- Reactions of bielectrophiles (ClCH2CH2)2Y with sulfur in basic reducing systems
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A simple procedure was developed for preparing bis(β-mercaptoethyl) ether and bis(β-mecraptoethyl) sulfide from commercially available chemicals: elemental sulfur, alkali, and bis(β-chloroethyl) ether or sulfide, based on thiylation with elemental sulfur of these substrates in the aqueous system hydrazine hydrate-alkali, with initial formation of the corresponding polysulfide polymers (thiokols). Their reduction with the system hydrazine hydrate-alkali, followed by acidification of dithiolate anions, yields the corresponding dithiols. Thiokols based on bis(β-chloroethyl) ether are soluble in organic solvents; they were studied by 1H NMR.
- Korchevin,Russavskaya,Alekminskaya,Deryagina
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- Enhanced thermal degradation of 2,2′-dichlorodiethyl sulfide (sulfur mustard, HD) with the presence of metal oxides
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Thermal degradation of sulfur mustard (2,2′-dichlorodiethyl sulfide, HD) in the presence of metal oxide adsorbents was investigated by thermal desorption in conjunction with gas chromatography–mass spectrometry (GC-MS). Zr(OH)4, Al2O3, Al2CoO4, MgO, CeO2, and V2O5were used as metal oxide adsorbents. Neat HD was spiked onto the metal oxides packed in glass tubes, which were kept at room temperature and then heated at moderately elevated temperatures of 100°C by a thermal desorption system. The products of thermal degradation were directly transferred and analyzed by GC-MS. 1,4-Dithiane and 1,4-oxathiane were characterized as the major products of the thermal degradation of HD in the presence of Zr(OH)4, Al2O3, Al2CoO4, and CeO2adsorbents. No effective degradation was observed with MgO and V2O5. Of particular note is Zr(OH)4, which extremely enhanced the thermal degradation of HD.
- Jung, Hyunsook,Lee, Hae Wan,Jeong, Eun Ah
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- Degradation of Sulfur Mustard on KF/Al2O3: The Role of Organic Solvents and Active Species
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Solvent effects on the ability of KF/Al2O3 supports to degrade the warfare agent sulfur mustard (HD) were explored. RP-KF/Al2O3 possessing hydroxide ions and ECUF/KF/Al2O3 holding fluoride
- Fridkin, Gil,Columbus, Ishay,Yehezkel, Lea,Zafrani, Yossi
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p. 10541 - 10545
(2018/07/25)
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- Destruction of chemical warfare agent simulants by air and moisture stable metal NHC complexes
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The cooperative effect of both NHC and metal centre has been found to destroy chemical warfare agent (CWA) simulants. Choice of both the metal and NHC is key to these transformations as simple, monodentate N-heterocyclic carbenes in combination with silver or vanadium can promote stoichiometric destruction, whilst bidentate, aryloxide-tethered NHC complexes of silver and alkali metals promote breakdown under mild heating. Iron-NHC complexes generated in situ are competent catalysts for the destruction of each of the three targetted CWA simulants.
- Weetman, Catherine,Notman, Stuart,Arnold, Polly L.
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supporting information
p. 2568 - 2574
(2018/02/28)
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- Synthesis of cyclic ethers from diols in the presence of copper catalysts
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A number of cyclic ethers, namely tetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxepane, oxocane, and 1,4-oxathiane, have been synthesized in high yields by intramolecular dehydration of diols in the presence of copper-based catalysts.
- Bayguzina,Gimaletdinova,Khusnutdinov
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p. 1840 - 1843
(2018/02/06)
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- Metal ferrite nanoparticles: Synthesis, characterization, and studies on decontamination of sulfur mustard
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Mg, Ca, Mn, Co, Ni, Cu, Zn, Mn-Zn, and Co-Zn metal ferrite and mixed metal ferrite nanoparticles were synthesized by co-precipitation method and were characterized by using transmission electron microscopy, X-ray diffraction, and nitrogen adsorption techn
- Praveen Kumar,Prasad,Ramacharyulu,Singh, Beer,Anchal Roy
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p. 833 - 840
(2016/09/28)
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- Facile hydrolysis-based chemical destruction of the warfare agents VX, GB, and HD by alumina-supported fluoride reagents
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(Chemical Equation Presented) A facile solvent-free hydrolysis (chemical destruction) of the warfare agents VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate), GB (O-isopropyl methylphosphonofluoridate or sarin), and HD (2,2′-dichloroethyl sulfide or sulfur mustard) upon reaction with various solid-supported fluoride reagents is described. These solid reagents include different alumina-based powders such as KF/Al2O3, AgF/KF/Al2O3, and KF/Al2O3 enriched by so-called coordinatively unsaturated fluoride ions (termed by us as ECUF-KF/Al2O3). When adsorbed on these sorbents, the nerve agent VX quickly hydrolyzed (t1/2 range between 0.1-6.3 h) to the corresponding nontoxic phosphonic acid EMPA as a major product (>90%) and to the relatively toxic desethyl-VX (1/2 range between 2.2-161 h). The reaction rates and the product distribution were found to be strongly dependent on the nature of the fluoride ions in the KF/Al2O 3 matrix and on its water content. All variations of the alumina-supported fluoride reagents studied caused an immediate hydrolysis of the highly toxic GB (t1/2 31P, 13C, and 19F MAS NMR.
