The Oxidation of Thioanisole by Peroxomolybdate in Micelles of Cetylpyridinium Chloride

Chiarini, Marco; Gillitt, Nicholas D.; Bunton, Clifford A.

doi:10.1021/la0117404

Cited by 49 publications

(54 citation statements)

References 51 publications

(121 reference statements)

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“…The most ecologically favorable oxidizing agent is hydrogen peroxide, which, however, has only low reactivity by itself. Bicarbonates [2, 3], molybdates [4,5], phthalates [6], and nitrites [7], which form highly reactive peroxo acids upon reaction with H 2 O 2 , are used to activate hydrogen peroxide. Boric acid, B(OH) 3 , which forms peroxoborates upon reaction with hydrogen peroxide under mild conditions, is a promising activator [8-10].…”

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confidence: 99%

Kinetics of the oxidation of diethyl sulfide in the B(OH)3-H2O2/H2O system

et al. 2007

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Data obtained for the kinetics of oxidation of diethyl sulfide (Et 2 S) by hydrogen peroxide in aqueous solution catalyzed by boric acid indicate that monoperoxoborates B(O 2 H)( ) OH 3 − and diperoxoborates B O H OH ( ) ( ) 2 2 2 − are the active species. The rates of the reactions of Et 2 S with B(O 2 H)( ) OH 3 − and B O H OH ( ) ( ) 2 2 2 − are 2.5 and 100 times greater than with H 2 O 2 .The search for new systems to effect rapid selective oxidation of sulfides and sulfoxides is important for solving the problem of the decomposition of pesticides and poisonous substances, whose active components are organic sulfides. Chloramines, commonly used for this purpose, are highly toxic and corrosive [1]. The most ecologically favorable oxidizing agent is hydrogen peroxide, which, however, has only low reactivity by itself. Bicarbonates [2, 3], molybdates [4,5], phthalates [6], and nitrites [7], which form highly reactive peroxo acids upon reaction with H 2 O 2 , are used to activate hydrogen peroxide. Boric acid, B(OH) 3 , which forms peroxoborates upon reaction with hydrogen peroxide under mild conditions, is a promising activator [8-10]. These compounds, in particular Na 2 [B 2 (O 2 ) 2 (OH) 4 ]·6H 2 O [11], are strong oxidizing agents and are used as industrial bleaches. No information is available on the kinetics and mechanisms of oxidation of thioethers by peroxyborates. The chemistry of peroxyborates is complicated. Depending on the ratio of the starting concentrations of B(OH) 3 and H 2 O 2 and the pH of the medium, either peroxoborates [B(O 2 H) n (OH) 4-n ] -(n = 1-4) or polyperoxoborates [B 2 (O 2 ) 2 (O 2 H) n (OH) 4-n ] 2-(n = 0, 2, or 4) are formed [10]. At relatively low concentrations of B(OH) 3 and H 2 O 2 (£1 mol/L) at pH 6-14, the major products are monoperoxoborate B(O H)(OH) 2 3 − (MPB) anions and diperoxoborate B(O H) (OH) 2 2 2 − (DPB)anions. Polyperoxoborates are the major products at higher reagent concentrations.In the present work, we studied the effect of boric acid on the rate of oxidation of diethyl sulfide (Et 2 S), which serves as a model for yprite, by hydrogen peroxide in aqueous solution in a broad pH range to establish the nature of the active species and find optimal reaction conditions. EXPERIMENTALDiethyl sulfide was prepared according to a standard procedure [12]. The working solutions were prepared using doubly distilled water, 35% hydrogen peroxide, and chemically-pure grade samples of boric acid, sodium perchlorate, H 3 PO 4 , and NaOH. 440040-5760/07/4301-0044

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Kinetics of the oxidation of diethyl sulfide in the B(OH)3-H2O2/H2O system

et al. 2007

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“…The presence of a thickener in the poison adds constraints to the conception of an efficient decontamination medium. [53][54][55][56][57] The choice of mustard gas analogue will be critical: indeed, the model must present a lipophilicity near that of yperite, and must also allow similar solubilization of the polymer (Paraloid K125). The rheology and the behavior of the couple polymer/model substrate must be as near as possible to those of the thickened mustard gas.…”

