Nonbenzenoid aromatic systems. VIII. Buffered acetolysis of 2-(4- and 2-(6-azulyl)ethyl arenesulfonates and 3-(4-azulyl)-1-propyl nosylate. Examples of Ar3-5 and Ar3-6 mechanisms
Kinetics and mechanism of reactions between 2-phenylethyl benzenesulphonates and anilines in methanol
作者:Ikchoon Lee、Yong Hoon Choi、Hai Whang Lee、Byung Choon Lee
DOI:10.1039/p29880001537
日期:——
Kinetics of reactions between 2-phenylethyl benzenesulphonates and anilines in methanol at 65.0 °C have been studied; the mechanism is discussed on the basis of crossinteractionconstants, ρij. The overall reaction was found to proceed by a dissociative SN2 mechanism with a relatively small degree of aryl participation. The fraction of the phenonium ion intermediate captured by the nucleophile, aniline
研究了在65.0°C下2-苯乙基苯磺酸盐与苯胺在甲醇中的反应动力学。该机构被交叉相互作用常数,ρ的基础上讨论IJ。发现整个反应是通过离解的S N 2机理进行的,其中芳基的参与程度相对较小。亲核辅助途径中,亲核试剂苯胺所捕获的苯离子中间体的分数已显示出随着亲核试剂的增强而增加,并且对于芳基-建议在分子间S N i机理中出现四中心过渡态。无辅助路径。
Mild Electrochemical Deprotection ofN-PhenylsulfonylN-Substituted Amines Derived from (R)-Phenylglycinol
作者:Vincent Coeffard、Christine Thobie-Gautier、Isabelle Beaudet、Erwan Le Grognec、Jean-Paul Quintard
trifluoromethanesulfinates to trifluoromethanesulfones (“triflones”) was developed as a synthetic method for obtaining these compounds Their utility as reagents for the construction of carbon skeletons is explored with regard to reactions such as alkylation, conjugation addition, and cycloaddition. In addition, the conversion of triflones to more common functionality is described.
Photooxidation of Alkyl 4-Nitrophenyl Sulfides and Sulfoxides. Observation of Oxidative C-S Bond Cleavage and Rearrangement Reactions
作者:Daniel J. Pasto、Francois Cottard、Laurent Jumelle
DOI:10.1021/ja00099a015
日期:1994.10
Alkyl 4-nitrophenyl sulfides and sulfoxides undergo a self-photoinduced, singlet oxygen oxidation to produce a variety of products, including sulfonates and carbonyl compounds formed by the oxidative cleavage of the C-S bond of the sulfides and sulfoxides. Structural rearrangements are observed in the resulting carbonyl compounds formed in the oxidative cleavage of the C-S bond in the tert-amyl and 2-phenylethyl sulfides. An overall mechanism is proposed which involves the formation of peroxysulfoxides and peroxysulfones which undergo heterolytic C-S bond cleavage to form ion pairs which recombine to form persulfenates or persulfinates which then undergo photo- and/or thermally-induced homolytic O-O bond cleavage to form alkoxy and sulfinyl or sulfonyl radicals. The alkoxy radicals undergo beta-scission, disproportionation, or recombination with the sulfonyl radical to form the observed products. These C-S oxidative cleavage reactions have only been rarely observed in the earlier studies on the singlet oxygen oxidation studies of dialkyl sulfides, and are attributed, in part, to the presence of the 4-nitro group on the aromatic ring which greatly affects the susceptibility of the sulfur atom of the sulfides and sulfoxides toward nucleophilic attack, and on the reactivity of the peroxysulfoxides and peroxysulfones toward heterolytic cleavage of the O-S bond.