1186-09-0Relevant academic research and scientific papers
A Robust Methodology for the Synthesis of Phosphorothioates, Phosphinothioates and Phosphonothioates
Jones, David J.,O'Leary, Eileen M.,O'Sullivan, Timothy P.
, (2020)
A robust methodology for the synthesis of phosphorothioates, phosphinothioates and phosphonothioates, including those bearing low molecular weight S-alkyl side-chains, is presented. Application of the “caesium effect” in conjunction with the disulfide 3,3’-dithiobis(propionitrile), which acts as a shelf-stable sulfur source, avoids recourse to malodorous alkanethiols and toxic P?Cl precursors. A diverse range of sulfur-containing organophosphorus targets, including phosphorus-based heterocycles, may be prepared in consistently high yields. This chemistry also provides ready access to the corresponding DBU salts which are potential substrates for Pd-catalysed coupling reactions. (Figure presented.).
Detailed investigation of the radical-induced destruction of chemical warfare agent simulants in aqueous solution
Abbott, Amberashley,Sierakowski, Tim,Kiddle, James J.,Clark, Kristin K.,Mezyk, Stephen P.
, p. 7681 - 7685 (2010)
The persistence of delivered chemical warfare agents (CWAs) in a variety of environmental matrices is of serious concern to both the military and civilian populations. Ultimately understanding all of the degradation pathways of the various CWAs in different environmental matrices is essential for determining whether native processes would offer sufficient decontamination of a particular material or if active chemical decontamination is required. Whereas much work on base-promoted chemical degradation has been reported, additional remediation strategies such as the use of advanced oxidation or reduction process free radical treatments may also be a viable option. We have examined here the primary kinetics and reaction mechanisms for an extensive library of chemical warfare agent simulants with the oxidizing hydroxyl radical and reducing hydrated electrons in water. From these values, it is seen that the reductive destruction occurs primarily through a single mechanism, consisting of hydrated electron capture at the phosphorus group with subsequent elimination, whereas hydroxyl radical oxidation shows two separate reaction mechanisms, dependent on the aqueous pKa of the leaving group. ? 2010 American Chemical Society.
A quantitative synthesis of β-carboxylated thiolophosphates via a Michael reaction
Desforges, Elisabeth,Grysan, Alexandre,Oget, Nicolas,Sindt, Michèle,Mieloszynski, Jean-Luc
, p. 6273 - 6276 (2003)
Reactions of O,O′-dialkylthiophosphoric acids with acrylates provide a direct synthetic route to β-carboxylated thiolophosphates. This Michael addition, without solvent, is quantitative at 90°C in 1 h for the 2/1 thiophosphoric acid/acrylate ratio. Moreover, this excess of thiophosphoric acid can be reused for further reactions.
Sulfur phosphate compound, non-aqueous lithium ion battery electrolyte containing sulfur phosphate compound and lithium ion battery
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Paragraph 0040-0042; 0098; 0102; 0118-0119; 0122-0131, (2020/12/14)
The invention discloses a thiophosphate compound, a synthesis method and a non-aqueous electrolyte. After the compound is applied to a battery with the non-aqueous electrolyte, even if the battery isunder high voltage, an electrode/electrolyte interface of a lithium ion battery is effectively improved, so that an electrode surface film is stabilized, side reactions are reduced, the stability of the battery under high temperature and high voltage is improved, and the cycling stability of the battery is improved, and meanwhile, the self-extinguishing time of the non-aqueous electrolyte after combustion is shortened, the flame retardance is improved, and the safety performance of the battery is improved.
Benign synthesis of thiophosphates, thiophosphinates and selenophosphates in neat condition using N-chalcogenoimides as the source of electrophilic sulfur/selenium
Mondal,Saha, Amit
supporting information, (2019/08/08)
A neat reaction protocol has been developed for synthesis of thiophosphate, thiophosphinate and selenophosphate compounds. N-chalcogenoimides have been used for chalcogenylation of P(O)H moieties of various H-phosphonates under solvent, catalyst and base free condition at room temperature in aerial atmosphere. Both S-aryl and S-alkyl phosphorothioate compounds were prepared by this method in good yields. Selenophosphates were also synthesized using N-(phenylseleno)phthalimide under solvent free condition.
Reaction of Three-coordinate Phosphorus Compounds with Organophosphorus Pseudohalogens. 3. Phosphonium and Phosphorane Intermediates in the Desulfurization and Dehalogenation of Bis(phosphinoyl) Disulfides. Influence of Lewis Acids on the Reaction Chemoselectivity
Krawczyk, Ewa,Skowronska, Aleksandra,Michalski, Jan
, p. 89 - 100 (2007/10/02)
The reactions of bis(phosphinoyl) disulfides RR1P(O)S-S-P(O)RR1 1 with PIII compounds have been investigated and various mechanistic features have been elucidated by variable-temperature 31P NMR spectroscopy.These studies show that in most cases phosphonium intermediates 5 and 6 are involved.In cases were ligands on PIII increase the stability of the five coordinate structures phosphorane intermediates are observed.In the isomerization 5 -> 6, the mode of decomposition (desulfurization, deoxygenation or dealkylation) to give stable end products is influenced by electronic and steric factors.The presence of the Lewis acid BF3 influences considerably the stability of the transient species 5 and 6 and the chemoselectivity of the reaction.
PRODUCTS OF THE ALKALINE HYDROLYSIS OF S-CHLOROMETHYL AND S-(N-ETHOXYCARBONYL-N-METHYLCARBAMOYLMETHYL) O,O-DIETHYLPHOPHORODITHIOATE
Hudson, Harry R.,Lynch, Vincent P.,Pianka, Max,Soares, Vera M.
, p. 277 - 281 (2007/10/02)
The alkaline hydrolysis of S-chloromethyl O,O-diethyl phosphorodithioate (chlormephos) and of S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl) O,O-diethyl phosphorodithioate (mecarbam) may involve attack by hydroxide ion at phosphorus with phosphorus-sulfur cleavage, at the substituted S-methyl carbon atom with sulfur-carbon cleavage or, in the case of mecarbam, at the carbonyl carbon atom with carbonyl-nitrogen cleavage.Further reaction of the initially-formed O,O-diethyl hydrogen phosphorodithioate with chlormephos may lead to the formation of additional products.
