F:Flammable;
75-18-3Relevant articles and documents
Krueger
, p. 132,134-136 (1966)
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
Nuzzo et al.
, p. 568,569 (1977)
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.
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.
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.
Fahmy,M.A.H. et al.
, p. 617 - 625 (1972)
Coordination Chemistry of Borane in Solution: Application to a STING Agonist
Lemaire, Sébastien,Zhdanko, Alexander,van der Worp, Boris A.
, (2022/04/09)
Equilibrium constants were determined for ligand exchange reactions of borane complexes with various oxygen, sulfur, nitrogen, and phosphorus nucleophiles in solution, and a binding affinity scale was built spanning a range of 12 orders of magnitude. While the Keq are minimally dependent on the solvent, the rate of ligand exchange varies significantly. The fastest and slowest rates were observed in THF and CDCl3, respectively. Moreover, the ligand exchange rate differs in a very broad range depending on stability of the starting complex. Binding of BH3 was found to be much more sensitive to steric factors than protonation. Comparing nitrogen bases having equal steric properties, a linear correlation of BH3 binding affinity vs. Br?nsted acidity was found. This correlation can be used to quickly estimate the BH3 binding affinity of a substrate if pKa is known. Kinetic studies suggest the ligand exchange to occur as a bimolecular SN2 reaction unless other nucleophilic species were present in the reaction mixture.
Dynamics of the dimethyl sulfide exchange of (1,3-diphenylallyl)dimethylsulfonium ions
Jüstel, Patrick M.,Mayr, Herbert,Ofial, Armin R.,Rovó, Petra
, (2021/08/12)
The dynamics of the allylic rearrangement of the (1,3-diphenylallyl)dimethylsulfonium ion in CD2Cl2, which proceeds via intermediate 1,3-diphenylallyl cations, has been investigated by variable temperature 1H NMR spectroscopy. At low temperature, the three allylic protons give rise to an AMX system, and the two diastereotopic S-methyl groups resonate at different frequencies. At higher temperature, an AX2 system for the allylic protons and a single signal for the S-methyl groups are observed. The resulting exchange rate constant of (364 ± 2) s–1 at 25°C, which corresponds to the rate of the heterolytic cleavage of the C–S bond, was used to explore the range of validity of the linear free energy relationship log khet(25°C) = sf (Nf + Ef), which describes the rates of heterolytic cleavages by the electrofugality parameter Ef and the solvent-dependent nucleofuge-specific parameters Nf and sf. The observed rate constant corroborates a previous conclusion that two different sets of Nf and sf parameters may exist for the same nucleofuge. Knowledge of whether the reverse bond-forming reaction occurs under activation or under diffusion control is crucial for the choice of the appropriate set of nucleofugality parameters.
Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications
Clarke, Aimee K.,Parkin, Alison,Rossi-Ashton, James A.,Taylor, Richard J. K.,Unsworth, William P.
, p. 5814 - 5820 (2020/07/21)
The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.
