

Removal of Organophosphorus Pesticides from Aqueous Solution by Using Adsorptive Bubble Separation Techniques

Abstract Two organophosphorus pesticides, ddvp (phosphoric acid 2,2-dichlorovinyl dimethyl ester) and phorate (phosphorodithioic acid o,o-diethyl s-[(ethylthio)methyl] ester) were removed from aqueous solution by three adsorptive bubble separation techniques: air stripping, solvent sublation, and adsorbing colloid flotation. The effects of pH, flow rate, surfactant, ethanol, ionic strength, and coprecipitant concentration on the efficiency of pesticide removal were studied. Over 97% of phorate was removed in 30 min by solvent sublation, and 90% of phorate was removed in 10 min by adsorbing colloid flotation with Fe(OH)3, floc. The separations of ddvp by these techniques were not effective.

Modeling of extraction equilibrium and computer simulation of extraction-stripping systems for nickel extraction by di-n-butylphosphorodithioate

A chemical model for nickel(II) extraction from acidic sulfate solutions with phosphorodithioic acid di-n-butyl ester (O,O-di-n-butyl phosphorodithioate) is presented and used for discusion of extraction-stripping systems with either conventional sequential stages of extraction and stripping or with unconventional cross-current and combined flows. A good agreement of the model with experimental extraction data is observed

Fate of malathion andO,O,S-trimethyl phosphorothioate by-product in Hawaiian soil and water

The fate of malathion (I) and a formulation byproduct,O,O,S-trimethyl phosphorothioate (II), were determined in soil and water from an agricultural area on Kauai, Hawaii. Rapid degradation of I was observed in laboratory soil microcosms (t1/2 = 8.2 h) and in the field (t1/2 = 2 h) and dimethyl phosphorodithioic acid and diethyl fumarate were identified as degradation products. Degradation of II was relatively slow in laboratory soil microcosms (t1/2 = 6.4 d) and the degradation rate of both I and II decreased significantly after γ irradiation. Degradation of I in river, ground and seawater (avg. t1/2 = 4.7 d) was controlled by an elimination reaction; photolysis and biodegradation played minor roles. Dissipation of II in river water was primarily by biodegradation. Strong sorption of I to Lihue silty clay soil (Koc = 405) was determined while II was weakly bound (Koc = 9.8). Rapid degradation and strong sorption of I suggest a low potential for groundwater contamination. Although II degrades slowly and is weakly bound to Lihue soil, the extremely low concentrations found in the dilute formulations applied in fruit-fly control should not present a groundwater problem.

Determination of O,O-Bis(2-Ethylhexyl)Phosphorodithioic Acid in Water at the ppt Level by GC/ECD After Reactive Extraction and Pre-Column Derivatization

Abstract A procedure for the determination of O,O-bis(2-ethylhexyl)phosphorodithioic acid (EPDTH) in water has been developed. It includes the extraction of the analyte as its Bi(III) complex followed by derivatization with pentafluorobenzylbromide and subsequent GC separation and electron capture detection. The formation of a Bi(III) complex of EPDTH ensures quantitative extraction and derivatization also at very low concentrations, whereas the use of a reagent leading to a halogen-containing derivative allows the application of the highly sensitive and selective ECD. The good linearity is characterized by a value of 0.9993 of the linear correlation coefficient in the 0.05-1000 ppb analyte concentration range. The mass detection limit for the pentafluorobenzylester of EPDTH is 1 pg for a signal-to-noise ratio of 3. With this method, the determination of EPDTH below the maximum admissible concentration of 100 ppt established for organophosphorous compounds in drinking water is possible. Non-contaminated g...

Studies on the Reaction of Sugar Aziridines with Organophosphorus Acids. Regio- And Stereo-Selective Ring-Opening of Methyl 4, 6-0-Benzylidene-2, 3-Dideoxy-2, 3-Epimino-α-D-Manno-and Allopyranosides with 0,0-Dialkylphosphorodithioic Acids

ABSTRACT Ring-opening reactions of methyl 2,3-N-acetylepimino-4,6-O-benzylidene-2,3-dideoxy-α-D-mannopyranoside (2) and-α-D-allopyranoside (4) with phosphorodithioic acids 5 and 6 proceed smoothly at ambient temperature to give exclusively products of altro configuration in quantitative yields. A similar stereoselective reaction between methyl 4,6-O-benzylidene-2,3-dideoxy-2,3-epimino-α-D-mannopyranoside (1 and -α-D-allopyranoside (3) and the alkylammonium salt of the acid 6 requires more vigorous conditions.

