Kinetics and equilibrium of the nitroform-aldehyde-alcohol reaction

✍ Scribed by C.S. Rondestvedt Jr.; M. Stiles; A.L. Krieger

• Book ID: 104207239
• Publisher: Elsevier Science
• Year: 1963
• Tongue: French
• Weight: 860 KB
• Volume: 19
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(63)80055-1

✦ Synopsis

The reaction of nitroform.van aldehyde, and an alcohol yields a trinitroether in a reversiblereaction. The probable mechanism involves rapid formation of the hemiacetal, conversion to an alkoxycarbonium ion, and reaction with nitroformate anion.

The product is attacked by excess alcohol and is converted reversibly to acetal. Reaction of the acetal with nitroform is the most convenient method of preparing trinitroethers in high yield, since the water can be disposed of during the acetal preparation.

The kinetics of the acetal-nitroform and the trinitroether-alcoholreactionhave been studied in dioxane solution. The rate expressions obtained are interpreted in terms of a mechanism involving several equilibria centering around the alkoxycarbonium ion RCHOR'.