32568-51-7Relevant academic research and scientific papers
A safe and compact flow platform for the neutralization of a mustard gas simulant with air and light
Bianchi, Pauline,Emmanuel, Noémie,Legros, Julien,Monbaliu, Jean-Christophe M.
supporting information, p. 4105 - 4115 (2020/07/30)
A low footprint, mobile, robust and frugal chemical neutralization technology is reported for the oxidative neutralization of a mustard gas simulant. It relies on the inherent properties of a highly engineered continuous flow setup and carefully optimized and simple, yet robust, experimental conditions. The neutralization protocol uses only non-toxic, widely available and cheap chemicals. The continuous flow setup integrates a singlet oxygen generator and exploits its oxidative power to neutralize 2-chloroethyl ethyl sulfide (CEES), the most common thioether mustard gas simulant. The flow reactor can be connected to either pressurized oxygen or air and handles CEES as a 1 M solution in EtOH containing a trace amount (0.06 molpercent) of a non-toxic and widely available photosensitizer (Methylene Blue). Upon irradiation with visible light (orange or white light), total and highly selective neutralization towards the corresponding non-toxic sulfoxide (1-chloro-2-(ethylsulfinyl)ethane, CEESO) is obtained with reactor effluents containing less than 1percent of the corresponding potentially toxic sulfone (1-chloro-2-(ethylsulfonyl)ethane, CEESO2). With a low footprint (L × W × H 94 × 42 × 40 cm), this neutralization technology can be equipped on a vehicle for on-site interventions, localized at a neutralization facility or both. This experimental work is also supported with the computational rationalization of the reactivity of CEES towards singlet oxygen.
A Polyoxoniobate–Polyoxovanadate Double-Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants
Dong, Jing,Hu, Jufang,Chi, Yingnan,Lin, Zhengguo,Zou, Bo,Yang, Song,Hill, Craig L.,Hu, Changwen
supporting information, p. 4473 - 4477 (2017/04/11)
A novel double-anion complex, H13[(CH3)4N]12[PNb12O40(VVO)2?(VIV4O12)2]?22 H2O (1), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2-chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H2O2 with a turnover frequency (TOF) of 16 000 h?1. Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by-product. A three-step oxidative mechanism is proposed.
A porphyrin molecule that generates, traps, stores, and releases singlet oxygen
Changtong, Chuchawin,Carney, Daniel W.,Luo, Lan,Zoto, Christopher A.,Lombardi, John L.,Connors, Robert E.
, p. 9 - 13 (2013/07/05)
Tetraphenylporphyrin (H2TPP), covalently linked to four 2-pyridone moieties was synthesized (II) and studied. This composite molecule, in combination with light and ground state oxygen, has the ability to generate, trap, store, and release singlet oxygen. The process can be operated reversibly without detectable decomposition or side reactions using light with wavelength greater than 500 nm. Oxidation of the target molecule, 2-chloroethyl ethyl sulfide (CEES), by singlet oxygen released from the endoperoxide of the porphyrin-2-pyridone molecule (I) is demonstrated. Spectroscopic and kinetic data do not reveal evidence of perturbation between the porphyrin and pyridone ring systems of II. The decomposition kinetics for the endoperoxide adduct I are first order with activation parameters ΔH? = 26.7 (kcal/mol) and ΔG? = 24.0 (kcal/mol). Experimental and computational studies of unattached N-benzyl-2-pyridone peroxide are reported and compared to the experimental data for I.
Oxidation of organic sulfides by N-halamine compounds
Akdag, Akin,Liang, Jie,Worley
, p. 1525 - 1533 (2008/02/10)
N-halamine chemistry has been an important research topic in these laboratories for over two decades, offering many exciting opportunities both from practical and pedagogical points of view. One of these opportunities is in the use of polymer- and silica gel-bound N-halamines as selective oxidizing agents for organosulfur compounds. In this study, they have been employed to selectively oxidize organic sulfides including dimethyl sulfide and chloroethyl ethyl sulfide, the chemical mustard stimulant. The latter oxidation produced the less toxic sulfoxide derivative with about 70% conversion, with no sulfone produced, and only about 30% accompanying conversion to sulfoxide hydrolysis products. In this article, we report a combination of experimental and computational results. Copyright Taylor and Francis Group, LLC.
Mechanistic organic chemistry in a microreactor. Zeolite-controlled photooxidations of organic sulfides
Clennan, Edward L.,Zhou, Wenhui,Chan, Jacqueline
, p. 9368 - 9378 (2007/10/03)
The intrazeolite and solution photooxygenations of a series of sulfides have been compared. The unusual zeolite environment enhances the rates of reaction, it suppresses the Pummerer rearrangements, and it has a dramatic effect on the sulfoxide/sulfone ratio. A detailed kinetic study utilizing trapping experiments and intramolecular competition provides evidence for cation complexation to a persulfoxide intermediate as the underlying phenomenon for the unique intrazeolite behavior. For example, the enhanced rate of reaction is traced to the cation stabilization of the persulfoxide toward unproductive decomposition to substrate and triplet oxygen.
The reactions of singlet oxygen with β-chlorosulfides. The role of hydroperoxy sulfonium ylides in the oxidative destruction of chemical warfare simulants
Toutchkine, Alexei,Clennan, Edward L.
, p. 6519 - 6522 (2007/10/03)
The reactions of singlet oxygen with 2-chloroethyl ethyl sulfide and 3- chlorothiane are reported, In both cases elimination of HCl to produce α,β- unsaturated sulfoxides is observed. The experimental results implicate a hydroperoxy sulfonium ylide as a transition state or intermediate in an E2 or E1cb elimination, respectively.
