Organic Solid-State Reactions with 100% Yield

Abstract

Environmentally benign gas–solid, solid–solid, and intracrystalline (thermal and photochemical) reactions that give 100% yield of only one product are summarized for almost all important reaction types. Their mechanistic background is evaluated on the basis of supermicroscopic studies and crystal packing analyses, which helps in predicting good solid-state performance on the basis of phase rebuilding, phase transformation, and crystal disintegration and in engineering solid-state reactions in the case of difficulties. This allows one to profit from the bargain of the crystal packing for reactions with unsurpassed atom economy, in most cases without any auxiliary or purifying workup necessity, mostly close to room temperature and with short reaction times. The experimental techniques are described in some detail including the scale-up. Preparative use is made of known and new reactions, and many products cannot be prepared by any other technique or they are only stable in the solid state, but they are quantitatively obtained and ready for further syntheses due to their very high reactivity. “Solvent-free” reactions that pass through a liquid phase are generally excluded, but some comparisons with important quantitative stoichiometric melt reactions are made. Numerous new solid-state reactions are described here for the first time.