Displacements at the Nitrogen of Lithioalkoxylamides by Organometallic Reagents

Article abstract of DOI:10.1021/jo00284a034

The conversions of N-(o-bromobenzyl)methoxylamine to N-acetylbenzoazetine (1), of N-<3-(o-bromophenyl)-n-propyl>methoxylamine to N-acetyltetrahydroquinoline (2), and N-<4-(o-bromophenyl)-n-butyl>methoxylamine to N-acetylbenzazapine (3) illustrate the use of this displacement reaction to form nitrogencontaining rings in an exocyclic reaction mode.An X-ray structural determination is reported for 1.The formations of anilides by amination of aromatic organolithium reagents with lithium methoxylamide is also reported.Lithium reagents are found to be more effective than Grignard, copper, or zinc reagents in these displacement, and the yields decrease as the size of the substituents around nitrogen increases.The endocyclic restriction test is used to show that this displacement on nitrogen cannot occur within the endocyclic confines of a seven-membered ring.A S_N2 reaction pathway in a lithium complex is considered to be supported by these results.