REACTIONS AND ANALYSIS OF β-CHLOROETHYL SULFIDE IN WATER<sup>1</sup>

Price, Charles C.; Wakefield, L. B.

doi:10.1021/jo01166a005

Cited by 9 publications

(4 citation statements)

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“…[23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] The kinetics and mechanisms of such a hydrolysis process for sulfur mustard (HD) and its monochloro derivative (CEES) have been extensively investigated. [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] These studies have confirmed that the first step is the rapid equilibrium formation of the sulphonium cation (Fig. 3, b).…”

Section: Stability and Aquationmentioning

confidence: 99%

Sulfur, oxygen, and nitrogen mustards: stability and reactivity

et al. 2012

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Mustard gas, bis(β-chloroethyl) sulfide (HD), is highly toxic and harmful to humans and the environment. It comprises one class of chemical warfare agents (CWAs) that was used in both World Wars I and II. The three basic analogues or surrogates are: the monochloro derivative, known as the half mustard, 2-chloroethyl ethyl sulfide (CEES); an oxygen analogue, bis(β-chloroethyl) ether (BCEE); and several nitrogen analogues based on the 2,2'-dichlorodiethylamine framework (e.g., HN1, HN2, and HN3). The origin of their toxicity is considered to be from the formation of three-membered heterocyclic ions, a reaction that is especially accelerated in aqueous solution. The reaction of these cyclic ion intermediates with a number of important biological species such as DNA, RNA and proteins causes cell toxicity and is responsible for the deleterious effects of the mustards. While a number of studies have been performed over the last century to determine the chemistry of these compounds, early studies suffered from a lack of more sophisticated NMR and X-ray techniques. It is now well-established that the sulfur and nitrogen mustards are highly reactive in water, while the oxygen analog is much more stable. In this study, we review and summarize results from previous studies, and add results of our own studies of the reactivity of these mustards toward various nonaqueous solvents and nucleophiles. In this manner a more comprehensive evaluation of the stability and reactivity of these related mustard compounds is achieved.

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Section: Stability and Aquationmentioning

confidence: 99%

Sulfur, oxygen, and nitrogen mustards: stability and reactivity

et al. 2012

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“…By extrapolation of the rate in aqueous dioxane solutions it has been estimated that the first-order rate constant in water at 25°s hould be about 0.4 min.-1. This is four times that of /3-chloroethyl sulfide, k25 = 0.10 min.-1 [half-life at 25°, seven to eight minutes (2,3,4)], and about twice the value reported for ß-(/3'-chloroethyIthio)ethyl ether (X) by Brookfield and Moelwyn-Hughes (5).…”

mentioning

confidence: 60%

“…In connection with speculation concerning the mechanism of hydrolysis of /3-chloroethyl sulfides (2,3,4), it is of interest to compare this order of reactivity for chloro compound and sulfonium salt with examples known to proceed by Sni and by Sn2 mechanisms.…”

Section: Cl-xiiimentioning

confidence: 99%

SOME REACTIONS OF 1,2-bis(β-CHLOROETHYLTHIO)ETHANE¹

Price¹,

Roberts²

1947

J. Org. Chem.

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“…Reactions (1) and (2) [Is+1 * [C1--[HDko -( k3 ) k1 k (7) in which [HD]o is the initial concentration of mustard. This is the integrated rate equation for a sequence of two, consecutive, unimolecular reactions specifically applied to the mechanism shown in Figure 1.…”

Section: -15mentioning

confidence: 99%