The levelling effect of solvational imbalances in the reactions of oximate α-nucleophiles with electrophilic phosphorus centers. Relevance to detoxification of organophosphorus esters

Terrier, François; Guével, Eric Le; Chatrousse, Alain‐Pierre; Moutiers, Gilles; Buncel, Erwin

doi:10.1039/b212160n

Cited by 44 publications

(26 citation statements)

References 17 publications

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“…More recently, we showed that fenitrothion degradation was catalyzed by alkali metal ethoxides in ethanol (4). The ethanolysis was shown to proceed via three different routes (Scheme 1): (1) attack at the phosphorus center; (2) attack at the aliphatic carbon of the methoxy group; and (3) attack at the C-1 position of the aromatic ring. However, at higher concentrations of catalyst, we reported a regioselectivity in attack at the phosphorus center.…”

Section: Introductionmentioning

confidence: 98%

Micellar Catalyzed Degradation of Fenitrothion, an Organophosphorus Pesticide, in Solution and Soils

Balakrishnan

Buncel

vanLoon

2005

Environ. Sci. Technol.

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We report on a study of the decomposition of fenitrothion (an organophosphorus pesticide that is a persistent contaminant in soils and groundwater) as catalyzed by cetyltrimethylammonium (CTA+) micelles. The CTA micelles were associated with two types of counterions: (1) inert counterions (e.g. CTABr) and (2) reactive counterions (e.g. CTAOH). The reactive counterion surfactants used were hydroxide anion (HO-) as a normal nucleophile and hydroperoxide anion (HOO-) and the anion of pyruvaldehyde oxime (MINA-) as two alpha-nucleophiles. The reactivity order followed: CTABr < CTAOH < CTAMINA << CTAOOH. Treatment of the rate data using the Pseudo-Phase Ion Exchange (PPIE) model of micellar catalysis showed the ratio k2M/k2w to be less than unity for all the surfactants employed. Rather than arising from a "true catalysis", we attributed the observed rate enhancements to a "concentration effect", where both pesticide and nucleophile were incorporated into the small micellar phase volume. Furthermore, the CTAOOH/CTAOH pair gave an alpha-effect of 57, showing that the alpha-effect can play an important role in micellar systems. We further investigated the effectiveness of reactive counterion surfactants in decontaminating selected environmental solids that were spiked with 27 ppb fenitrothion. The solids were as follows: the clay mineral montmorillonite and SO-1 and S0-2 soils (obtained from the Canadian Certified Reference Materials Project). The reactive counterion surfactant solutions significantly enhanced the rate of fenitrothion degradation in the spiked solids over that obtained when the spiked solid was placed in contact with either 0.02 M KOH or water. The rate enhancements followed the order CTAOOH >> CTAMINA approximately CTAOH > KOH >> water. We conclude that reactive counterion surfactants, especially with alpha-nucleophiles, hold great potential in terms of remediating soils contaminated by toxic organophosphorus esters.

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Section: Introductionmentioning

confidence: 98%

Micellar Catalyzed Degradation of Fenitrothion, an Organophosphorus Pesticide, in Solution and Soils

Balakrishnan

Buncel

vanLoon

2005

Environ. Sci. Technol.

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“…We and others have previously studied nucleophilic catalysis and degradation pathways of organophosphorus esters including OP pesticides. [18][19][20][21][22][23] Importantly, both types of processes, H/D exchange and nucleophile catalysis, involve coordination of a metal ion into a Lewis base site (N, O, S) in the heterocyclic residue and ester moiety, respectively.…”

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confidence: 99%

Rapidly formed quinalphos complexes with transition metal ions characterized by electrospray ionization mass spectrometry

Keller

Esbata

Buncel

et al. 2013

Rapid Comm Mass Spectrometry

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ESI-MS/MS of complexes formed from PA-Q and transition metal ions is a formidable technique to probe initial formation of these complexes in solution. Previous work from other groups established structural requirements that enable charge-state reduction from Cu(II) to Cu(I) in ligand complexes during transition into the gas phase, and these rules allow us to propose structural features of PA-Q complexes with copper ions in solution.

