Bis(dialkylamide)hydrogen Dibromobromate Precursors of Hypobromite Ion in Reactions with Nerve and Blister Agent Simulants

Simanenko, Yuri S.; Savëlova, V. A.; Prokop’eva, T. M.; Mikhailov, V. A.; Turovskaya, M. K.; Karpichev, Yevgen; Popov, A. F.; Gillitt, Nicholas D.; Bunton, Clifford A.

doi:10.1021/jo0402430

Cited by 16 publications

(9 citation statements)

References 14 publications

(14 reference statements)

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“…Moreover the conjugate acids of hypohalite anions show clearly oxidative properties, so that the HOHal/HalOcouple may act as nucleophile and/or oxidant depend on the pH of the medium. As has been shown previously [7], the molecular complexes of the trihalide ions I and II, which are stable for long periods in the crystalline form, are capable of generating the ion pair HOBr/BrO -quantitatively, the fraction of the components of which depends on the pH of the medium.…”

supporting

confidence: 55%

Micellar effects of cetyltrimethylammonium dibromobromate in phosphoryl group transfer reactions

et al. 2007

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The nucleophilic reactivity of cetyltrimethylammonium dibromobromate (CTABr 3 ) with respect to organophosphorus compounds -4-nitrophenyl esters of diethylphosphoric (NPDEP) and diethylphosphonic acids (NPDEPN) -has been studied. Solution of CTABr 3 in aqueous alkali solutions generated the hypobromite anion, which permitted the formation of a micellar system with reactive a-nucleophilic counterion. The kinetics of this system was described in terms of a simple pseudo-phase model, the half-life for the conversion of the organophosphorus substrates into reaction products was 95 s (NPDEP) and 12 s (NPDEPN).The influence of micelles and other microheterogeneous aggregates on the rate of chemical reactions has been intensively studied in the last decade which has provided a basis for the development of quantitative descriptions of the observed effects and proposals for methods for the practical use of micellar systems [1,2]. Micellar effects of surfactants in the reactions of anionic nucleophiles may be used to create systems capable of rapid and irreversible decomposition of toxic organophosphorus compounds -esters and haloid anhydrides of phosphorus acids. The use of toxic pesticides, a number of which include esters of dialkylphosphoric acid (paraoxon), dialkylthiophosphoric acid (metaphos, parathion, phenitrothion) and dialkyldithiophosphoric acid (timet), accompanied by contaminated soil and ground water, while enormous stores of these substances require treatment for ecologically well-based recovery [3].0040-5760/07/4304-0241

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supporting

confidence: 55%

Micellar effects of cetyltrimethylammonium dibromobromate in phosphoryl group transfer reactions

et al. 2007

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“…The determination of active halogen and acid was carried out by iodometric titration. The preparation and purification of dibromobromates I-IV were described in our previous work [12]. Solvent purification was described in our earlier work [29].…”

Section: Methodsmentioning

confidence: 99%

“…Hence, knowledge of the state of dibromobromate anions in solution is important for the application of these salts. We previously proposed bis(N,N-dimethylacetamide) hydrogen dibromobromate for use as an efficient brominating agent and component in compositions for the decomposition of toxic pollutants [12]. Not only the anion but also the cation is complex in this compound, which introduces additional complexity in the behavior of this compound in solution.…”

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confidence: 99%

Reversible dissociation of dibromobromates in organic solvents

et al. 2008

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A study was carried out on the reversible decomposition of dibromobromate anions in organic solvents and we found the equilibrium constants for the processes responsible for the distribution of active halogen and hydrogen halide between their different forms in solution. The capacity of the solvent to form hydrogen bonds with the bromide anion, the feasibility of forming a molecular complex with bromine, and the structure of the cation (in solutions with low ionizing capacity) were all found to affect the reversible decomposition of the dibromobromate anion.Organic salts with the dibromobromate anion, Br 3 − , have a set of unique properties, which open the way for their use in a very broad variety of applications [1]. The vapor pressure of bromine above solid crystalline dibromobromates is very low. Many of these salts are suitable for prolonged storage and safe for handling. Numerous studies have shown that the applicability of dibromobromates as electrolyte components for chemical power sources and materials for water purification, brominating agents differing from elemental bromine in their reaction mechanism [2, 3]. The profound differences in the reaction mechanisms of dibromobromates and bromine are seen in differing kinetic behavior, smaller reactivity and greater selectivity in the dibromobromate reactions [4][5][6]. However, there is a special feature in the behavior of dibromobromate solutions, which can cancel out all their advantages relative to molecular bromine. These complexes are capable of reversible dissociation in solution to give bromide anion and molecular bromine [1]. The state of these complexes has been studied in greatest detail for aqueous solution [1, 7-9]. There have been fewer measurements for solutions in organic solvents. Such measurements have far from always been the major concern in these studies. This perhaps accounts for the circumstance that determinations of equilibrium constants and even extinction coefficients do not always agree with one another. The formation of dibromobromates from bromide anion and bromine molecules may reliably be considered to be an exothermal [9], rapid [10] and equilibrium [1] reaction. The equilibrium constants vary in a very broad range depending on the solvent [11]. We can clearly imagine that the concentration of molecular bromine in the case of considerable dissociation of the dibromobromate anion becomes sufficient so that the contribution of the reaction involving bromine, which is much more reactive in many bromination reactions [3][4][5], becomes predominant. The advantages of using dibromobromates in this case would be eliminated. Hence, knowledge of the state of dibromobromate anions in solution is important for the application of these salts. We previously proposed bis(N,N-dimethylacetamide) hydrogen dibromobromate for use as an efficient brominating agent and component in compositions for the decomposition of toxic pollutants [12]. Not only the anion but also the cation is complex in this compound, which introduces additional complexit...

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“…OPs have binding affinities similar to that of the neurotransmitter acetylcholine, allowing OPs to inhibit the action of acetylcholinesterase in neuromuscular junctions, disrupting the breakdown of the neurotransmitter [2][3][4]. The neutralization of OP compounds can be achieved through oxidation [5,6], enzyme degradation [7][8][9], hydrolysis [10][11][12], and incineration [13]. Nevertheless, each method is not without its limitations.…”

Section: Introductionmentioning

confidence: 99%

Quantum Calculations of VX Ammonolysis and Hydrolysis Pathways via Hydrated Lithium Nitride

Leverant

Priest

Greathouse

et al. 2021

IJMS

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Recently, lithium nitride (Li3N) has been proposed as a chemical warfare agent (CWA) neutralization reagent for its ability to produce nucleophilic ammonia molecules and hydroxide ions in aqueous solution. Quantum chemical calculations can provide insight into the Li3N neutralization process that has been studied experimentally. Here, we calculate reaction-free energies associated with the Li3N-based neutralization of the CWA VX using quantum chemical density functional theory and ab initio methods. We find that alkaline hydrolysis is more favorable to either ammonolysis or neutral hydrolysis for initial P-S and P-O bond cleavages. Reaction-free energies of subsequent reactions are calculated to determine the full reaction pathway. Notably, products predicted from favorable reactions have been identified in previous experiments.

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Bis(dialkylamide)hydrogen Dibromobromate Precursors of Hypobromite Ion in Reactions with Nerve and Blister Agent Simulants

Cited by 16 publications

References 14 publications

Micellar effects of cetyltrimethylammonium dibromobromate in phosphoryl group transfer reactions

Micellar effects of cetyltrimethylammonium dibromobromate in phosphoryl group transfer reactions

Reversible dissociation of dibromobromates in organic solvents

Quantum Calculations of VX Ammonolysis and Hydrolysis Pathways via Hydrated Lithium Nitride

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