Formation of 1,3-dioxolenium salts by the AdE-reaction of nitronium Tetrafluoroborates with allyl esters

✍ Scribed by I.G. Murskulov; A.G. Talybov; W.A. Smit

• Publisher: Elsevier Science
• Year: 1982
• Tongue: French
• Weight: 160 KB
• Volume: 23
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)87592-9

✦ Synopsis

Nitration of ally1 esters with N02BF4 proceeds with nucleophilic participation of carbonyl and yields nitro-substituted oxonium salts.

Nitration of alkenes with N02BF4 1 may yield nitroalkenes 'a, 1,2-fluoronitroderivatives lb or solvoadducts I'. Here we report results showing that the interaction of 1 with ally1 esters proceeds by electrophilic attack of NO: at the double bond with mcleophilic participation of the neighbouring carbonyl group leading to formation of nitrosubstituted oxonium salts.

Thus the nitration of methallyl esters 2a_c with 'J in liquid SO2 at -4O'C produces 2-alkyl-4-methyl-4-nitromethyl-l,3-dioxolenium tetrafluoroborates 3a_c formed as the only products (PIKR-data). These salts could be isolated as stable solids, their structure being ascertained by PMR data3 (see Table ).