Section: Proposed Next Class Of Mes: Decontamination Of Polymer-thickmentioning

confidence: 99%

Ionic Liquids as Solvent, Catalyst Support Chemical Agent Decontamination and Detoxification

Nelson¹

2004

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As the results after one year will indicate, this project will provide the information and outline for development of a novel decon/detox cleaning formulation. The emphasis during this year has been on the oxidative decontamination/detoxification of surrogates for mustard and phosphorous nerve agents. More work was expended in developing a literature survey, because the ability to do laboratory work was restricted by competing projects. The intent was to resume in the fall, but the second year's funding was cut. Therefore, this final report will be a complete literature presentation and a detailed outline of future work. BackgroundWe established our goal to develop formulations of superior cleaning agents that catalyze chemical reactions. In order to accomplish this we reasoned that the ability of room temperature ionic liquids (ILs) dissolved in aqueous ethanol (aq EtOH) to solubilize and promote the oxidation of three chemical agent surrogates was feasible. Such a series of cleaning agents, we believe, would have immediate use in chemical detoxification and decontamination of a wide range of contaminants of importance to the Department of Defense (DoD).The ILs, as will be seen, bear strong chemical resemblance to surfactants.

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“…[3][4][5][6][7][8][9][10] They are widely used in stoichiometric as well as catalytic oxidation in organic and biochemistry, 11 for example, in the oxidation of thioanisole, 12,13 methylbenzenes, 14 tertiary amines, alkenes, alcohols, 15,16 bromide 17 and also in olefin epoxidations. [18][19][20][21][22] There has been a continuous upsurge in interest in peroxo compounds of vanadium since it has been demonstrated that vanadate and peroxovanadates are capable of inhibiting the hydrolysis of phosphoproteins [23][24][25][26] and exhibit insulin-like properties.…”

Section: Introductionmentioning

confidence: 99%

Diperoxo Complexes of Vanadium(V) Containing Mannich Base Ligands

et al. 2011

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The vanadium(V) peroxo complexes containing Mannich base ligands having composition Na[VO(O 2 ) 2 (L-L)]•H 2 O [where L-L＝morpholinobenzyl acetamide (MBA), piperidinobenzyl acetamide (PBA), morpholinobenzyl benzamide (MBB), piperidinobenzyl benzamide (PBB), morpholinomethyl benzamide (MMB), piperidinomethyl benzamide (PMB), morpholinobenzyl formamide (MBF), piperdinobenzyl formamide (PBF)] have been reported. The complexes have been prepared by stirring vanadium pentoxide with excess of 30% aqueous-H 2 O 2 followed by treatment with ethanolic solution of the ligand and finally maintained the pH of the reaction mixture by adding dilute solution of sodium hydroxide. The synthesized complexes have been characterized by various physico-chemical techniques, via elemental analysis, molar conductivity, magnetic susceptibility measurements, infra red, electronic, mass, 1 H NMR spectral and TGA/DTA studies. These studies revealed that the synthesized complexes are uni-univalent electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode through carbonyl oxygen and the ring nitrogen. Thermal analysis result provides conclusive evidence for the presence of one molecule of lattice water in the complexes. Mass spectra confirm the molecular mass of the complexes.

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The Oxidation of Thioanisole by Peroxomolybdate in Micelles of Cetylpyridinium Chloride

Cited by 49 publications

References 51 publications

Kinetics of the oxidation of diethyl sulfide in the B(OH)3-H2O2/H2O system

Kinetics of the oxidation of diethyl sulfide in the B(OH)3-H2O2/H2O system

Ionic Liquids as Solvent, Catalyst Support Chemical Agent Decontamination and Detoxification

Diperoxo Complexes of Vanadium(V) Containing Mannich Base Ligands

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