2955-69-3Relevant articles and documents
Structure-reactivity correlations in the aminolysis of aryl dithiomethyl- and dithiophenylacetates with anilines in acetonitrile
Oh, Hyuck Keun,Kim, Sun Kyung,Lee, Hai Whang,Lee, Ikchoon
, p. 1753 - 1757 (2001)
The kinetics and mechanism of the anilinolysis (XC6H4NH2) of dithio esters, RC(=S)SC6H4Z with R = C2H5 and C6H5CH2 are investigated in acetonitrile at 45.0 deg C. By application of various structure-reactivity correlations, selectivity parameters ρX, βX, ρZ, βZ and ρXZ are determined. The reactions are predicted to proceed stepwise with rate-limiting expulsion of the ArS- group. The dithio ester with R = C2H5 exhibits the fastest rate and the largest positive ρXZ value; this is interpreted to result from the strongest electron donating ability of the ethyl group in the intermediate and a crowded tetrahedral intermediate and transition state in which the nucleophile (X) and leaving group (Z) are in close proximity due to the bulky C2H5 group. Much faster rates are observed for the thiocarbonyl (C=S) rather than carbonyl (C=O) esters in the stepwise nucleophilic substitution reactions, which may be ascribed to the lower ?*C=S and ?*C-LG levels than those of the corresponding antibonding levels in the carbonyl esters. The normal kinetic isotope effects, kH/KD > 1.0, involving deuterated anilines suggest concurrent proton transfer with the expulsion of the ArS- leaving group in a four-center hydrogen bonded transition state.
Visible-Light Carbon Nitride-Catalyzed Aerobic Cyclization of Thiobenzanilides under Ambient Air Conditions
Bai, Jin,Yan, Sijia,Zhang, Zhuxia,Guo, Zhen,Zhou, Cong-Ying
supporting information, p. 4843 - 4848 (2021/06/28)
A metal-free heterogeneous photocatalysis has been developed for the synthesis of benzothiazoles via intramolecular C-H functionalization/C-S bond formation of thiobenzanilides by inexpensive graphitic carbon nitride (g-C3N4) under visible-light irradiation. This reaction provides access to a broad range of 2-substituted benzothiazoles in high yields under an air atmosphere at room temperature without addition of a strong base or organic oxidizing reagents. In addition, the catalyst was found to be stable and reusable after five reaction cycles.
Ketoximes to N-substituted thioamides via PSCl3 mediated Beckmann rearrangement
Pathak, Uma,Pandey, Lokesh Kumar,Mathur, Sweta,Suryanarayana
scheme or table, p. 5409 - 5411 (2009/12/08)
N-Substituted thioamides were accessed from ketoximes by utilising PSCl3 as a uniquely capable reagent to induce Beckmann rearrangement as well as to capture the intermediate nitrilium ion. The Royal Society of Chemistry 2009.