938-09-0Relevant articles and documents
Remarkable efficiency of iron(III) versus manganese(III) tetraphenylporphyrins as catalysts for fast and quantitative oxidation of sulfides into sulfones by hydrogen peroxide
Marques, Antonio,Di Matteo, Massimo,Ruasse, Marie-Francoise
, p. 770 - 775 (1998)
The efficiency of various metallo-phtalocyanines (Pht) and - tetraphenylporphyrins (TPP) as catalysts for the H2O2 oxidations of dibenzylsulfide, phenylchloroethylsulfide, and thioanisole is investigated in ethanol and acetonitrile, using imidazole as a cocatalyst. Neither PhtNi(II) nor TPPCo(II) exhibits any catalytic activity. PhtMn(II) and TPPMn(III)Cl accelerate markedly these reactions but do not promote quantitative oxidations, at most 70% of the sulfides being transformed into sulfoxides. In contrast, with PhtFe(II) sulfoxides are obtained with a 100% yield from sulfides. Finally, the only catalyst able to oxidize sulfides rapidly (5 min), completely and quantitatively (100% sulfone) is TPPFe(III)Cl in EtOH. The absence of any by-product, disulfide in particular, suggests that a free sulfenium radical cation is not an active intermediate in these reactions. The marked differences in the behaviour of TPPMn(III)Cl and TPPFe(III)Cl are analyzed by comparing the rates of the catalyst decomposition, of the sulfoxide and sulfone formation as a function of the hydrogen peroxide concentration. The results are discussed in terms of a competition between the several oxidative pathways and a possible mechanism for the oxygen transfer to sulfides.
Oxidative Neutralization of Mustard-Gas Simulants in an On-Board Flow Device with In-Line NMR Monitoring
Picard, Baptiste,Gouilleux, Boris,Lebleu, Thomas,Maddaluno, Jacques,Chataigner, Isabelle,Penhoat, Ma?l,Felpin, Fran?ois-Xavier,Giraudeau, Patrick,Legros, Julien
supporting information, p. 7568 - 7572 (2017/06/13)
The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea–H2O2 adduct/MeSO3H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25 g of pure CEES within 46 minutes in a 21.5 mL millireactor (tR=3.9 minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.
By means of a micro channel reactor method of preparing sulfoxide or sulfone
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Paragraph 0090-0094, (2017/04/11)
The invention discloses a method for preparing sulfoxide or sulfone by using a micro-channel reactor. The invention provides a method for preparing sulfoxide or sulfone. The method comprises the following steps: respectively feeding a homogeneous solution prepared from thioether 1 and a solvent, and an oxidant into the micro-channel reactor, and contacting the homogeneous solution with the oxidant in a micro-channel for oxidation reaction so as to obtain sulfoxide or sulfone, wherein the oxidation reaction time is 1-300 seconds. The method disclosed by the invention is very short in reaction time, precise in reaction condition control, high in security, applicable to rapid preparation of kilogram-scale products and capable of realizing continuous production; the sulfoxide and sulfone are high in selectivity, high in yield, good in purity and applicable to on-scale industrial production.
Synthesis of a new class of arylsulfonylethylsulfonylmethyloxazolines and thiazolines
Padmavathi, Venkatapuram,Venkatesh, Bhumireddy Chinnachennaiahgari,Premakumari, Chokkappagari,Padmaja, Adivireddy
scheme or table, p. 646 - 651 (2012/09/07)
A new class of arylsulfonylethylsulfonylmethyl oxazolines and thiazolines were prepared using multistep, one-pot methodologies exploiting lanthanide alkoxides and under microwave irradiation. The microwave method provides an excellent approach in a single step with high yields.
L-Gel formulation and decontamination reaction of its active ingredient (oxone) against mustard and VX nerve agent simulants
Farahipour, Mahdi,Fakhraian, Hossein,Mirzaei, Akbar,Hosseini, Morteza Ali
experimental part, p. 2303 - 2310 (2012/03/27)
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.
