Boundary conditions on the partitioning of deaminatively generated benzyl cations.

Autor: Darbeau RW; Department of Chemistry, McNeese State University, Lake Charles, LA 70609, USA. rdarbeau@mail.mcneese.edu, Heurtin DJ, Siso LM, Pease RS, Gibble RE, Bridges DE, Davis DL, Gbenekama DG, Darbeau NR
Jazyk: angličtina
Zdroj: The Journal of organic chemistry [J Org Chem] 2001 Apr 20; Vol. 66 (8), pp. 2681-5.
DOI: 10.1021/jo001458m
Abstrakt: Nitrogenous entity-separated ion pairs (NESIPs) containing benzyl cations, nitrogen gas, and pivalate anions were generated via thermal deamination of N-benzyl-N-nitrosopivalamide. Some decompositions were performed in methanolic solutions saturated with selected nucleophiles: acetate, azide, or cyanide ions. Trace amounts of benzyl cyanide and tolunitriles were observed; no corresponding products were detected in the acetate and azide cases. Other decompositions were performed in the absence of traditional solvent but in the presence of the nucleophilic salts; again only poor cyanide interception of the cation was observed. The poor showing of the nucleophilic ions, when present, is discussed in the context of the lifetime of the cation, effective nucleophilicity, and cage effects in deamination.
Databáze: MEDLINE