Nucleophilic reactivity of the peroxide anion in aqueous-alcoholic solutions in the presence of detergents

Vakhitova, L. N.; Skrypka, A. V.; Bogutskaya, K. V.; Taran, N. A.; Popov, A. F.

doi:10.1007/s11237-007-0047-6

Cited by 2 publications

(3 citation statements)

References 4 publications

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“…The progress of oxidation and nucleophilic substitution was monitored by spectrophotometry according to the procedure described previously [31,38]. Nucleophilic substitution was monitored by measuring the absorbance at λ max 405 nm (4-nitrophenoxide ion) at…”

Section: IImentioning

confidence: 99%

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Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

et al. 2011

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The kinetics of oxidation of methylsulfanylbenzene and nucleophilic decomposition of diethyl 4-nitrophenyl phosphate with hydrogen peroxide in the presence of ammonium hydrogen carbonate or boric acid in aqueous, aqueous-alcoholic, micellar, and microemulsion media were studied. Quantitative parameters of the examined processes were determined, and the possibility of using hydrogen peroxide for the design of oxidative nucleophilic decontaminating systems was demonstrated.Taking into account huge worldwide stocks of chemical weapons [1-6], the problem implying utilization of highly toxic chemical agents has recently become especially important. The most common chemical weapons may be divided into three main groups: (1) phosphorus acid esters (neurotoxins and structurally similar pesticides, e.g., GB, GD, and Metaphos); (2) organosulfur compounds (blister agents, e.g., Yperite or HD); and (3) compounds with combined (neuroparalytic) action (VX).The optimal system for decontamination of toxic chemical agents should ensure their solubilization and simultaneously high rate of decomposition. Therefore, organized nanosize systems such as micellar solutions and microemulsions are promising from the viewpoint of development of ecologically safe decontaminating compositions [11,12,[15][16][17][18][19][20][21]; these systems provide increased reagent concentration at the phase boundary between micelles (oil drop) and water and create favorable conditions for nucleophilic attack on electrophilic centers of toxic substrates [21,22].While searching for chemically active components capable of rapidly and irreversibly decomposing toxic chemicals, specific attention is now given to the design of universal oxidative nucleophilic systems for degradation of chemical agents of different natures. For example, nucleophilic reagents are efficient toward phosphorus acid esters and halides (GB) [23,24], dialkyl sulfides like HD are decomposed by the action of oxidants [16,25,26], whereas oxidative nucleophilic systems containing an HOX-OX -couple (X = OH, Hlg, etc.) are preferred for decontamination of chemical agents like VX or mixtures of compounds belonging to the above three types (GB, HD, VX) [20,27]. In this respect, hydrogen peroxide due to its dual nature (it is an effective oxidant toward HD analogs [15,25] and reactive α-nucleophile toward phosphorus acid esters [1,24,28]) may be regarded as universal agent in the design of mild and ecologically safe decontami-

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Section: IImentioning

confidence: 99%

“…As the latter we used cetyl(trimethyl)ammonium bromide and Triton X-100 [4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol], taking into account that anionic surfactants were shown previously [37][38][39] to inhibit processes in the above systems.…”

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Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

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“…Nevertheless the practical utilization of hydrogen peroxide for the decomposition of toxic substances is restricted by their comparatively low solubility in the investigated systems [3][4][5].…”

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Nucleophilic reactivity of the peroxide anion in microemulsions of the “oil-in-water” type in the decomposition of phosphate and toluenesulfonate esters

et al. 2010

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The kinetics of the reaction of the 4-nitrophenyl esters of diethylphosphoric and 4-toluenesulfonic acids with HO -and HOO -anions in microemulsions of the "oil-in-water" type was studied. It was shown that the reactivity of the HOO -anion depends on the nature of the detergent forming the microemulsion and decreases in the order cetyltrimethylammonium bromide > Triton X-100 > sodium dodecyl sulfate. It was established that concentration of the reagents on the surface of the microdrops leads to an increase of 2-3 orders of magnitude in the rate during the transition from aqueous solutions to the microemulsion.Hydrogen peroxide (H 2 O 2 ) is arousing more and more interest as a degassing agent in oxidative-nucleophilic systems for the decomposition of ecotoxicant substrates of the HD (yperite, 2,2¢-dichlorodiethyl sulfide), GB (sarin, O-isopropyl methylphosphonofluoridate), and VX (O-ethyl-S-[2-(diisopropylamino)ethyl]methylthiophosphonate) types [1,2].In addition to meeting all the ecological safety requirements demanded of a degassing agent systems based on hydrogen peroxide are attractive primarily in their versatility -an effective oxidizing agent in the form of H 2 O 2 [2] and a supernucleophilic agent in the ionic HOO -form for oxidative-nucleophilic processes in water [3], water-alcohol [4], and micellar [5] media. Nevertheless the practical utilization of hydrogen peroxide for the decomposition of toxic substances is restricted by their comparatively low solubility in the investigated systems [3][4][5].One of the most urgent tasks for the application of hydrogen peroxide in technological degassing processes is therefore to select a reaction medium that would dissolve the hydrophilic nucleophile and the hydrophobic substrates as much as possible while preserving the supernucleophilic characteristics of the HOO -anion -the a effect, which manifests itself in the anomalously high reactivity [6].Of interest in this respect are microemulsions (ME) of the oil-in-water type, which have high solubilizing ability toward hydrophobic compounds and dissolve hydrogen peroxide without restriction [7].The aim of the present work is to study the reactivity of OH -and HOO -anions toward electrophilic substrates -4-nitrophenyl diethyl phosphate (I, paraoxone) and 4-nitrophenyl toluenesulfonate (II)

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Nucleophilic reactivity of the peroxide anion in aqueous-alcoholic solutions in the presence of detergents

Cited by 2 publications

References 4 publications

Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

Nucleophilic oxidizing systems based on hydrogen peroxide for decomposition of ecotoxicants

Nucleophilic reactivity of the peroxide anion in microemulsions of the “oil-in-water” type in the decomposition of phosphate and toluenesulfonate esters

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