505-29-3Relevant articles and documents
Formation of Chlorosulfonium Salt of 1,5-Dithiacyclooctane and Transannular Sulfur-Sulfur Interaction in Hydrolysis of Its Salt
Fujihara, Hisashi,Akaishi, Ryouichi,Furukawa, Naomichi
, p. 4451 - 4452 (1987)
The reaction of 1,5-dithiacyclooctane 1-oxide (2) with thionyl chloride afforded the corresponding chlorosulfonium chloride as a stable salt and an evidence for the intermediary formation of the bis-sulfide dication with an equilibrium mixture of the chlorosulfonium salt was found.In contrast to 2, 1,4-dithiacyclohexane 1-oxide (6) reacts with thionyl chloride like a simple sulfoxide.
Enhanced thermal degradation of 2,2′-dichlorodiethyl sulfide (sulfur mustard, HD) with the presence of metal oxides
Jung, Hyunsook,Lee, Hae Wan,Jeong, Eun Ah
, p. 1137 - 1141 (2016/07/27)
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.
Novel 1,5,3-dithiazepanes: Three-component synthesis, stereochemistry, and fungicidal activity
Akhmetova,Murzakova,Tyumkina,Khabibullina,Bushmarinov,Korzhova,Galimzyanova
, p. 2140 - 2148 (2013/10/01)
Three-component heterocyclization of hydrazine with formaldehyde and ethane-1,2-dithiol gave previously unknown 3,3′-bi(1,5,3-dithiazepane). Its stereochemistry was determined by X-ray diffraction. The reaction with higher aliphatic aldehydes RCHO (R = Me
A highly efficient carbon-sulfur bond formation reaction via microwave-assisted nucleophilic substitution of thiols to polychloroalkanes without a transition-metal catalyst
Cao, Yi-Ju,Lai, Yuan-Yuan,Cao, Hong,Xing, Xiao-Ning,Wang, Xiang,Xiao, Wen-Jing
, p. 1529 - 1533 (2007/10/03)
An efficient carbon-sulfur bond formation reaction has been developed under microwave irradiation. This reaction affords a novel and rapid synthesis of thioacetals and sulfides under mild conditions. This method is particularly noteworthy given its experimental simplicity and high generality, and no transition-metal catalysts were needed under our conditions.
Ionic liquid as catalyst and reaction medium: A simple, convenient and green procedure for the synthesis of thioethers, thioesters and dithianes using an inexpensive ionic liquid, [pmIm]Br
Ranu, Brindaban C.,Jana, Ranjan
, p. 1811 - 1818 (2007/10/03)
An easily accessible and inexpensive room temperature ionic liquid, 1-pentyl-3-methylimidazolium bromide, [pmIm]Br efficiently catalyzes the reaction of alkyl halides or acyl halides with thiols without any solvent at room temperature leading to the synthesis of thioethers and thioesters in high yields. This reaction has also been extended for the preparation of dithianes and transthioetherification. The ionic liquid is recovered and recycled for subsequent runs.
Synthetic potentialities of sulfonylsulfonium salts: A new approach to the preparation of disulfonium dications
Shevchenko,Nenaidenko,Balenkova
, p. 1415 - 1420 (2007/10/03)
A new efficient method for the generation of disulfonium dications whose subsequent hydrolysis selectively affords monosulfoxides was developed based on the oxidation of bis-sulfides by trifluoromethanesulfonic anhydride.
Thermal degradation of bis (2-chloroethyl) sulfide (mustard gas)
Wagner, George W.,Maciver, Brian K.,Rohrbaugh, Dennis K.,Yang, Yu-Chu
, p. 65 - 76 (2007/10/03)
The thermal degradation of mustard gas (ClCH2CH2SCH2CH2Cl, HD ), with and without 5% added water, is examined. GC/MS, LC/MS and NMR were employed to comprehensively analyze the products. After 75 days at 90°C, 91% HD remains (80% with 5% water). After 40 days at 140°C, 30% HD remains (24% with 5% water) and black tar precipitates form. The apparent Ea is 22.4 kcal/mol. Major products include Q (ClCH2CH2SCH2CH2SCH2CH2Cl), 1,2-dichloroethane, polysulfides and 1,4-dithiane. With 5% water, oxygenates such as 1,4-thioxane and 2-chloroethanol are produced as are numerous sulfonium ions, including S-(2-chlorethyl)-1,4-dithianium, a major component of mustard heels. The decomposition does not go to completion due to the equilibrium nature of the reaction at these temperatures.
The macrocyclization reaction of terminal dibromoalkanes with sulfide on alumina. The use of a solid support as an alternative to the high dilution technique
Tan,Pagni,Kabalka,Hillmeyer,Woosley
, p. 7709 - 7712 (2007/10/02)
The reaction of a series of terminal dibromoalkanes with S-2 on Al2O3 has been examined. The use of a solid support for the macrocyclization represents a viable alternate procedure to the more traditional high dilution technique in solution. The cyclization also occur with thioacetamide on unactivated alumina.
1H NMR kinetic study of ligand exchange on bis(1,4-dithiane)platinum(II), bis(1,4-dithiane)palladium(II), and tetrakis(dimethyl sulfide)platinum(II)
Frey, Urban,Elmroth, Sofi,Moullet, Bertrand,Elding, Lars I.,Merbach, André E.
, p. 5033 - 5037 (2008/10/08)
Ligand exchange on square-planar Pt(1,4-dithiane)22+, Pd(1,4-dithiane)22+, and Pt(Me2S)42+ has been studied as a function of temperature and pressure by 1H NMR line-broadening, isotopic labeling, and magnetization transfer experiments with deuteriated nitromethane as solvent. Second-order rate constants and activation parameters are as follows: for 1,4-dithiane exchange on Pt(1,4-dithiane)22+, k2298 = 28.8 ± 4.8 m-1 s-1, ΔH? = 32.9 ± 3.6 kJ mol-1, ΔS? = -106 ± 11 J K-1 mol1, and ΔV? = -12.6 ± 1.1 cm3 mol1; for 1,4-dithiane exchange on Pd(1,4-dithiane)22+, k2298 = 9780 ± 300 m-1 s-1, ΔH? = 22.9 ± 0.6 kJ mol-1, ΔS? = -91.6 ± 2.1 J K-1 mol-1, and ΔV? = -9.8 ± 0.4 cm3 mol-1; for Me2S exchange on Pt(Me2S)42+, k2298 = 1.54 ± 0.07 m-1 s-1, ΔH? = 42.1 ± 0.7 kJ mol-1, ΔS? = -100.2 ± 2.2 J K-1 mol-1, and ΔV? = -22.0 ± 1.3 cm3 mol-1. Second-order kinetics and negative entropies and volumes of activation indicate associative, Ia or A, exchange mechanisms. For both metal centers, exchange of the chelated and strongly bound 1,4-dithiane, corrected for statistics, is faster than that of Me2S, probably due to steric factors. The ratio in reactivity for Pd/Pt is only ca. 1300 for Me2S and 340 for 1,4-dithiane, indicating a more pronounced sensitivity of Pt(II) to the electronic properties of the coordinated and entering ligands. Accordingly, activation volumes are more negative in the case of platinum. ΔV? for the Me2S exchange on Pt(II) is the most negative one reported so far for a square-planar solvent exchange.
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...
Nevalainen, Vesa,Pohjala, Esko,Maelkoenen, Pentti,Hukkanen, Heikki
, p. 591 - 602 (2007/10/02)
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.
