Milieux hyperbasiques: préparation de carbanions en α d'amides N,N-disubstitués. Synthèse de β- et γ-hydroxyamides et de γ-butyrolactones

Abstract

The α anions of N,N-disubstituted carboxamides can be conveniently prepared by treatment with "activated" lithium dialkylamides in HMPT. They react with aldehydes and ketones and lead to β-hydroxyamides; furthermore the ring opening of epoxides affords γ-hydroxyamides which may be cyclized in situ to γ-butyrolactones

Vapor–Liquid Equilibria, Excess Enthalpy, and Density of Aqueous γ-Valerolactone Solutions.

“…(a) Temperature range 275–470 K; (b) enlargement of the previous figure for 390–322 K temperature range with the literature values for the GVL vapor pressure. The shown numbers of the points (Δ) correspond to the following references: 1, 2, 3, 4, 5, 6, 7, and 9 …”

“…The DIPPR pressure correlation 5 predicts a higher pressures at a low temperatures in comparison with the Emel'yanenko's correlation, but the Emel'yanenko's correlation underestimates pressures at high temperatures. A new GVL pressure correlation was optimized by the minimization of the deviation between the calculated pressures and experimental 36 2, 37 3, 38 4, 39 5, 40 6, 41 4. Two types of equations were used for the fitting.…”

Reactivity of Oxiranes with Organolithium Reagents

“…To circumvent this lack of reactivity, the use of malonates or sulfur-containing dianions 204 has proven to be efficient (Scheme 44). By contrast, lithium enolates derived from tertiary amides do react with oxiranes 193,213,214 . The diastereoselectivity in the reaction of simple amide enolates with terminal oxiranes has been addressed and found to be low 215 (Scheme 45).…”