7560-59-0Relevant articles and documents
Reactions of chlorine dioxide with organic compounds: Selective oxidation of sulfides to sulfoxides by chlorine dioxide
Kutchin,Rubtsova,Loginova
, p. 432 - 435 (2007/10/03)
A novel method for the selective oxidation of various types of sulfides to sulfoxides using chlorine dioxide as the oxidant is proposed.
Oxidation of thioethers and sulfoxides with hydrogen peroxide using TS-1 as catalyst
Hutchings,Lee,McMorn,Page,Robinson,Willock,Davies,Watson,McGuire,Lee,Bethell
, p. 1523 - 1529 (2007/10/03)
A combined experimental and molecular simulation study of the oxidation of thioethers with H2O2 was conducted using titanium-containing zeolites as catalysts. Regioselectivity was investigated for the oxidation of allyl methyl thioether using TS-1 as catalyst. Only products for the oxidation of sulfur, such as sulfoxide and sulfolane, were found. Shape-selective oxidation was studied with four isomeric butyl methyl thioethers. For n-, iso-, and sec-butyl methyl thioethers, the principal product for the TS-1 catalyzed reaction was the sulfone, but that for tert-butyl methyl thioether was from partial oxidation to sulfoxide. The origin of this effect was evaluated using molecular simulations. Thioether oxidation to sulfoxide readily occurred via a non-catalyzed solution reaction, while the oxidation of sulfoxide to sulfone was only observed in the catalyzed reactions. The non-catalyzed reaction can be suppressed by conducting the catalyzed reaction in the presence of a base, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), that is too large to diffuse into the intracrystalline pore structure of TS-1. With DBU, the reaction rate with TS-1 as catalyst was much lower. The relative ratios of the sulfoxide and sulfone products can be elucidated through intramolecular steric hindrance and the shape selectivity of the zeolite. TS-1 has been used for the oxidation of alkenes, alcohols, allylic alcohols, phenols, and benzene.
New procedures for the oxidation of sulfides to sulfoxides and sulfones
Drabowicz, Jozef,Lyzwa, Piotr,Luczak, Jerzy,Mikolajczyk, Marian,Laur, Peter
, p. 425 - 426 (2007/10/03)
New reagents for the oxidation of sulfides to the corresponding sulfoxides and sulfones are presented.
Cathodic cleavage of heteroarylalkylsulfones: A facile route to long chain aliphatic sulfinates and relevant sulfones
Delaunay,Mabon,Chaquiq El Badre,Orliac,Simonet
, p. 2149 - 2150 (2007/10/02)
Heteroarylalkylsulfones - mainly pyridylalkylsulfones - exhibit a cathodic cleavage reaction producing alkanesulfinate anion in high yield. This reaction is tested with long chain alkyl groups and allows an easy synthesis of aliphatic sulfinic acids.
Ultrasonically Dispersed Potassium in Organic Synthesis. Water-Acceleration in Reductive C-S Bond Cleavage Reactions
Chou, Ta-shue,Hung, Shao-Hwa,Peng, Man-Li,Lee, Shwu-Jiaun
, p. 3551 - 3554 (2007/10/02)
The slow addition of a pre-measured amount of water in THF can greatly enhance the UDP induced C-S bond cleavage reactions of cyclic sulfones.This reaction can be used in the synthesis of open chain sulfones with γ-, δ- or ε-deuteration.
Search for New Membrane-active Substances: Synthesis of Tropan-3-ols with Alkyl, Alkenyl and Alkenynyl Groups at the Bridgehead
Dharanipragada, Ramalinga,Fodor, Gabor
, p. 545 - 550 (2007/10/02)
The synthesis of tropan-3-ols with alkyl, alkenyl and alkynyl groups at the bridgehead is described.The new compounds have been considered as new membrane-active substances that would serve as model compounds for histrionicotoxin (1).Application of the Noyori route to 2-substituted pyrroles was unsuccessful.In order to avoid difficulties in obtaining individual long-chain 4-keto aldehydes for the Robinson condensation of each new model compound a key tropane intermediate (8) was prepared instead.The first attempts to extend the chains of the mesyl ester of the diol (8b) and iodomethyltropanol (9b) by Grignard type coupling failed.Therefore we embarked on a Wittig reaction of the tropane-1-carbaldehyde (11) synthesized in high yield from the diol (8).Indeed, both pent-1-enyl- and pentyl-tropanols, (12) and (13) were obtained.Coupling with an acetylenic phosphorane led to the pent-1-enynyltropanol (14).A further new key compound, namely 3β-acetoxytropan-1-ylacetaldehyde (15) was also synthesized as a precursor to conjugated tropanyl enynes which would more closely resemble the natural product (1).