- Gershonov,Columbus,Zafrani
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supporting information; experimental part
p. 329 - 338
(2009/04/10)
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- Reactions of β,β′-dichlorodiethyl ether with elemental chalcogens and dimethyl dichalcogenides in the system hydrazine hydrate-base
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β,β′-Dichlorodiethyl ether reacted with elemental selenium or tellurium, as well as with binary chalcogen mixtures (S/Se, S/Te, or Se/Te), activated in the system hydrazine hydrate-base to give oligomeric products containing oxygen and polychalcogenide fr
- Vshivtsev,Levanova,Grabel'Nykh,Klyba,Zhanchipova,Sukhomazova,Tatarinova,Albanov,Russavskaya,Korchevin
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- Direct transformation of 1,3-dihalides into dithianes and dithiepines via a novel one-pot reaction with carbon disulfide and sodium borohydride
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1,3-Dithianes and -dithiepines are prepared via an experimentally simple and efficient direct transformation of 1,n-alkyl dihalides utilizing carbon disulfide and sodium borohydride.
- Wan, Yongqin,Kurchan, Alexei N.,Barnhurst, Loren A.,Kutateladze, Andrei G.
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p. 1133 - 1135
(2007/10/03)
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- PHENYLATION OF PLATINUM(II) THIOETHER COMPLEXES BY TETRAPHENYLBORATE(III) IN SOLID STATE AND NITROMETHANE SOLUTION
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Platinum(II) complexes of the type (1+) (thioether = dimethyl sulfide, thioxane) are capable of abstracting a phenyl group from the BPh4(1-) counterion with formation of trans- compounds.Thermal reactions proceed both in the solid phase and in nitromethane solution at elevated temperature and have preparative importance.Phenylation of the Pt(II) centre also occurs in reaction between and AgBPh4 in CH2Cl2 suspension.Brief X-ray crystallographic structural data for trans- and X (thioether = Me2S, tx, X=SO3CF3; thioether = Me2S, X=PF6) are reported. Key words: Platinum(II) thioether complexes; phenyl abstraction; tetraphenylborate ion; synthesis of thioether complexes; silver tetraphenylborate; X-ray structures.
- Kukushkin, Vadim Yu.,Loevqvist, Karin,Noren, Bertil,Oskarsson, Ake,Elding, Lars Ivar
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p. 253 - 256
(2007/10/02)
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- Studies on the Preparation of Dihydro-1,4-oxathiines. Computer-Assisted Evaluation of the Results of Retrosynthetic Analysis Verified by Synthetic Experiments and By-Product Analyses. Synthetic Pathways Involving α-Sulfenylated Ketones and 1,3-Oxathiolanes of α-Halo and α-Hydroxy K...
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The preparation of 2- and 2,3-substituted 5,6-dihydro-1,4-oxathiines has been studied by computer simulation and by experiment.Three major synthetic pathways, involving 2-(1-hydroxyalkyl)-1,3-oxathiolanes, 2-(1-haloalkyl)-1,3-oxathiolanes, 2-hydroxyethylthiomethyl ketones, methanesulfonates of 2-hydroxyethylthiomethyl ketones and 2-choroethylthiomethyl ketones as intermediates, were evaluated, by running the program CAMEO, and by experiment.The results of the two approaches were compared and the major by-products of the reactions were identified by GLC/MS.
- Nevalainen, Vesa,Pohjala, Esko,Maelkoenen, Pentti,Hukkanen, Heikki
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p. 591 - 602
(2007/10/02)
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- ORGANOTINS AS ETHERIFICATION CATALYSTS. II. CATALYTIC CONVERSION OF ALCOHOLS TO OPEN-CHAIN AND CYCLIC ETHERS BY ORGANOTIN TRICHLORIDES
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1,5-Heptadien-4-ol and various 1,4- and 1,5-glycols are catalytically converted to open-chain and cyclic ethers respectively in the presence of butyltin trichloride.The dehydration of alcohols is mediated by formation of organoalkoxytin dihalides BuSn(OR)Cl2.A mechanism for the formation of these ethers is proposed.The catalytic activity of ether organotins together with SnCl4 has been examined for the conversion of 1,5-pentanediol to THP; the scale of the catalytic efficiency is: MeSnCl3 >= PhSnCl3 > SnCl4 > BuSnCl3 > Me2SnCl2 > Bu2SnCl2 >> (Bu2SnCl)2O.
- Tagliavini, Giuseppe,Marton, Daniele,Furlani, Donatella
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p. 1187 - 1196
(2007/10/02)
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