Gas/Solid Reactions with Acetone

Abstract

AbstractGas/solid reactions of acetone vapor with neutral organic compounds, salts, or host crystals with strict exclusion of solvents are reported. This gas/solid technique largely avoids waste formation and saves resources. Starting hydrochlorides or hydrobromides are also synthesized by gas/solid techniques. Dihydrohalides of o‐phenylenediamines give 1,5‐benzodiazepines 3, aromatic and aliphatic 1,2‐aminothiols (o‐aminothiophenol, penicillamines, cysteine) yield five‐membered thiazolines and thiazolidines 7, 9, 11, 13. Virtually all carbonyl reagents of the primary amino type 14 give quantitatively the imino derivatives 15 and water. Salt formation may be helpful for increasing melting points and sometimes reactivity as in 8, 10, and 12 if surface passivation has to be overcome. In the case of solid 14 the free bases react equally well. Acetone (2) may be quantitatively removed from exhaust gases by using hydroxylaminium phosphate with formation of free acetone oxime at high flow rates. Inclusion of acetone into various hosts (17‐20, but not 16) is more efficient by imbibition from the gas phase than by crystallization from acetone as the solvent. This advantage may be utilized for gas separations. Some further gases (vapors) coexist in imbibed clathrates whereas others do not. The mechanisms of the gas/solid reactions are elucidated using atomic force microscopy (AFM). Phase rebuildings involve anisotropic movements of molecules over large distances and the formation of characteristic features. In some cases surface hydrates catalyze the gas/solid reaction. Solid‐state mechanisms for imbibition from the gas phase into host crystals with formation of clathrates are similar in nature to those of the covalent reactions. These results are correlated with known X‐ray crystal structures where available.