1618-26-4Relevant articles and documents
Stereoelectronic Effects in the Gas Phase. 2. Negative Ion Reactions of 1,3-Dithianes and 1,3-Dithiane 1-Oxides
Fisher, Cindy L.,Kahn, Scott D.,Hehre, Warren J.,Caserio, Marjorie C.
, p. 7379 - 7387 (1989)
Reactions of gaseous anions (methoxide, hydroxide, and thermal electrons) with cis-4,6-dimethyl-1,3-dithiane and the corresponding axial and equatorial 1-oxides have been investigated using the techniques of ion cyclotron resonance (ICR) spectroscopy and pulsed positive-negative ion chemical ionization (PPNICI) spectroscopy.Deprotonation to (M-H)(1-) ions and extensive fragmentation to ions m/z 99 and 101 were observed for all three compounds with all three reactant anions.When compounds labeled with deuterium specifically at the C2 position were used, it was foundthat deprotonation occurred at C2 and elsewhere in the molecule.The axial hydrogen at C2 was removed as readily or more so than the equatorial hydrogen, depending on the reactants and conditions of ion generation. (These results differ from the corresponding condensed-phase reactions, which show strong selectivity for C2 equatorial deprotonation).Deuterium isotope effects were estimated to be 1.2 and 1.3 for ions generated by MeO(1-) and e, respectively.Exchange (H/D) between hydroxide and cis-4,6-dimethyl-1,3-dithiane-2-d2 was insignificant, although exchange was observed in comparable reactions of hydroxide with 1,3-dithiane-d2 and bis(methylthio)methane-d2.Stereoelectronic effects that may contribute to selectivity in solution do not account for the gas-phase results.Ab initio calculations at the 3-21G(*) level applied to methanedithiol and the anion (HS)2CH(1-) (as models for the 1,3-dithiane system) provide insight into the nature of the gas-phase reactions.Possible reaction pathways are discussed.
Lambert,J.B. et al.
, p. 4689 - 4695 (1979)
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Haszeldine,R.N. et al.
, p. 249 - 250 (1972)
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Formation of Dithioacetals by Treatment of Sulfoxides Carrying α-Hydrogens with Magnesium Amides
Kobayashi, Kazuhiro,Kawakita, Masataka,Mannami, Tohru,Morikawa, Osamu,Konishi, Hisatoshi
, p. 1551 - 1554 (1994)
Sulfoxides carrying α-hydrogens were allowed to react with magnesium amides generated in situ by the treatment of ethylmagnesium bromide with secondary amines such as 2,2,6,6-tetramethylpiperidine or diisopropylamine in diethyl ether to give the corresponding dithioacetals in moderate to good yields.
Effect of Zinc Oxide on the Thermal Decomposition of Dimethyl Sulfoxide
Chen, Liping,Chen, Wanghua,Guo, Zichao,Li, Huabo,Weng, Shichun,Wu, Wenqian
, (2022/03/14)
Dimethyl sulfoxide (DMSO) is widely used in the chemical industry. However, it has a non-neglectful thermal runaway risk due to the nature of self-accelerating decomposition near the boiling point. Under the background that zinc oxide (ZnO) may extend the isothermal induction period of thermal decomposition of DMSO, this article conducts an in-depth study for the phenomenon with the techniques such as differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), gas chromatography-mass spectrometry (GC-MS), X-ray photoelectron spectroscopy (XPS), and X-ray diffractometry (XRD). After being mixed with ZnO, the maximum decomposition rate of DMSO was significantly reduced and the adiabatic induction period of DMSO decomposition was extended by 3.27 times, indicating that the thermal decomposition intensity of DMSO was obviously reduced. It was experimentally demonstrated that ZnO did not change the decomposition pathways of DMSO, but it could promote the decomposition of methanethiol, which was a decomposition intermediate of DMSO and could potentially serve as a promoter on the decomposition of DMSO.
Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2pressure
Fujita, Shu,Mitsudome, Takato,Mizugaki, Tomoo,Yamaguchi, Sho,Yamasaki, Jun,Yamazoe, Seiji
supporting information, p. 8827 - 8833 (2020/11/23)
Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2. This journal is
Deoxygenation of sulfoxides to sulfides in the presence of zinc catalysts and boranes as reducing reagents
Enthaler, Stephan,Krackl, Sebastian,Irran, Elisabeth,Inoue, Shigeyoshi
, p. 1003 - 1010 (2012/10/29)
In the present study, the zinc-catalyzed deoxygenation of aliphatic and aromatic sulfoxides in the presence of boranes as reducing reagent has been explored. After investigation of different reaction parameters the abilities of catalytic amounts of Zn(OTf)2 has been demonstrated in the deoxygenation of various sulfoxides. Moreover, various experiments have been performed to shed light on the underlying reaction mechanism.