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The formation of peroxyacids by the reaction of a persalt (sodium percarbonate, sodium perborate,…) with an initiator (TAED, TAGU, NOBS, ISNOBS, PAG, acylsugars) has been developed. The reactivity of these peroxyacids generated “in situ” has been studied in the destruction of paraoxon (0,0-diethyl O-paranitrophenylphosphate) with some long chain tetraalkylammonium salts.

A new peroxyacid-ester series has been obtained and used in the destruction of toxic agents. These structures oROCOC6H4CO3H and ROCO(CH2)nCO3H are more stable than the unsubstituted compounds. The reaction with paraoxon (0,0-diethyl 0-paranitrophenylphosphate) and HD (2,2′-dichlorodiethylsulfide) goes to completion in a very short time. The influence of the R group and the length of the chain (n = 2……12) has been studied. The addition of some long chain tetraalkyl-ammonium salts enhances the rate of the reaction by micellar catalysis.

Some complexed stable hydrogen peroxides (percarbonates, perhydrol, DABCO,2 H2O2) have been studied in the destruction of paraoxon (O,O-diethyl paranitrophenylphosphate) and PhCH2CH2SCH2CH2CI. The reaction goes to completion in a short time specially in the presence of long chain tetraalkyl ammonium salts. With other peroxides (alkyl or arylhydroperoxides, bis-trimethylsilyl- or bis-triethylgermylperoxides) the reaction is slower.

Reactions of O-ethyl S-(2-diisopropyl-amino)ethyl methylphosphonothiolate, VX 1, were investigated with five oxidizing agents. In all the cases, the formation of the VX N-oxide 7 was observed prior to the subsequent oxidation and hydrolysis into the nontoxic O-ethyl methylphosphonate 2. Magnesium monoperoxyphthalate (MMPP) is probably one of the most active reagents to achieve the complete detoxification of VX 1. The decontamination using MMPP was also extended with success to soman 13, a G-type agent. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:485–490, 2001

H3PO5, monoperoxyphosphoric acid easily prepared by the reaction of H2O2 with P2O5 in acetonitrile, is a very good decontamination agent. The destruction of toxic sulfur and phosphorus agents is completly achieved in very short time.

A new and efficient method for oxidising sulfides selectively to sulfoxides has been developed with atmospheric oxygen, in the presence of isobutyraldehyde and catalysed by NiII complexes such as bis[1,3-bis-(p-methoxyphenyl)-1,3-propanedionato]nickel, [Ni(dmp)2], and bis[acetylacetonato]nickel, [Ni(acac)2].

Chemical decontamination of toxic compounds (chemical warfare agents and/or insecticides) is of increasing importance. In this study, we report the use of ω-phthalimidoperoxyalkanoic acids 2 in the destruction of paraoxon (O,O-diethyl-O-para-nitrophenylphosphate), a well-known insecticide, and 2-chloro-2′-phenyldiethyl sulfide (a half mustard). We show that while all the peroxyacids used in this series allow the destruction of toxic compounds, the length n of the alkanoic side chain is important to the choice of the optimal industrial compound, which is 2d (n = 5). Synthese et reactivite d'une nouvelle serie d'ω-phtalimidoperacides. Application a la destruction de polluants organophosphores et organosoufres. La decontamination chimique de composes toxiques dans les series des organophosphores et organosoufres est d'une grande importance. Nous decrivons ici nos resultats sur la recherche de reactifs susceptibles de detruire des composes dans ces familles de toxiques; il s'agit d'une serie d'acides ω-phtalimidoperalcanoiques 2. Nous rationalisons, optimisons et justifions le choix du meilleur candidat en fonction de la longueur de la chaine alkyle du peracide 2d (n = 5).

Reactions of O-ethyl S-(2-diisopropyl-amino)ethyl methylphosphonothiolate, VX 1, were investigated with five oxidizing agents. In all the cases, the formation of the VX N-oxide 7 was observed prior to the subsequent oxidation and hydrolysis into the nontoxic O-ethyl methylphosphonate 2. Magnesium monoperoxyphthalate (MMPP) is probably one of the most active reagents to achieve the complete detoxification of VX 1. The decontamination using MMPP was also extended with success to soman 13, a G-type agent. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:485–490, 2001

Nous decrivons ici les conditions optimales de destruction totale et douce du paraoxon et du parathion par le monoperphtalate de magnesium et le monopersulfate de potassium dans differents milieux micellaires. C'est le premier de ces peracides qui se revele le plus efficace avec des temps de demireaction de destruction des deux toxiques, respectivement de 3 et 9 secondes.

The behaviour of N,N -diisopropyl-2-aminoethyl p- fluorobenzene thiosulfonate 3 , which may be considered as a weakly toxic chemical analogue of VX agent, was investigated against oxidising agents. As VX 1 , this compound exhibits the same tendency to give S–S bond cleavage. Its degradation by Curox® shows the formation of the N- oxide 6 which subsequently gives the sulfonate 7 by hydrolysis. The action of hydrogen peroxide, with or without boric acid, leads to the sulfinate 4 by S-S bond cleavage. Its oxidation gives sulfonate 7 . Finally, reactions of MMPP and m- CPBA afford sulfonate 7 but no intermediates are highlighted with these reagents.

Despite its self-decomposition, Magnesium MonoPeroxyPhtalate 4 is an excellent reagent to totally detoxify phosphonothiolate 1 and fluoridate 2 in basic aqueous medium.