Optically active tripodal dendritic polyoxometalates: Synthesis, characterization and their use in asymmetric sulfide oxidation with hydrogen peroxide
Jahier, Claire,Coustou, Marie-Flora,Cantuel, Martine,McClenaghan, Nathan D.,Buffeteau, Thierry,Cavagnat, Dominique,Carraro, Mauro,Nlate, Sylvain
experimental part, p. 727 - 738 (2011/04/26)
A series of structurally well-defined enantiopure tripodal allyl dendritic structures bearing three amine groups have been synthesized. The hydrogenation of the allyl groups in the presence of a Pd/C catalyst gave the corresponding enantiopure n-propyl counterparts. Treatment of these n-propyl amino dendrimers with heteropolyacid H3PW12O40 and excess H 2O2 gave the enantiopure n-propyl {PO 4[WO(O2)2]4}3- salts. Characterization of these dendritic POM hybrids in solution by NMR spectroscopy, elemental analysis, UV/Vis spectrophotometry, circular dichroism (CD), vibrational circular dichroism (VCD) and fluorimetry indicates the presence of POM-ligand interactions and confirms their optical and chiroptical properties. The hybrid compounds selectively oxidized sulfides to the corresponding chiral sulfoxides with up to 13% enantiomeric excess (ee), highlighting the transfer of chirality from the dendritic wedges to the inorganic cluster. The properties of the POM anion, especially its solubility and regio-and stereoselectivity, are sensitive to the structure of the cation. The catalyst was recovered by precipitation without any discernible loss in activity, selectivity or enantioselectivity over three catalytic cycles at-50 °C. Interestingly, a dendritic effect was noted in the enantioselectivity as the dendritic-POM hybrids are more selective than their non-dendritic counterparts. The ee resulting from chirality transfer to the anionic POM unit is comparable to that obtained in our previous work with monopodal dendritic polyoxometalates (14%) despite the polyvalency of the highly charged tripodal ligand, which is rationalized by different spectroscopic methods. Copyright
Locus-specific microemulsion catalysts for sulfur mustard (HD) chemical warfare agent decontamination
Fallis, Ian A.,Griffiths, Peter C.,Cosgrove, Terence,Dreiss, Cecile A.,Govan, Norman,Heenan, Richard K.,Holden, Ian,Jenkins, Robert L.,Mitchell, Stephen J.,Notman, Stuart,Platts, Jamie A.,Riches, James,Tatchell, Thomas
scheme or table, p. 9746 - 9755 (2011/03/20)
The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (Kow), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t1/2 (HD) ～ 18 s, (2-chloroethyl phenyl sulfide, C6H5SCH2CH 2Cl) ～ 15 s, (thiodiglycol, S(CH2CH 2OH)2) ～ 19 s {20°C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.
WO3 Nanoparticles on MCM-48 as a Highly Selective and Versatile Heterogeneous Catalyst for the Oxidation of Olefins, Sulfides, and Cyclic Ketones
Koo, Dong Hyun,Kim, Min,Chang, Sukbok
, p. 5015 - 5018 (2007/10/03)
It is shown that nanosized WO3 particles supported on MCM-48 work as a highly efficient and selective heterogeneous catalyst for the oxidation of olefins, sulfides, and cyclic ketones using hydrogen peroxide or peracetic acid. The catalytic activity of the supported tungstate was dependent on the nature of the supporting materials and particle size. The catalyst system employs environmentally benign oxidants in halide-free solvents, and it does not require phase-transfer agents and pH control.
Highly efficient utilization of H2O2 for oxygenation of organic sulfides catalyzed by [γ-SiW10O34(H 2O)2]4-
Phan, Tuan D.,Kinch, Mark A.,Barker, Julia E.,Ren, Tong
, p. 397 - 400 (2007/10/03)
Remarkable efficiency of hydrogen peroxide utilization is reported for oxygenation of four organic sulfides catalyzed by a divacant lacunary silicotungstate, (Bu4N)4[γ-SiW10O 34(H2O)2] (1), under mild conditions. The addition of imidazole, phosphate, or carboxylates significantly enhances the rate of organic sulfide oxygenation. Most notably, use of 1 and imidazole, both at 1% molar concentration, resulted in the quantitative conversion of phenylsulfide to sulfoxide with 1 equiv of H2O2 in 3 h, and to sulfone with 2 equiv of H2O2 in 6 h.
Synthesis and pharmacological properties of benzamide derivatives as selective serotonin 4 receptor agonists
Sonda, Shuji,Katayama, Kenichi,Kawahara, Toshio,Sato, Noriko,Asano, Kiyoshi
, p. 2737 - 2747 (2007/10/03)
A series of 4-amino-5-chloro-2-methoxy-N-(piperidin-4-ylmethyl)benzamides with a polar substituent group at the 1-position of the piperidine ring was synthesized and evaluated for its effect on gastrointestinal motility. The benzoyl, phenylsulfonyl, and benzylsulfonyl derivatives accelerated gastric emptying and increased the frequency of defecation. One of them, 4-amino-N-[1-[3-(benzylsulfonyl)propyl]piperidin-4-ylmethyl]-5-chloro-2- methoxybenzamide (13a, Y-36912), was a selective 5-HT4 receptor agonist offering potential as a novel prokinetic with reduced side effects derived from 5-HT3- and dopamine D2 receptor-binding affinity. In the oral route of administration, this compound enhanced gastric emptying and defecation in mice, and has a possibility as a prokinetic agent, which is effective on both the upper and the lower gastrointestinal tract.