ChemInform Abstract: Synthesis of Phosphorodithioic Acid O,O‐Di(1,1,3‐trihydroperfluoropropyl) Ester.

ChemInformVolume 20, Issue 45 Organoelement Compounds ChemInform Abstract: Synthesis of Phosphorodithioic Acid O,O-Di(1,1,3-trihydroperfluoropropyl) Ester. I. G. MASLENNIKOV, I. G. MASLENNIKOV Leningradskii tekhnol. inst. im. LensovetaSearch for more papers by this authorA. N. LAVRENT'EV, A. N. LAVRENT'EV Leningradskii tekhnol. inst. im. LensovetaSearch for more papers by this authorL. N. KIRICHENKO, L. N. KIRICHENKO Leningradskii tekhnol. inst. im. LensovetaSearch for more papers by this author I. G. MASLENNIKOV, I. G. MASLENNIKOV Leningradskii tekhnol. inst. im. LensovetaSearch for more papers by this authorA. N. LAVRENT'EV, A. N. LAVRENT'EV Leningradskii tekhnol. inst. im. LensovetaSearch for more papers by this authorL. N. KIRICHENKO, L. N. KIRICHENKO Leningradskii tekhnol. inst. im. LensovetaSearch for more papers by this author First published: November 7, 1989 https://doi.org/10.1002/chin.198945218Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume20, Issue45November 7, 1989 RelatedInformation

ChemInform Abstract: Stereoselective Synthesis of S‐(2‐Deoxy‐α‐D‐glycosyl)‐phosphorodithioates and of Their (2R)‐2‐Deoxy‐2‐deuterio Analogues. Novel Route to C‐2 Deuterium Labeled 2‐Deoxy Monosaccharides.

AbstractTreatment of unsaturated pyranoses such as (I) or (IV) with phosphorodithioic acids results in cis addition and predominant (→ (III)) or exclusive (→ (VI)) formation of the very stable α anomers.

Rotational isomerism of O,O′-dialkyl esters of phosphorodithioic acid

Compounds (RO) 2 P(:S)SH, RPr i , Bu n , and Oct n , exhibit rotational isomerism about PO and PS bonds. Temperature-dependence studies of band intensities indicate values of Δ H for the equilibria between isomers to be 2.5 kJ mol −1, RPr i ; 3.0 kJ mol −1, RBu n ; and ∼4.5 kJ mol −1, ROct n .

First Stereqselective Synthesis of Nitrophenyl 2-Deoxy- β-D-glycosides

Abstract α-Dithiophosphates of peracetylated 2-deoxyhexc-pyranoses, 1a, 1b and 2, uhich are easily prepared by addition of organic phosphorodithioic acids to glycais react smoothly with resin-bound 2- and 4-nitrophenoxides to give stereoselectively the respective nitrophenyl 2-deoxy-β-D-hexopyranosides (3, 4, 5 and 6) in high yields. Glycosylation of the 2, 4-dinitro'phenoxide, however, leads with comparable stereoselectivity to 2,4-dinitrophenyl 2-deoxy- α-D-hexopyranosides (7 and 8). Glycosides 3 - 6 are quantitatively deacetylatec by Amberlyst A-26 (OH-), whereas glycosides 7 and 8, under the same reaction conditions undergo splitting of the O-glycosidic bond.

Farm worker exposure to terbufos [phosphorodithioic acid, S-(tert-butylthio) methyl O,O-diethyl ester] during planting operations of corn.

