F:Flammable;
75-18-3Relevant articles and documents
Karl-Fischer-Reaction in Dimethyl Sulfoxide
Fischer, Wolfgang,Beil, Stefanie,Krenn, Karl-Dieter
, p. 266 - 268 (1995)
The water equivalent (titer) of methanolic Karl-Fischer-reagents rises if dimethyl sulfoxide (DMSO) is used as an additional solvent.It is shown that the probable reason for this observation is the formation of iodine by the reaction between DMSO, iodide and sulfur trioxide.
Efficient uptake of dimethyl sulfoxide by the desoxomolybdenum(iv) dithiolate complex containing bulky hydrophobic groups
Hasenaka, Yuki,Okamura, Taka-Aki,Onitsuka, Kiyotaka
, p. 6260 - 6267 (2015)
A desoxomolybdenum(iv) complex containing bulky hydrophobic groups and NH...S hydrogen bonds, (Et4N)[MoIV(OSitBuPh2)(1,2-S2-3,6-{(4-tBuC6H4)3CCONH}2C6H2)2], was synthesized. This complex promotes the oxygen-atom-transfer (OAT) reaction of DMSO by efficient uptake of the substrate into the active center. The clean OAT reaction of Me3NO is also achieved. This journal is
Reaction of Thioanisol with Antimony Pentachloride
Hartke, Klaus,Zerbe, Horst-Georg
, p. 153 - 156 (1982)
The reaction of antimony pentachloride with thioanisole (5) at -70 deg C leads to the formation of the sulfonium salt 6, whereas at 0 deg C the chlorosulfonium salt 7 is formed.Under similar conditions 4-methylthioanisole (9) is converted into the expected chlorosulfonium salt 10, which decomposed, however, during isolation experiments.
Synthesis, crystal structure and reactivity of a new pentacoordinated chiral dioxomolybdenum(VI) complex
Pedrosa,Escribano,Aguado,Sanz,Díez,Arnáiz
, p. 841 - 849 (2010)
The novel tridentate chiral ligand 2,6-bis{[(1R,2S,4R)-2-hydroxy-1,3,3-trimethyl-bicyclo[2.2.1]hept-2-yl]}pyridine (1) was readily prepared by reaction of 2,6-dilithiopyridine with (R)-(-)-fenchone. Reaction of 1 with [MoO2(acac)2] resulted in the formation of the new metal-oxo five-coordinated complex [MoO2(ONO)] (2) [ONO = (1 - 2H)]. The reactivity of 2 has been studied and the derivatives [MoS2(ONO)] (3) and [MoO(O2)(ONO)] (4) were prepared. The compounds 1-4 have been characterised by 1H and 13C{1H} NMR, microanalysis and IR spectroscopy. Furthermore, the molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction. The behaviour of 2 as catalyst in oxotransfer and in nucleophilic substitution of propargylic alcohols reactions has been tested.
Evolution of the surface sulfur composition of a Ru sulfide particle during CH3SH condensation reaction: Sulfur migration from the bulk to the surface
Berhault,Lacroix
, p. 308 - 312 (2001)
The condensation of methanethiol (CH3SH) into dimethylsulfide (CH3SCH3), which is a useful test reaction for probing the acid-base character of transition metal sulfide catalysts for carbon-heteroatom hydrogenolysis reactions, shows a systematic deactivation process at the beginning of the reaction before reaching steady-state activity. The solid surface of RuS2 catalyst in equilibrium with the gas phase was examined by various techniques with the aim of understanding the mechanism responsible for this loss of activity, e.g. coke formation, poisoning by the reactant or the products, change in particle size, etc. X-Ray diffraction and elemental analysis showed neither the formation of carbonaceous deposits nor a sintering effect during the catalytic run. In contrast, a modification of the surface composition of the catalyst induced by the reaction was observed using temperature programmed reduction (TPR). This technique showed that large amounts of H2S are detectable after performing the catalytic test. Sulfur mass balance analyses demonstrate that these sulfur species are an integral part of the total sulfur content of the ruthenium sulfide particles. These surface modifications arise from sulfur migration from the bulk to the surface of the particles during reation. Based on these experimental data and on a crystallographic model developed for RuS2, it is proposed that the methanethiol condensation reaction proceeds on monovacant Ru sites.
