114097-28-8Relevant articles and documents
Tosyl oxygen transfer and ion-neutral complex mediated electron transfer in the gas-phase fragmentation of the protonated N-phenyl p-toluenesulfonamides
Wang, Shanshan,Guo, Cheng,Zhang, Ningwen,Wu, Yanqing,Zhang, Huarong,Jiang, Kezhi
, p. 6 - 12 (2015)
In this work, an interesting oxygen transfer reaction in the gas phase dissociation of N-phenyl p-toluenesulfonamides has been explored by combination of the ESI-MS techniques and theoretical calculations. The protonated molecules underwent dissociation reactions, upon collisional activation, to give the [tosyl cation/aniline] ion-neutral complex (INC), in which the coupling reactions subsequently occurred to afford an ionic species of toluenesulfinate. The subsequent reactions of the toluenesulfinate species resulted in generation of the protonated 6-iminocyclohexa- 2,4-dienone or the 2-aminophenol radical cation, via cleavage of the SO bond. The above processes involved the tosyl oxygen transfer, and calculation results indicated that both the ortho- and the para- positions at the aniline ring are favorite for the tosyl oxygen transfer, and formation of radical cation involved an INC mediated electron transfer. The isomeric N-methylphenyl p-toluenesulfonamides behaved significant difference in the CID-MS spectra, indicating that the three isomers can be distinguished by ESI-MS.
Nitrosoarenes as Nitrogen Source for Generation of Sulfonamides with the Insertion of Sulfur Dioxide under Metal-Free Conditions?
Wang, Xuefeng,Lin, Yanmei,Liu, Jin-Biao,He, Fu-Sheng,Kuang, Yunyan,Wu, Jie
supporting information, p. 1098 - 1102 (2020/07/06)
A metal-free reaction of nitrosoarenes, aryldiazonium tetrafluoroborates, and sulfur dioxide under mild conditions is developed, giving rise to sulfonamides in moderate to good yields. This transformation proceeds efficiently at room temperature in the presence of cyclohexa-1,4-diene with a broad reaction scope. Good functional group compatibility is observed, including cyano, halo, and ester. A plausible mechanism involving a radical process with the insertion of sulfur dioxide is proposed, and cyclohexa-1,4-diene serves as the reductant during the transformation.
Triple Mode of Alkylation with Ethyl Bromodifluoroacetate: N, or O-Difluoromethylation, N-Ethylation and S-(ethoxycarbonyl)difluoromethylation
Polley, Arghya,Bairy, Gurupada,Das, Pritha,Jana, Ranjan
supporting information, p. 4161 - 4167 (2018/09/21)
In this report, we have explored a triple mode of chemical reactivity of ethyl bromodifluoroacetate. Typically, bromodifluoroacetic acid has been used as a difluorocarbene precursor for difluoromethylation of soft nucleophiles. Here we have disclosed nucleophilicity and base dependent divergent chemical reactivity of ethyl bromodifluoroacetate. It furnishes lithium hydroxide and cesium carbonate promoted difluoromethylation of tosyl-protected aniline and electron-deficient phenols respectively. Interestingly, switching the base from lithium hydroxide to 4-N,N-dimethylamino pyridine (DMAP) tosyl-protected anilines afforded the corresponding N-ethylation product. Whereas, highly nucleophilic thiophenols furnished the corresponding S-carboethoxydifluoromethylation product via a rapid SN2 attack to the bromine atom prior to the ester hydrolysis. This mechanistic divergence was established through several control experiments. It was revealed that difluoromethylation reaction proceeds through a tandem in situ ester hydrolysis/decarboxylative-debrominative difluorocarbene formation and subsequent trapping by the soft nucleophile-NHTs or electron-deficient phenolic ?OH groups. In the presence of DMAP the hydrolysis of the ester is perturbed instead a nucleophilic attack at the ethyl moiety provides the N-ethylation product. Hence, besides the development of a practical base-promoted N-difluoromethylation of amines and electron-deficient phenols, divergent reactivity pattern of inexpensive and user-friendly ethyl bromodifluoroacetate has been explored. (Figure presented.).
