Nitration by oxides of nitrogen, part 3: Reactions of dinitrogen pentoxide with mono- and dioxacycloalkanes with 5-, 6- & 7-membered rings

✍ Scribed by P Golding; Rw Millar; NC Paul; Dh Richards

• Publisher: Elsevier Science
• Year: 1989
• Tongue: French
• Weight: 202 KB
• Volume: 30
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)93914-0

✦ Synopsis

Reaction of medium ring cyclic ethers with N205 in halogenated solvents gave only low yields of the corresponding dinitrates.

On the other hand, cyclic formals (1,3dioxolane and its homologues) gave moderate yields of unstable ring-opened products (hemiformal nitrates), together with variable amounts of rearranged products containing formate ester groups.

The formates are believed to result from attack of N205 on the heterooycle by a hydride abstraction route.

* All nmr samples were run as CDCI 3 solutions. Shifts are reported in ppm downfield from TMS (internal standard). ** All i.r. spectra were recorded as liquid films on KBr plates unless otherwise shown.

Absorbances were strong unless otherwise indicated (m/w) t Product mixtures containing both hemiformal nitrate and formate esters, although obtained in good (50-70%) yields, decomposed within several hr, precluding accurate yield measurements.