THE REACTIONS OF 2- AND 4-PICOLINE N-OXIDES WITH PHENYLACETIC ANHYDRIDE.
Abstract
The reactions of 2- and 4-picoline N-oxide with phenylacetic anhydride yield the oxidation-reduction products, benzaldehyde, carbon dioxide, picolines and small quantities of diphenylmaleic anhydride (XII), in addition to rearrangement products. The latter consist predominatly of 2-pyridinemethanol phenylacetate (X) and 2-phenylethylpyridine (XI) in the case of 2-picoline N-oxide and of 4-pyridinemethanol phenylacetate (XIV) and 4-phenylethylpyridine (XV) in the case of 4-picoline N-oxide. The product composition is unchanged when the reactions are performed in the presence of the radical trap m-dinitrobenzene. The rearrangement but not the oxidation products are thought to arise via the anhydrobase intermediates XIX and XX. The ester products in this case and in the corresponding acetic anhydride reactions are thought to be formed by non-radical paths while the phenylethylpyridines are probably formed by geminate recombination of benzyl and picolyl radicals which are produced by fragmentation of the anhydrobases XIX and XX. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1965
- Accession Number
- AD0625035
Entities
People
- John H. Fager
- Theodore A Cohen
Organizations
- University of Pittsburgh