Cobalt hexaamine mediated electrocatalytic voltammetry of dimethyl sulfoxide reductase: Driving force effects on catalysis
Chen, Kuan-I.,McEwan, Alastair G.,Bernhardt, Paul V.
, p. 227 - 234 (2011)
The bacterial molybdoenzyme dimethyl sulfoxide (DMSO) reductase from Rhodobacter capsulatus catalyzes the reduction of DMSO to dimethyl sulfide in anaerobic respiration. In its native state, DMSO reductase is reduced to its active state by a pentaheme cytochrome (DorC). Alternatively, we show that DMSO reductase catalysis may be driven electrochemically using a series of homologous coordination compounds as mediating synthetic electron donors. All mediators are macrocyclic hexaaminecobalt(II) complexes in their active form, differing principally in their redox potentials over a range of about 250 mV. Thus, each complex presents a different reductive driving force to DMSO reductase and this leads to pronounced differences in the electrocatalytic behavior as measured by cyclic voltammetry. Digital simulation of the experimental voltammetry enables the critical features of the catalytic cycle to be extracted.
FACILE DEOXYGENATION OF SULFOXIDES BY USING METAL/CHLOROMETHYLSILANES
Nagasawa, Kazuo,Yoneta, Akemi,Umezawa, Toshiyuki,Ito, Keiichi
, p. 2607 - 2609 (1987)
Deoxygenation of a various kind of sulfoxides including optically active one by Zinc/Dichlorodimethylsilane proceeds under very mild conditions to furnish the corresponding sulfides in high yields.
Dynamics of Competitive Reactions: Endothermic Proton Transfer and Exothermic Substitution
Ren, Jianhua,Brauman, John I.
, p. 2640 - 2646 (2004)
Dynamics of an endothermic proton-transfer reaction, F- with dimethyl sulfoxide, and an endothermic proton-transfer reaction with a competing exothermic substitution (SN2) channel, F- with borane-methyl sulfide complex, were investigated using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) and kinetic modeling. The two proton-transfer reactions have slightly positive and a small negative overall free energy changes, respectively. Energy-dependent rate constants were measured as a function of F- ion translational energy, and the resulting kinetics were modeled with the RRKM (Rice-Ramsperger-Kassel-Marcus) theory. The observed rate constants for the proton-transfer reactions of F - with dimethyl sulfoxide and with borane-methyl sulfide complex are identical, with a value of 0.17 × 10-9 cm3 molecule-1 s-1; for the SN2 reaction, k = 0.90 × 10-9 cm3 molecule-1 s-1 at 350 K. Both proton-transfer reactions have positive entropy changes in the forward direction and show positive energy dependences. The competing SN2 reaction exhibits negative energy dependence and becomes less important at higher energies. The changes of the observed rate constants agree with RRKM theory predictions for a few kcal/mol of additional kinetic energy. The dynamic change of the branching ratio for the competing proton transfer and the substitution reactions results from the competition between the microscopic rate constants associated with each channel.
Catalytic synthesis of dimethyl sulfi de from dimethyl disulfi de and methanol
Mashkina,Khairulina
, p. 926 - 932 (2012)
The reaction of dimethyl disulfi de with methanol was studied at atmospheric pressure and temperature of 350°C in the presence of catalysts containing acid and basic sites.
Novel oxidation of hydrogen sulfide by dimethyl sulfoxide in presence of β-cyclodextrin
Yang, Xiaoxia,Zhang, Jianbin,Chang, Yan,Li, Qiang
, p. 7040 - 7042 (2014)
Dimethyl sulfoxide is used as an oxidizing agent to oxidize hydrogen sulfide to solid sulfur at room temperatures and normal pressures, in which, β-cyelodextrin plays an important role in this reaction. in this work, when GC-MS, SEM and FTIR spectroscopic
