- Oxygen-17 Nuclear Magnetic Resonance Spectroscopy of Sulfoxides and Sulfones. Alkyl Substituent Induced Chemical Shift Effects.
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Oxygen-17 NMR chemical shifts have been determined for a number of cyclic and acyclic as well as aliphatic, olefinic, and aryl sulfoxides and sulfones.The (17)O NMR chemical shifts for the acyclic, aliphatic, and aromatic sulfoxides reported here absorb in the narrow range between δ -20 and +20, while the cyclic, aliphatic sulfoxides absorb between δ -13 and +66 relative to external (but naturally abundant) H2(17)O.The sulfonyl oxygens are deshielded relative to sulfinyl oxygens, exhibiting chemical shifts for acyclic and cyclic sulfonyl oxygens between δ 120 and 183 for the sulfones reported here.Diastereotopic sulfonyl oxygens exhibit chemical shift nonequivalence.Substituent-induced chemical shift effects by a methyl or methylene group on the sulfinyl and sulfonyl oxygens are discussed.
- Dyer, John C.,Harris, David L.,Evans, Slayton A.
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- ULTRA LONG-RANGE THROUGH-BOND INTERACTIONS IN DITHIASPIRANE DISULFOXIDES AS REVEALED BY PHOTOELECTRON SPECTROSCOPY
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Ultraviolet photoelectron spectra of the disulfoxides of 2,6-dithiaspiro heptane, 2,8-dithiaspiro decane, and 2,10-dithiaspiro tridecane show that there are substantial trough-bond interactions of the sulfur lone-pairs, ran
- Baker, A. D.,Scharfman, Renee,Stein, C. A.
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- Vanadium (IV) complexes with Schiff base ligands derived from 2,3-diaminopyridine as catalyst for the oxidation of sulfides to sulfoxides with H2O2
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Sulfoxides are substances used in the synthesis of valuable complexes and as drugs in medicine. Sulfides were selectively oxidized to the corresponding sulfoxides in proper yields with (H2O2) hydrogen peroxide applying a vanadium (IV) Schiff base complex in the role of a catalyst in glacial acetic acid in the role of solvent beneath mild conditions. For the conversion of sulfides to sulfoxides of various catalysts are applied. It must be noted that in our previous article, the vanadyl complexes (VOY1) synthesized were applied as a catalyst in the epoxidation of styrene (Zabardasti and Shangaie, J Iran Chem Soc 13:1875–1886, 2016) but in the new work, vanadium (IV) complexes with Schiff base ligands derived from 2,3-diaminopyridine were used to as catalyst for the oxidation of sulfides to sulfoxides with H2O2. To the most of our information, there is not any literature description on the selective oxidation of sulfides to sulfoxides by means of a vanadium (IV) Schiff base complex with N, O donor ligand derived from 2,3-diaminopyridine catalyst beneath these conditions. Dimethyl sulfide was chosen as a pattern substrate for optimization experiments. Oxidation of sulfides was functioned at 25?°C temperature in the attendance of a catalytic quantity of the vanadium (IV) complex or (VOY1) utilizing 20% H2O2 in the role of the oxidant, Scheme 1 and glacial acetic acid in the role of the solvent.
- Zabardasti, Abedien,Shangaie, Sayed Asad
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- Straightforward access to 4-membered sulfurated heterocycles: Introducing a strategy for the single and double functionalization of thietane 1-oxide
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A strategy for the stereoselective functionalization of thietane 1-oxide has been developed. Mono (C2 substituted) and doubly (C2, C4 disubstituted) functionalized thietanes have been obtained from the readily available thietane 1-oxide by using the corre
- Carroccia, Laura,Degennaro, Leonardo,Romanazzi, Giuseppe,Cuocci, Corrado,Pisano, Luisa,Luisi, Renzo
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- Inhibition by carboxamides and sulfoxides of liver alcohol dehydrogenase and ethanol metabolism
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Sulfoxides and amides were tested as inhibitors of liver alcohol dehydrogenase and ethanol metabolism in rats. With both series of compounds, increasing the hydrophobicity resulted in better inhibition, and introduction of polar groups reduced inhibition. Of the cyclic sulfoxides, tetramethylene sulfoxide was the best inhibitor as compared to the tri- and pentamethylene analogue and other compounds, and it may be a transition-state analogue. The most promising compounds, tetramethylene sulfoxide and isovaleramide, were essentially uncompetitive inhibitors of purified horse and rat liver alcohol dehydrogenases with respect to ethanol as substrate. These compounds also were uncompetitive inhibitors in vivo, which is advantageous since the inhibition is not overcome at higher concentrations of ethanol, as it is with competitive inhibitors, such as pyrazole. The uncompetitive inhibition constants for tetramethylene sulfoxide and isovaleramide for rat liver alcohol dehydrogenase were 200 and 20 μM, respectively, in vitro, whereas in vivo the values were 340 and 180 μmol/kg. The differences in the values may be due to metabolism or distribution of the compounds. Further studies will be required to determine if isovaleramide or tetramethylene sulfoxide is suitable for therapeutic purposes.
