116849-48-0Relevant articles and documents
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 (2011/06/11)
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.
Radical 1,2-o→c transposition for conversion of phenols into benzoates by o-neophyl rearrangement/fragmentation cascade
Baroudi, Abdulkader,Alicea, Jeremiah,Alabugin, Igor Y.
supporting information; experimental part, p. 7683 - 7687 (2010/08/22)
Figure Presented Radical merry-go-round! Diaryl thiocarbonates, available in a single step from phenols, can be directly transformed into benzoates by a new radical cascade that transposes O and C atoms at the aromatic core. The cascade bypasses the common Barton McCombie fragmentation in favor of the usually unfavorable O-neophyl rearrangement, which is rendered irreversible and efficient by a highly exothermic C-S bond scission in the O-centered radical (see scheme; FG = functional group).
Kinetics and mechanism of the aminolysis of phenyl and 4-nitrophenyl ethyl thionocarbonates
Castro, Enrique A.,Cubillos, Maria,Santos, Jose G.
, p. 3501 - 3505 (2007/10/03)
The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0°C, ionic strength 0.2 M (KCl). Under amine excess, pseudo-first-order rate coefficients (kobsd) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T±) and an anionic (T-) one, whereby amine catalysis (deprotonation of T± to give T-) is kinetically important. Both the pKa of T± and the rate coefficient for proton transfer (k3 ca. 1010 s-1 M-1) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dithiocarbonates (PDTC and NPDTC, respectively). The Broensted type plots for amine basicity have slopes βN ca. 0.2 for rate-determining amine attack (k1) and βN ca. 0.8 for amine expulsion from T± (k-1), in accord with the βN values found in similar aminolyses. The general base catalysis by amine found in the aminolysis of NPTOC, in contrast with the lack of such catalysis in the aminolysis of 4-nitrophenyl methyl carbonate, is explained by a smaller rate coefficient for expulsion of 4-nitrophenoxide (k2) from T±(which competes with amine deprotonation of T±) relative to the same expulsion from the analogous oxy intermediate.
