- L-Gel formulation and decontamination reaction of its active ingredient (oxone) against mustard and VX nerve agent simulants
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L-Gel is an effective decontamination reagent against chemical and biological warfare agents. To achieve optimized formulation of L-Gel, several formulations with different proportional amounts of oxone (oxidizer) and Cab-O-Sil (gelling agent) were prepared and their viscosities and densities were measured. Final optimized formulation of gel was obtained as a 0.25 M aqueous solution of oxone gelled with 13%W/W of Cab-O-Sil EH-5. The L-Gel active ingredient (oxone) was tested against O,O,S-triethyl phosphorothioate (TEPT) as VX simulant and methyl phenyl sulfide (MPS) and chloroethyl phenyl sulfide (CEPS) as HD simulants. Decontamination of TEPT by a 10-fold excess amount of oxone was completed within 7.5 min with a kinetic rate constant of 0.097 S -1. In the presence of oxone, MPS was converted to methyl phenyl sulfoxide and methyl phenyl sulfone with a higher reaction rate than CEPS, decontaminated product of which was chloroethyl phenyl sulfone. Copyright Taylor & Francis Group, LLC.
- Farahipour, Mahdi,Fakhraian, Hossein,Mirzaei, Akbar,Hosseini, Morteza Ali
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- Selective oxidation reactions of diaryl- and dialkyldisulfides to sulfonic acids by CH3ReO3/hydrogen peroxide
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Diaryl- and dialkyl disulfides were oxidized in acetonitrile at 20 °C by CH3ReO3/H2O2 oxidant system to yield selectively the corresponding sulfonic acids in short reaction times and in high yields.
- Ballistreri, Francesco P.,Tomaselli, Gaetano A.,Toscano, Rosa M.
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experimental part
p. 6231 - 6232
(2010/01/11)
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- Oxidative hydrolysis of phosphorus(V) esters of thiols by peroxymonosulfate ion. Reactions of peroxymonosulfate ion with phosphorus(V) esters of thiols
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Peroxymonosulfate ion, HSO5-, as Oxone, readily converts phosphorus(V) esters of thiols into the phosphorus(V) and sulfonic acids. The esters were Ph2PO·SC6H4R(p) with R=MeO (1a), Me (1b), H (1c), Cl (1d) and NO2 (1e), (EtO)2PO·SPh (2), Ph2OI·SEt (3) and PhPO(OEt)SEt (4). Reactions are first order in each reactant and second-order rate constants, k2, for 1a-e fit the Hammett equation with ρ=-0.46. The rate constants increase markedly with increasing water content of H2O-MeCN, the activation enthalpies are low and the entropies are negative. Despite the low value of -ρ, these esters are much less reactive than thiol ethers, but the rate constants of reactions of these compounds and acyl thiols qualitatively follow the ionization potentials of the ethers and the esters.
- Blasko, Andrei,Bunton, Clifford A.,Kumar, Anurag
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p. 427 - 434
(2007/10/03)
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- Mechanisms of hydrolysis and related nucleophilic displacement reactions of alkanesulfonyl chlorides: pH dependence and the mechanism of hydration of sulfenes
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pH-rate profiles, primary kinetic isotope effects, deuterium substitution patterns, and pH-product ratios in the presence of added nucleophiles provide evidence for the following overlapping set of mechanisms for the hydrolysis of methanesulfonyl chloride (1) (in 0.1 M KCl at 25 °C): (a) pH ≤ 1-6.7, reaction with water by direct nucleophilic attack on the sulfonyl chloride; (b) pH ≥ 6.7-11.8, rate-determining attack by hydroxide anion to form sulfene (2), which is then trapped by water in a fast step; and (c) pH ≥ 11.8, sulfene formation and sulfene trapping by hydroxide anion; careful inspection showed no sign of sulfene formation in the reaction with water or of direct displacement by hydroxide anion. This pattern, with appropriate variations in the values of pHi (the pH at which two competing mechanisms have the same rate), is apparently general for simple alkanesulfonyl chlorides having at least one hydrogen on the carbon bearing the sulfonyl group. Azide and acetate anions react with 1 below pHi for 1 (6.7) by direct nucleophilic substitution at the sulfur, but above pHi by trapping of the sulfene. 2-Chlorophenoxide anion reacts with 1 below pH 6.7 by both (a) direct displacement to form the ester and (b) elimination to form the sulfene. Above pH 6.7, sulfene is formed from the sulfonyl chloride by reaction with either 2-chlorophenoxide or hydroxide ion; this is followed by trapping of the sulfene with 2-chlorophenoxide, water, or hydroxide. The possibility of the 2-chlorophenoxide anion acting as a general base promoting the reaction of water with either 1 and 2 was examined, but no sign of either process was detected.
