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41.
《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2441-2446
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. 相似文献
42.
43.
S. Trippett 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):89-98
Abstract In order to dicuss mechanism in organophosphorus chemistry a number of assumptions have to be made. Among them are: (a) that substitutions at tetrahedral phosphorus proceed via five-coordinate intermediates; (b) these intermediates are trigonal bipyramidal; (c) they are formed by apical attack and decompose by apical loss; and (d) if sufficiently long-lived, they may undergo permutational isomerization, that is the ligands may alter their relative dispositions round the phosphorus, before going on to products or back to reactants. Assuming that the course of a given substitution is dictated primarily by thermodynamic considerations, in order to understand the course of that substitution one needs to know how to assess the relative stabilities of the four isomeric tbps (trigonal bipyramids) that can be formed initially and of the others that could be formed by subsequent isomerization, the barriers to those isomerizations, and the relative rates of the various product-forming steps. We have concentrated on the first of these factors and this lecture describes our attempts to provide the necessary data. The energy difference between two isomeric tbps can be analyzed in terms of changes in the relative apicophilicities1 of the groups occupying apical positions, changes in ring-strain as small rings move between apical-equatorial and diequatorial positions, and changes in steric strain. I shall consider each of these in turn. Ligand subset symmetry may also have to be taken into account.1,2 相似文献
44.
Giovanna Delogu Ottorino De Lucchi Maria Paola Fois Giovanni Valle 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):417-425
Abstract Ketimines la-d derived from ortho-aminosubstituted phenylthioethers were prepared in order to determine the degree of chirality transfer from the chiral auxiliary to the sulfur atom in the formation of the sulfoxide or to the α-carbon atom in the reaction of the anion with alkyl halides or benzaldehyde. Oxidation to the sulfoxide occurred with little or no asymmetric induction. The crystalline benzyl sulfone 4c was deprotonated by alkyllithium or Grignard reagents and reacted with alkyl halides and benzaldehyde, in all cases with little to fair transfer of chirality. The major diastereoisomer from methylation of the anion of 4c with methyl iodide, was isolated, and afforded the enantiomerically pure amine 5 after removal of the chiral auxiliary. An X-ray structure determination of 4d allowed the assignment of the absolute configuration of the asymmetric carbon and revealed that the conformation of the ketimine in the crystal state is not homogeneous. 相似文献
45.
Cheng-Xia Tan Li-Yan Pan Guo-Fu Zhang Yong-Shu Li 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):16-21
Abstract A convenient and facile catalytic oxidation of thiols to the corresponding disulfides is described using CoSalen as the catalyst and air as the oxidizing agent. This new approach provides an efficient method for the preparation of symmetrical disulfides in high yields and under mild conditions. [Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Spectroscopic Identification of Products 3a–3l.] 相似文献
46.
47.
George Bratulescu 《合成通讯》2013,43(16):2748-2752
Aromatic aldehydes were synthesized by oxidation of corresponding halides with dimethyl sulfoxide on potassium bicarbonate by microwave irradiation. Short reaction time and high yields were obtained. 相似文献
48.
A simple and efficient protocol for preparing benzimidazoles via Fe(NO3)3 · 9H2O-catalyzed aerobic oxidation reaction of imine derivatives with o-phenylenediamine. This process uses air as an economical and green oxidant, tolerates a wide range of substrates, and affords the targeted benzimidazoles in moderate to excellent yields. 相似文献
49.
Lalthazuala Rokhum 《合成通讯》2013,43(4):548-552
Abstract A simple, straightforward, and environmentally benign protocol for the synthesis of adipic acid from oxidation of cyclohexanone with Oxone® in the presence of 0.5 mol% RuCl3 · nH2O is reported. The reaction completes within a very short time even at room temperature. The generality of the method is shown successfully for synthesis of other C-5 to C-8 dicarboxylic acids. 相似文献
50.
C. Zhu A. Javed P. Li G. Y. Liang P. Xiao 《Surface and interface analysis : SIA》2013,45(11-12):1680-1689
In this study, the initial oxidation behaviour of laser‐treated Al/NiCrAlY bond‐coat is investigated. Two approaches, (i) Al film sputtering on the surface of bond‐coat and (ii) laser treatment, have been taken to enhance the oxidation resistance of NiCrAlY bond‐coat. Experimental results showed that after laser treatment, the Al/NiCrAlY bond‐coat exhibited a columnar dendritic microstructure without cracks and voids. A dense and continuous α‐Al2O3/Cr2O3 multilayer was found to form on the bond‐coat surface. Results on the cyclic oxidation at 1200 °C (for time ≤ 204 h) revealed that the laser‐treated Al/NiCrAlY bond‐coat exhibited better oxidation resistance compared to as‐sprayed NiCrAlY, Al/NiCrAlY and laser‐remelted NiCrAlY bond‐coat. The formation of θ‐Al2O3, NiO, Cr2O3 and NiCr2O4 spinel oxides was observed to be suppressed due to the preformed α‐Al2O3 scale during initial oxidation on the surface of laser pre‐oxidized Al/NiCrAlY bond‐coat. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献