Kinetics of Hydrolysis and Displacement Reactions of β,β′-Dichlorodiethyl Sulfide (Mustard Gas) and of β-Chloro-β″-hydroxydiethyl Sulfide (Mustard Chlorohydrin)

Bartlett, Paul D.; Swain, C. Gardner

doi:10.1021/ja01172a076

Cited by 142 publications

(96 citation statements)

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“…Once dissolved, HD undergoes rapid hydrolysis (Bartlett and Swain 1949). However, the overall process of hydrolytic destruction is limited by the very low water solubility of HD.…”

Section: Sulfur Mustardmentioning

confidence: 99%

Reevaluation of 1999 Health-Based Environmental Screening Levels (HBESLs) for Chemical Warfare Agents

Watson¹,

Dolislager²

2007

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“…Once dissolved, HD undergoes rapid hydrolysis (Bartlett and Swain 1949). However, the overall process of hydrolytic destruction is limited by the very low water solubility of HD.…”

Section: Sulfur Mustardmentioning

confidence: 99%

Reevaluation of 1999 Health-Based Environmental Screening Levels (HBESLs) for Chemical Warfare Agents

Watson¹,

Dolislager²

2007

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“…[2]). The rate constant for the acetophenone oximate (Ox-) free anion was obtained from the slope of the linear plot in Fig.…”

Section: O X -+ K + + S Productsmentioning

confidence: 99%

“…During the last several decades a number o f reports have appeared in the literature o n the nucleophilic reactions of 2-chloroethyl sulfide derivatives, as models o f sulfur mustard, 2,2'-dichlorodiethyl sulfide (1)(2)(3)(4)(5)(6)(7)(8)(9).…”

Section: Introductionmentioning

confidence: 99%

Solvent and crown ether/cryptand effects on the oximate-promoted 1,2-elimination from β-phenylmercaptoethyl p-nitrophenolate. Formation and reactivity of a crown ether-complexed potassium oximate ion pair

Buncel¹,

Kumar²,

Xie³

et al. 1994

Can. J. Chem.

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. 72,437 (1994). The reactions of P-phenylmercaptoethyl p-nitrophenolate (1) with three potassium oximates, viz. potassium 2,3-butanedione monoximate (BDOK), acetophenone oximate (APOK), and acetone oximate (AOK) have been investigated in two nonhydroxylic dipolar aprotic solvents, tetraglyme and dimethyl sulfoxide (DMSO). The reaction products, as determined by 'H NMR spectroscopy, were p-nitrophenoxide ion and phenyl vinyl sulfide, in accord with an elimination process. A kinetic spectrophotometric study showed that in tetraglyme, the addition of oxime and water in small amounts drastically decreased the rate of reaction of 1 with APOK as a result of hydrogen-bonding interactions with the oximate anion. In tetraglyme as solvent the addition of 2.2.2 cryptand greatly enhanced the reactivity of the oximates but the macrocyclic crown ether DC-18-C6 had much smaller effect on rate. The results are consistent with formation of a crown ether-complexed potassium oximate ion pair, which is much less reactive than the free anion formed in the presence of 2.2.2 cryptand but more reactive than the potassium oximate ion pair. The kinetic data were analyzed to obtain specific rate coefficients for reaction of APOK as the dissociated anion, the ion-paired species, and as the crown ether-complexed oximate; equilibrium constants for potassium oximate ion pair formation and for the crown ether-complexed ion pair were obtained. In DMSO as solvent the rate of reaction remained unaffected on addition of the metal ion complexing agents, indicating that ion pairing is not important in this solvent. The reactivity of the free oximate anions in both solvents increased in the order BDOK < APOK < AOK, which parallels the pK,'s of the corresponding oximes in DMSO. The unusually high reactivity of oximates in the low polarity tetra 1 me compared to polar DMSO could be explained on the $2 basis of stabilization of the transition state in tetraglyme. Trends in k 1kDMS0 for the oximates follow reactivity-selectivity considerations.

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“…The persistence of mustard gas in the environment, however, has made it more difficult to destroy than other CW agents (despite its relatively rapid hydrolysis as indicated by a short half-life of 4-8 min) (Bartlett and Swain 1949); the low solubility in water (only about 900 mg/L) gives rise to its environmental stability. Therefore, SM is buried in the soil, where it cannot vaporize and can remain stable for years (Munro et al 1999).…”

Section: Introductionmentioning

confidence: 99%

A simple degradation method for sulfur mustard at ambient conditions using nickelphthalocyanine incorporated polypyrrole modified electrode

et al. 2012

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Electrocatalytic degradation of sulfur mustard (SM) was studied using a gold electrode modified with nickelphthalocyanine and polypyrrole (NiPc/pPy/Au) in the presence of a cationic surfactant cetyltrimethyl ammonium bromide. Several techniques such as cyclic voltammetry, scanning electron microscopy, electrochemical impedance spectroscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy have been employed for the characterization of modified electrodes. NiPc/pPy/Au modified electrode exhibited excellent electrochemical sensing and degradation ability towards SM. The present modification indicated two electron involvements in the electrocatalytic degradation of SM in addition to being an irreversible adsorption controlled process. Degraded products were identified by gas chromatographymass spectrometry. Moreover, electrochemical parameters of oxidation of SM such as heterogeneous rate constant (0.436 s -1 ), transfer coefficient (0.47) and the number of electrons involved (2) were deduced from cyclic voltammetry results. The NiPc/pPy/Au modified electrode showed excellent electrocatalytic degradation towards SM when compared to bare gold, pPy/Au and NiPc/Au modified electrode at ambient conditions.

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Kinetics of Hydrolysis and Displacement Reactions of β,β′-Dichlorodiethyl Sulfide (Mustard Gas) and of β-Chloro-β″-hydroxydiethyl Sulfide (Mustard Chlorohydrin)

Cited by 142 publications

References 0 publications

Reevaluation of 1999 Health-Based Environmental Screening Levels (HBESLs) for Chemical Warfare Agents

Reevaluation of 1999 Health-Based Environmental Screening Levels (HBESLs) for Chemical Warfare Agents

Solvent and crown ether/cryptand effects on the oximate-promoted 1,2-elimination from β-phenylmercaptoethyl p-nitrophenolate. Formation and reactivity of a crown ether-complexed potassium oximate ion pair

A simple degradation method for sulfur mustard at ambient conditions using nickelphthalocyanine incorporated polypyrrole modified electrode

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