Comparative Computational Study on the Reaction of Chloroacetone with Trimethylphosphite: Perkow versus Michaelis-Arbuzov Reaction Paths
| Autor: | Arturo Espinosa Ferao |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Michaelis–Arbuzov reaction
010405 organic chemistry Chemistry Perkow reaction Trimethyl phosphite 010402 general chemistry Photochemistry Rate-determining step 01 natural sciences 0104 chemical sciences chemistry.chemical_compound Chloroacetone Nucleophile Computational chemistry Electrophile Physical and Theoretical Chemistry Bond cleavage |
| Zdroj: | The journal of physical chemistry. A. 121(34) |
| ISSN: | 1520-5215 |
| Popis: | Two competitive mechanistic pathways for the reaction between trimethyl phosphite and chloroacetone are analyzed by high-level calculations. FMO analysis and HSAB-derived descriptors point to a preferential initial interaction of the nucleophile with the carbonyl group as electrophile. The Perkow reaction starts by chelotropic addition of the P atom to the carbonyl C-O bond, which is the rate determining step in THF solution, yielding an oxaphosphirane intermediate. The oxaphosphirane undergoes sequential P-C bond cleavage with elimination of chloride ion and O-demethylation. The alternative Michaelis-Arbuzov reaction involves nucleophilic displacement of chloride by the P atom and subsequent O-demethylation. The Perkow path is kinetically and thermodynamically favoured with respect to the Michaelis-Arbuzov path in the gas phase, but only kinetically preferred in polar (THF) solvents. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|