Mechanism of solvolysis of phenacyl halides in various solvents

Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode

“…The studied reactions cover a broad spectrum of reactions, featuring a rich set of bifurcating pericyclic processes (1-12, 23-34, 47-48), 14,43,44,45,46,47,48,49,50,51,52,53,54,55,56 nitrene insertions (35)(36)(37)(38), 57 rearrangement and fragmentation reactions (13-16, 39), 13,58,59,60 the branching in nucleophilic additions and substitutions (17-22, 46), 11,61 and solvent-dependent isomeric Pummerer rearrangements (40-44). 12 Page 11 of 35 Chemical Science…”

“…Cycloadditions are the archetypal and most widely explored reactions within this field. 2 Besides them, the palette of organic reactions known to possess branching PES features includes nucleophile substitution vs. addition in α-haloketones, 12 Beckmann and Schmidt rearrangements vs. fragmentation, and isomeric Pummerer rearrangements. 13 Metal-catalyzed reactions and biosynthetic routes are now recognized examples of bifurcating reactions, highlighting the ever-growing importance of non-equilibrium reactivity.…”

Correlation of the rates of solvolysis of α-bromoisobutyrophenone using both simple and extended forms of the Grunwald-Winstein equation and the application of correlation analysis to related studies

“…An S N 2 process had previously been proposed [7] for this process based on a study in three aqueous ethanol solvents leading to a very low m value of 0.20±0.01 when the one-term (simple) Grunwald-Winstein equation [2,3] (Equation 1) was applied to the specific rates (first-order rate coefficients) at three temperatures in the 55-80 °C range, coupled with a very low Hammett ϱ value [7] of +0.35 being obtained for solvolyses in 80% ethanol at 70 °C of the parent and five meta - and para -substituted derivatives.…”

Bromo–nitro substitution on a tertiary α carbon—a previously uncharacterized facet of the Kornblum substitution

“…It has been frequently noted that nucleophilic substitution reactions alpha to a carbonyl show atypical properties. 23,24 They are, in particular, unusually fast, [25][26][27][28][29][30][31] though how much so depends on the nucleophile and other circumstances. [32][33][34][35][36][37][38][39][40] Various mechanistic reasons have been proposed for this.…”