- Chadha,Leidal,Plapp
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- Reaction of singlet oxygen with thietane. A novel example of a self-catalyzed reaction which provides evidence for a thiadioxirane intermediate
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Singlet oxygen reacts with thietane, 1, to give the sulfoxide, 1SO, and a trace of sulfone, 1SO2. A mechanism which involves a novel substrate catalyzed interconversion of a persulfoxide and thiadioxirane intermediate is proposed. The data whic
- Clennan, Edward L.,Dobrowolski, Piotr,Greer, Alexander
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- Polyporphyrin thin films from the interfacial polymerization of mercaptoporphyrins
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Free-standing ultrathin films of aporphyrin homopolymer have been synthesized by interfacial polymerization of a mercaptoporphyrin. Coupling of 5,10,15,20-tetrakis(α-mercapto-p-tolyl)porphyrin at the water/ chloroform interface by copper acetate yields continuous, flexible films after drying with supercritical CO2. These films are amorphous and retain many characteristics of the monomeric porphyrin, such as the property that they may be metalated. Spectroscopic evidence suggests efficient cross-linking of thiols through disulfide coupling occurs in these polyporphyrins to form a network. Polymerization is accompanied by the introduction of carbonyl functionality, probably the transformation of residual thiols to thioacetate by metal-mediated reaction with excess acetate ion. As an example of the catalytic properties of these polymers, they are shown to promote photooxidation of thietane to the corresponding sulfoxide by sensitizing singlet oxygen production.
- Wen, Liqin,Li, Ming,Schlenoff, Joseph B.
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- A kinetic investigation, supported by theoretical calculations, of steric and ring strain effects on the oxidation of sulfides and sulfoxides by dimethyldioxirane in acetone
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The oxidations of alkyl 4-nitrophenyl, and dialkyl, sulfides and sulfoxides by dimethyldioxirane in acetone occur by concerted mechanisms but the sulfides respond differently from the sulfoxides to variation in the alkyl group. The reactions of the sulfides are inhibited by the steric effects of alkyl groups and these predominate over their inductive effects. By contrast, the reactions of these limited sets of sulfoxides are insensitive to alkyl steric effects but there is an indication of steric acceleration when a broader set of sulfoxides is considered. This behaviour is rationalised in terms of the differences in dipolar charge and its solvation between the ground state and transition state for the two types of substrate. The oxidations of cyclic sulfides and sulfoxides also exhibit contrasting behaviour. The reactivity of the sulfides is insensitive to ring strain but is explicable in frontier orbital terms whereas that of the sulfoxides is partly dependent upon the change in ring strain between reactant and product on oxidation, a difference rationalised in terms of the relative positions of the transition states in the reaction coordinates of the two oxidations. The reactivity of 4-, 5- and 6-membered cyclic sulfoxides is also dependent on a ring-size related property of the transition state. Calculations at the B3-LYP/6-31G* level of density functional theory on both ground states and transition states, including simulation of solvation by acetone, strongly support the mechanistic conclusions reached in this and earlier work.
- Hanson, Peter,Hendrickx, Ramon A. A. J.,Lindsay Smith, John R.
