Peroxyhydrolysis of nerve agent VX and model compounds and related nucleophilic reactions

Catalytic Decomposition of Simulants for Chemical Warfare V Agents: Highly Efficient Catalysis of the Methanolysis of Phosphonothioate Esters

“…4 Base hydrolysis of V agents and some simulants of these give products that comprise approximately 75–90 % of the desired P–SR cleavage products (R′OP(CH 3 )(O)(O − ) + − SR) and 10–25 % of the undesired P–OEt cleavage products (R′OH + − OP(CH 3 )(O)(SR)) 5. 6 The latter are anionic and resist further base‐promoted hydrolysis but nevertheless are extremely toxic. However, the methoxide reaction of these same VX simulants was shown to proceed with >93 % P–SR cleavage and yield (the other 7 %) a new, neutral transesterified methoxylated starting material, which subsequently can be methanolyzed to benign products 6.…”

“…6 The latter are anionic and resist further base‐promoted hydrolysis but nevertheless are extremely toxic. However, the methoxide reaction of these same VX simulants was shown to proceed with >93 % P–SR cleavage and yield (the other 7 %) a new, neutral transesterified methoxylated starting material, which subsequently can be methanolyzed to benign products 6. 7…”

A decontamination system for chemical weapons agents using a liquid solution on a solid sorbent

“…The concentration of HCO 4 − is maximized near pH 7 and goes to zero near pH 11 [21]. However, the active species in the perhydrolysis of VX is the HOO − ion [18,22,23]. Since H 2 O 2 is a weak acid (pK a = 11.75 at 20 • C) [24,25], a higher pH is needed in order to increase the concentration of the HOO − species.…”

Design and Synthesis of anα,α-Difluorophosphinate Hapten for Antibody-Catalyzed Hydrolysis of Organophosphorus Nerve Agents

“…Unlike the perhydroxide ion attack on VX, for which the concerted S N 2(P) mechanism has been demonstrated, it is still an open question whether this nucleophilic attack on phosphorus is concerted or occurs after pseudorotational interconversion. [19,20] However, this hydroxide ion attack is pH-dependent, and the pseudo-first-order rate constant k OH has been estimated as % 5 Â 10 À3 m À1 s…”