66300-17-2Relevant academic research and scientific papers
Radical OfC transposition: A metal-free process for conversion of phenols into benzoates and benzamides
Baroudi, Abdulkader,Alicea, Jeremiah,Flack, Phillip,Kirincich, Jason,Alabugin, Igor V.
, p. 1521 - 1537 (2011)
We report a metal-free procedure for transformation of phenols into esters and amides of benzoic acids via a new radical cascade. Diaryl thiocarbonates and thiocarbamates, available in a single high-yielding step from phenols, selectively add silyl radicals at the sulfur atom of the CdS moiety. This addition step, analogous to the first step of the Barton-McCombie reaction, produces a carbon radical which undergoes 1,2 OfC transposition through an O-neophyl rearrangement. The usually unfavorable equilibrium in the reversible rearrangement step is shifted forward via a highly exothermic C-S bond scission in the O-centered radical, which furnishes the final benzoic ester or benzamide product. The metal-free preparation of benzoic acid derivatives from phenols provides a potentially useful alternative to metal-catalyzed carbonylation of aryl triflates.
Preparation of alkyl and aryl chlorodifluoromethyl ethers using BrF 3
Hagooly, Youlia,Sasson, Revital,Welch, Michael J.,Rozen, Shlomo
experimental part, p. 2875 - 2880 (2009/04/07)
Both alkyl and aryl chlorothioformates could readily be obtained from the corresponding alcohols and thiophosgene. These families of compounds were treated with BrF3 to form the corresponding alkyl and aryl chlorodifluoromethyl ethers in 60-85% yields. The method is suitable for constructing a variety of aliphatic as well as electron-deficient aromatic chlorodifluoromethyl ethers. The reactions proceed under mild conditions and short reaction times. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
