Desilylation of α-trimethylsilyl nitramines: The first nitramine α-anion

✍ Scribed by C.Peter Lillya; Thomas P. Sassi

• Publisher: Elsevier Science
• Year: 1989
• Tongue: French
• Weight: 144 KB
• Volume: 30
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)93323-4

✦ Synopsis

Fluoride-induced desilylation of a trimethylsilylcyclopropyl nitramine generated the first known nitramine a-anion, which was trapped in situ by electrophiles (H20, D20, and CH3CHO). In contrast, a trimethylsilylmethyl nitramine gave a product resulting from elimination of the elements of trimethylsilyl nitrite under identical reaction conditions. Secondary nitramines, 1, have long been known to undergo decomposition in refluxing aqueous base to primary amines and aldehydes. 1 This process presumably occurs by elimination of the elements of nitrous acid, followed by hydrolysis of the resulting imine. 2. Grignard reagents2 and alkyllithiums3 give products which suggest attack by the organometallic on the nitramine nitro group. No evidence to date has been observed for the formation of a stable nitramine a-anion, even upon reaction with hindered bases at low temperature. In these latter cases, the imines 2 are isolated.394