Eleven farmers were monitored for dermal and respiratory exposure to terbufos [phosphorodithioic acid, S-(tert-butylthio) methyl O,O-diethyl ester] during a typical working day while planting corn and applying COUNTER® 15-G systemic insecticide-nematicide. The average estimated dermal exposure was 72 Μg/hr while the estimated respiratory exposure was 11 Μg/hr. The results of urinary alkyl phosphate analyses were all negative showing no detectable absorption of terbufos. Plasma and red blood cell cholinesterase values of exposed farmers showed no significant difference in activity when compared to either preexposure or control values indicating no adverse physiological effects from the exposure. Based on these results, the use of COUNTER 15-G does not present a significant hazard, in terms of acute toxicity, to farmers using this product for the control of corn insects.

Methods for the determination of total terbufos- [phosphorodithioic acid, S-(tert-butylthio)methyl O,O-diethyl ester], related residues in dermal exposure pads and air-collection tubes and related alkyl phosphate metabolites in urine

Methods for the determination of total terbufos- [phosphorodithioic acid, S-(tert-butylthio)methyl O,O-diethyl ester], related residues in dermal exposure pads and air-collection tubes and related alkyl phosphate metabolites in urine

EXTRACTIONOFTERVALENTLANTHANIDESWITH ACIDIC ORGANOPHOSPHORUS COMPOUNDS

The equilibrium.extraction behavior for a series of tervalent lanthanide ions (Ln3+) using a chloroform solution containing di(2-ethyl-hexyl) phosphoric acid (HDEHP), diphenylphosphinic acid (HDPP), dibutylphosphorothioic acid (HDBPT), di-n-octylphosphorodithoic acid (HDOPDT), or di(2-ethylhexyl)phosphorodithioic acid (HDEHPDT), either alone or combined with adduct forming agents is studied. The extracted species are Ln(DEHP) 3(HDEHP) 3, Ln(DPP)3 (HDPP)3, Ln(DBPT)3, and are Ln(DBPT)3(HDERP)3 in the presence of o-phen and its analogs (B). Extraction constants for the lanthanides follow the order HDPP > HDEHP > HDBPT » HDOPDT. HDPP was the most selective of all the extractants examined. HDOPDT and HDEHPDT were found to be ineffective lanthanide extractants.

Hydrolysis of the O,O-dialkyl phosphorodithioic acids used as extractants in liquid-liquid systems

Hydrolysis of the O,O-dialkyl phosphorodithioic acids used as extractants in liquid-liquid systems

Infrared and Raman spectroscopic studies of rotational isomers of O, O-diethyl phosphorodithioic acid

Infrared and Raman spectra of O, O-diethyl phosphorodithioic acid have been studied both at and below room temperature. The results show that the vibrations of P=S, P(-O)2, P-S and S-H groups give multiple bands and the relative intensities of these bands vary as the temperature of the sample changes. According to the experimental results, we suggest that there are four rotational isomers of O, O-diethyl phosphorodithioic acid. Reasons for splitting the vibrational bands of these groups are also discussed.

NUCLEOPHILIC SUBSTITUTION REACTIONS ON ANTIMONY(III) 0,0-DISUBSTITUTED PHOSPHORODITHIOATES

Abstract Antimony(III) tris(0,0-diisobutyl phosphorodithioate), 1 (R = i-Bu) has been found to undergo a nucleophilic displacement reaction with sodium 1-propanethiolate to give antimony(III) tris-(1-propanethiolate), 4, and sodium 0,0-diisobutyl phosphorodithioate (8, R = i-Bu). Reaction of 1 (R = i-Bu) with phenyllithium gave triphenylstibine and lithium 0,0-diisobutyl phosphorodithioate. Similar reactions of various compounds of type 1 with the sodium salts of carboxylic acids and with the sodium salt of pyrrole were also found to occur. Furthermore, antimony tris(0,0-diisobutyl phosphorodithioate), 1 (R = i-Bu), was found to undergo solvolysis with n-propyl mercaptan to give 4 and 0,0-diisobutyl phosphorodithioic acid 5. Compounds of type 1 are used as passivating agents in petroleum refining, and reactions of the types described for 1 with n-propyl mercaptan and with the salts of carboxylic acids probably occur when “Phil-Ad CA” is added to the feedstock of a fluid catalytic cracking unit.