1246615-87-1Relevant articles and documents
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.).
Facile synthesis of α,α-difluoroalkyl aryl thioethers and their oxidative desulfurization-fluorination to trifluorides
Hugenberg, Verena,Haufe, Günter
experimental part, p. 942 - 950 (2010/10/02)
Alkyl 2-arylthio-2,2-difluoroacetates are synthesized in 52-77% yield from alkyl 2-(arylthio)acetates via two succeeding fluoro-Pummerer rearrangements using the reagents combination of N-haloimides as electrophiles and excess Py·9HF as the fluoride source at room temperature. Subsequent treatment of the formed fluorinated thioethers with the same reagents at elevated temperature gave alkyl trifluoroacetates in almost quantitative yield under optimised conditions by oxidative desulfurization-fluorination.
