Gas-Solid Reactions in Organic Synthesis

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Abstract
Various new branches in the field of preparative scale organic gas-solid reactions (additions, substitutions, eliminations, condensations) are elaborated following a historical review. Polar gases (HBr, HCl, HI, HSCH3) react at 1 bar and temperatures from 40 to -80°C with gram quantities of crystalline N-vinylimides, -amides, -amines, and S-vinylthioethers usually in the Markovnikov orientation, but there is also an exception. The polar gases H2O and NH3 transform some of the crystalline addition products and H2O may be added catalytically to N-vinylphthalimide. All reactions run to high conversion rapidly and several of the highly sensitive products cannot be synthesized in solution. Liquid compounds like N-vinylpyrrolidinone which polymerize in solution crystallize and add polar gases smoothly upon freezing. Polar gases are applied to crystalline chalcone, cinnamic acid, and stilbenes with variable success. Pd-doped crystals are hydrogenated. Contrary to literature reports chlorine and bromine add to crystalline stilbene non-stereospecifically and without significant substitution. The results are discussed with respect to X-ray structures and powder diffraction patterns. Educt and product crystals are not isotypical. Various solid state decompositions are uncovered and the synthetic value is stressed.

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