- King,Lam,Skonieczny
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p. 1743 - 1749
(2007/10/02)
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- MECHANISTIC VARIATION IN ALKANESULFONYL CHLORIDE HYDROLYSIS AND RELATED REACTIONS
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Kinetic and product ratio studies are consistent with the following mechanisms for the hydrolysis of methanesulfonyl chloride: (a) in acidic medium (pH 1-6) via a direct substitution on sulfur (SN2-S), (b) in mildly basic medium (pH 8-10) by way of sulfene (CH2=SO2) formation followed by trapping with water, and (c) in strongly basic solution (pH >10) via sulfene with trapping by the hydroxide ion.The reactions of primary and secondary alkanesulfonyl chlorides are qualitatively similar.
- King, J. F.,Lam, J. Y. L.,Skonieczny, S.
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p. 177 - 180
(2007/10/02)
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- REACTION OF PROPOSED PHOSPHOROTHIOLATE S-OXIDE INTERMEDIATES WITH ALCOHOLS
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S-Oxide 2 is an extremely reactive intermediate.Its phosphorylation vs rearrangement rates, strongly depend upon the nature of the nucleophile.
- Segall, Yoffi,Casida, John E.
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p. 209 - 212
(2007/10/02)
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- Imidazolylmethyl methanobenzazocines
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1,2,3,4,5,6-Hexahydro-3-(Y)-6-(R1)-11-(R2)-2,6-methano-3-benzazocines, wherein Y is cycloalkyl-lower alkyl, lower alkyl-cycloalkyl-lower alkyl, carboxy-lower alkyl, cyano-lower alkyl, carbamyl-lower alkyl, tetrahydrofurylmethyl, 2-(2- or 3-indolyl)ethyl, amino-lower alkyl, butylcarbamyl, pyridinecarbonyl, (1-lower alkyl-imidazol-5-yl)methyl, 2,2-dimethoxyethyl, lower alkenyl, halo-lower alkenyl or cyano-lower alkenyl, R1 is lower alkyl and R2 is hydrogen or lower alkyl, are obtained starting with the corresponding 3-(H) compounds, in some instances via 3-acylated intermediate amides. The products have useful central depressant and psychomotor action, the preferred species wherein Y is cycloalkyl-lower alkyl or lower alkylcycloalkyl-lower alkyl being useful as analgesic agents in humans.
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- Oxidation of thiols and disulfides to sulfonic acids
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A process for formation of a sulfonic acid through oxidation of a thiol or disulfide. The process is carried out in the presence of a sulfoxide such as dimethyl sulfoxide, a halogen or hydrogen halide catalyst, and an excess quantity of water. The water acts as a moderator for the oxidation reaction to reduce the level of decomposition of the sulfoxide and, thereby, to improve the overall efficiency of the process. An intermolecular compound of an amino acid containing a sulfonic acid group and a carboxylic acid group with a sulfoxide in which the amino acid is at least moderately soluble. A method which comprises reacting an amino acid containing a sulfonic acid group and a carboxylic acid group with a sulfoxide in which the amino acid is at least moderately soluble. A method for recovering an amino acid containing a sulfonic acid group and a carboxylic acid group from an admixture of the amino acid with other ingredients by adding thereto a sulfoxide in which the amino acid is moderately soluble, with the sulfoxide being added in a sufficient amount to solubilize the amino acid, separating an intermolecular compound of the amino acid with the sulfoxide, and then recovering the amino acid from its intermolecular compound.
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