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“…This route enables convenient access to isotopically labelled product [4-13 C] (34) from commercially available [1-13 C]-2-propionic acid. 18 A novel and practical synthesis of S-(1-and 2-halogenoalkyl) sugars (43), including some at the anomeric center, has been developed. The 7-allyl compound ( mammalian protein-farnesyl transferase, but surprisingly the other analogues are effective alternative substrates for this enzyme (Figure 7).…”

Section: Phosphoric Acids and Their Derivativesmentioning

confidence: 99%

“…2 Â 10 3 times more reactive toward ion-paired EtO À Li 1 in anhydrous EtOH (Scheme 15). 43 A detailed study of the specific rates of solvolysis of N,N,N 0 ,N 0 -tetramethyldiamidophosphorochloridate (80) (TMDAPC) with analysis in terms of the extended Grunwald-Winstein equation has been reported (Scheme 19). 41 The same authors proposed catalytic methanolysis promoted by La 31 as a new method for controlled decomposition of paraoxon (74) (Scheme 17).…”

Section: Scheme 13mentioning

confidence: 99%

Organophosphorus Chemistry

Hall

Bricklebank

Grampel³

et al. 2006

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Organophosphorus compounds are ubiquitous in nature, and due to their innate chemical properties, serve a fundamental role in a number of important fields. Among the more prominent features that elevate their status as a unique and versatile class of compounds, include variable oxidation states, multivalency, asymmetry and metal-binding properties. Their presence in bioactive natural products, endogenous biomolecules, small molecule therapeutic agents and pro-drugs substantiates their role in modern synthetic chemistry and chemical biology. Moreover, their central use as ligands and effectors in asymmetric catalysis, as well as key functional groups for the development of new synthetic methods, has taken the field to new heights. This Thematic Series highlights and details some of the novel methods that are advancing the field of organophosphorus chemistry.The Thematic Series covers topics that range from new synthetic methods and phosphorus-based ligands in asymmetric catalysis to bisphosphonates as promising enzyme inhibitors. More specifically, the Thematic Series spans new methods in C-P bond formation, chiral phosphines in nucleophilic organocatalysis, chiral N-phosphinyl auxiliaries, cyclic phosphonamide reagents in the total synthesis of natural products, phosphinate-containing heterocycles, new routes to phosphinoyl-indoles and phosphinoyl-isocoumarins and new chemistries of H-phosphonates. The Thematic Series also details work on new metathesis-based reactions of vinyl phosphonates and phosphate tethers, novel phosphorus-based ligands in asymmetric catalysis, novel rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagents, the Atherton-Todd reaction, cyclic phosphonium ionic liquids with distinct properties, photo-removable phosphate protecting groups, new methods of C-H functionalization using phosphoryl-related directing groups, the exciting chemistry of substituted phosphanylidenecarbenes and phosphoryl azides, and bisphosphonate ethers as promising inhibitors of geranylgeranyl diphosphate synthase (GGDPS).The articles and reviews capture the emerging potential of organophosphorus compounds and exciting opportunities in the field, and hopefully, will inspire and motivate investigators in the field to investigate new chemistry in this area. Taken collectively, organophosphorus chemistry embodies a broad, vibrant and continual growing scientific area with this Thematic Series highlighting recent advances in the field. We are grateful and indebted to the authors for their hard work and exciting contri-

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The levelling effect of solvational imbalances in the reactions of oximate α-nucleophiles with electrophilic phosphorus centers. Relevance to detoxification of organophosphorus esters

Cited by 44 publications

References 17 publications

Micellar Catalyzed Degradation of Fenitrothion, an Organophosphorus Pesticide, in Solution and Soils

Micellar Catalyzed Degradation of Fenitrothion, an Organophosphorus Pesticide, in Solution and Soils

Rapidly formed quinalphos complexes with transition metal ions characterized by electrospray ionization mass spectrometry

Organophosphorus Chemistry

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