Reactions of VX, HD, and Their Simulants with NaY and AgY Zeolites. Desulfurization of VX on AgY

Abstract

The room-temperature reactions of the chemical warfare agents VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate), HD (2,2‘-dichloroethyl sulfide, or mustard), and their common simulants, O,S-diethyl phenylphosphonothioate (DEPPT) and 2-chloroethyl phenyl sulfide (CEPS), with NaY and silver-exchanged (AgY) zeolites have been studied using solid-state magic angle spinning NMR. VX hydrolyzes via exclusive cleavage of the P−S bond on both NaY and AgY to yield ethyl methylphosphonate (EMPA). The reaction is significantly faster on AgY than on NaY, suggesting catalysis by silver. On AgY, an intermediate silver salt of EMPA is apparently formed which is slowly converted to ethyl 2-(diisopropylamino)ethyl methylphosphonate (QB, the desulfurized analogue of VX) in about a 78% yield. DEPPT similarly hydrolyzes via P−S cleavage on AgY to yield an apparent silver salt of ethyl phenylphosphonate, which does not undergo further reaction to the desulfurized analogue. No reaction is observed for DEPPT on NaY. HD on AgY forms both vinyl sulfide and the cyclic ether 1,4-thioxane. HD reacts faster on NaY to exclusively form the CH-TG sulfonium ion (HOCH2CH2SCH2CH2S+[CH2CH2OH]2). CEPS also reacts faster on NaY, forming 2-hydroxyethyl phenyl sulfide. On AgY, CEPS does not give the vinyl product, but does yield the ether product PhSCH2CH2OCH2CH2SPh. A mechanism is proposed for the silver-catalyzed hydrolysis of VX, the desulfurization of the cleaved thiol, and the formation of QB.