3185-68-0Relevant academic research and scientific papers
Oxidative desulfurization-fluorination reaction promoted by [bdmim][F] for the synthesis of difluorinated methyl ethers
Bouvet, Sébastien,Pégot, Bruce,Diter, Patrick,Marrot, Jér?me,Magnier, Emmanuel
, p. 1682 - 1686 (2015/03/14)
A new ionic liquid [bdmim][F] has been prepared and fully characterized. Its potential as a fluoride source for the desulfurization-fluorination process has been evaluated with success. The carbon-sulfur double bond of xanthates and thiocarbonates has bee
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.
experimental part, p. 1521 - 1537 (2011/06/11)
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.
A General Synthesis of Very High Specific Activity Tritiomethyl Iodide
Saljoughian, Manouchehr,Morimoto, Hiromi,Williams, Philip G.
, p. 1803 - 1808 (2007/10/02)
A general synthesis of highly tritiated or deuteriated methyl iodide has been elaborated.Tritiodehalogenation of trichloromethyl biphenyl-4-yl ether with tritium gas over Pd/C in ethyl acetate yields the corresponding tritiomethyl biphenyl-4-yl ether of a very high specific activity.Reaction of this product with hydroiodic acid hydrolyses the ether, and quantitatively liberates tritiomethyl iodide.Alkylation of a secondary amine with freshly generated tritiomethyl iodide gives a high yield, and demonstrates the utility of the reagent.Radio-HPLC analysis of the intermediate labelled ether and the amine product showed complete radiochemical purity with full retention of specific activity, and the specificity of labelling was confirmed in both products by 3H NMR spectroscopy.Preparatory chemistry was performed with deuterium gas and the deuteriated reaction products, and analogous analyses performed by HPLC and 2H NMR spectroscopy.