CONVENIENT DESULFONYLATION REACTIONS OF CYCLIC SULFONES WITH ULTRASONICALLY DISPERSED POTASSIUM
Chou, Ta-shue,You, Mei-Li
, p. 4495 - 4498 (2007/10/02)
Ultrasonically dispersed potassium, generated in toluene with an ultrasonic cleaning bath, was found to be efficient and regioselective for desulfonylation of cyclic sulfones.
NUCLEOPHILIC REACTIONS AT A VINYL CENTER. XI. EXCHANGE IN β,β-DICHLOROVINYL SULFONES BY FLUORINE AND IODINE
Shainyan, B. A.,Mirskova, A. N.
, p. 1022 - 1026 (2007/10/02)
We studied the reaction of β,β-dichlorovinyl sulfones with potassium fluoride in dimethyl sulfoxide and dimethylformamide, and with sodium iodide in acetone.In the reaction with KF the sulfones RSO2CH2CF3 and RSO2CH3 are formed in a ratio that depends on the amount of water in the organic solvent.Organyl methyl sulfones are not formed in absolute DMSO.A mechanism was proposed for the reaction of β,β-dichlorovinyl sulfones with KF.In the reaction with NaI one chlorine atom is replaced to give the β-chloro-β-iodosulfone.The kinetics of the reactions of ethyl β,β-dichlorovinyl sulfone and ethyl β-chloro-β-iodovinyl sulfone with sodium methoxide in methanol at 0-40 deg C was studied.From a comparison of the activation parameters it follows that in the first step of the reaction of the dichlorovinyl sulfone the chlorine atom cis to the sulfo group is replaced by CH3O-, while in the first step of the reaction of the chloroiodovinyl sulfone the chlorine atom trans to the sulfo group is replaced by CH3O-.The iodine atom is replaced at a rate that is three orders of magnitude slower than that of the chlorine atom.
Chemistry of peroxyacyl nitrates. Part III. The oxidation of thioethers by peroxyhexanoyl nitrate
Noort, Paul C. M. van,Vermeeren, Hans P. W.,Louw, Robert
, p. 312 - 321 (2007/10/02)
The reaction of peroxyhexanoyl nitrate, 1a, a homologue of the atmospheric pollutant "PAN", 1b, with some twenty thioethers, is described.At 0-25 deg C, common thioethers such as Et2S or PhSMe are rapidly converted into sulfoxides in high yields in a variety of solvents, ranging from pentane and chloroform to acetic acid, methanol and aqueous acetonitrile.Rates are essentially solvent-independent, although the reaction is subject to marked steric hindrance.Relative rates for five p-substituted thioanisoles in MeOH at 22 deg C, leading to a Hammett ρ-value of -1.7, show that the sulfur atoms display nucleophilic character.Electron-attracting groups on α-carbon, such as in PhSCCl3 and in MeSCH2OC(O)Ph, inhibit the formation of sulfoxide.Addition of EtSH lowers the yield of sulfoxide, producing instead EtSSEt and EtSNO.Oxidation of Me2S by 1a with the NO2 group labelled by 18O does not give rise to 18O-enriched DMSO.Comparison of (CH3)2S with (CD3)2S revealed an inverse kinetic H/D isotope effect.The products obtained from 1a vary with solvent.In the presence of water or EtSH, hexanoic acid is formed, while methanol gives rise to methyl hexanoate, and in pentane/hexanoic acid, hexanoic anhydride is produced.In aprotic solvents, significant amounts of CO2 are formed.These observations can best be rationalized on the basis of an intermediate sulfurane R1R2S(ONO2)(OCOR), (I), produced from thioether R1SR2 and 1a, in the first step.The fate of (I) under various conditions is discussed.Finally, the features of the oxidation of thioethers by peroxyacylnitrate are compared with those of acyl peroxides and peroxy esters.It is suggested that in each case formation of a sulfurane may well be the first step.