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supporting information; scheme or table
p. 65 - 84
(2011/01/07)
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- Observed and calculated 1Hand 13C chemical shifts induced by the in situ oxidation ofmodel sulfides to sulfoxides and sulfones
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A series of model sulfides was oxidized in the NMR sample tube to sulfoxides and sulfones by the stepwise addition of meta-chloroperbenzoic acid in deuterochloroform. Various methods of quantum chemical calculations have been tested to reproduce the observed 1H and 13C chemical shifts of the starting sulfides and their oxidation products. It has been shown that the determination of the energy-minimized conformation is a very important condition for obtaining realistic data in the subsequent calculation of the NMR chemical shifts. The correlation between calculated and observed chemical shifts is very good for carbon atoms (even for the 'cheap' DFT B3LYP/6-31G* method) and somewhat less satisfactory for hydrogen atoms. The calculated chemical shifts induced by oxidation (the δd values) agree even better with the experimental values and can also be used to determine the oxidation state of the sulfur atom (-S-, -SO-, -SO2 -). Copyright
- Dracinsky, Martin,Pohl, Radek,Slavetinska, Lenka,Budesinsky, Milos
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experimental part
p. 718 - 726
(2011/05/15)
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- Synthesis of 2-alkyl(aryl)thietanes
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Thietane and its 2-substituted derivatives were synthesized. A general preparation procedure for the synthesis of thietanes bearing alkyl and aryl substituents in the α-position was developed. Using this procedure, 2-substituted thietanes can be obtained from cheap and easily accessible raw materials in three steps. 2-R-Thietanes (where R = H, CH3, C 4H9, C5H11, C6H 13, C6H5) and the corresponding sulfoxides and sulfones were synthesized and examined. Intermediate and by-products of the synthesis were studied. Nauka/Interperiodica 2007.
- Volynskii,Shevchenko
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p. 109 - 117
(2008/02/03)
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- Nitric acid in the presence of supported P2O5 on silica gel affords an efficient and mild system for oxidation of organic compounds under solvent-free conditions
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This paper describes an efficient and easy method for oxidation of alcohols 1 and sulfides 2 to their corresponding carbonyl compounds 3 and sulfoxides 4 with nitric acid in the presence of supported P2O5 on silica gel under solvent-free conditions in high yields.
- Hajipour, Abdol R.,Guo, Lian-Wang,Ruoho, Arnold E.
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- Nitric acid in the presence of supported P2O5 on silica gel: An efficient and novel reagent for oxidation of sulfides to the corresponding sulfoxides
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This paper describes an efficient and easy method for oxidation of sulfides 1 to their corresponding sulfoxides 2 with nitric acid in the presence of supported P2O5 on silica gel under solvent-free conditions in high yields.
- Hajipour, Abdol R.,Kooshki, Behzad,Ruoho, Arnold E.
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p. 5503 - 5506
(2007/10/03)
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- 1-Butyl-4-aza-1-azoniabicyclo[2.2.2]octane dichromate (BAAOD): An efficient and novel reagent for oxidation of sulfides to the corresponding sulfoxides
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This article describes an efficient and easy method for oxidation of sulfides 1 to their corresponding sulfoxides 2 with 1-butyl-4-aza-1- azoniabicyclo[2.2.2]octane dichromate (BAAOD) under nonaqueous conditions in high yields.
- Hajipour, Abdol R.,Bagheri, Hamid R.,Ruoho, Arnold E.
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p. 2441 - 2446
(2007/10/03)
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- Mechanism of the Oxidation of Sulphides with Sodium Periodate
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The kinetics of the oxidation of RSAr, R2S, and (CH2)nS sulphides with NaIO4 yielding sulphoxides were investigated in ethanol-water solutions, and the rate equation v = k2 was found to be valid.The observed substituent (ρ -1
- Ruff, Ferenc,Kucsman, Arpad
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p. 683 - 688
(2007/10/02)
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- Carbon-13 Chemical Shifts of 3-Substituted Thietanes, Thietane 1-Oxides and Thietane 1,1-Dioxides
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Carbon-13 chemical shifts of the α- and β-carbon atoms for 12 thietane 1,1-dioxides, 9 thietane 1-oxides and 7 thietanes with a variety of 3-substituents are correlated according to the nat
- Dittmer, Donald C.,Patwardhan, Bhalchandra H.,Bartholomew, John T.
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