100253-83-6Relevant articles and documents
Electronic effects in the N-nitrosation of N-benzylpivalamides
Darbeau, Ron W.,Pease, Rebecca S.,Perez, Edson V.
, p. 2942 - 2947 (2002)
A series of N-4-R-benzylpivalamides (R = MeO, Me, H, CF3, and NO2) was nitrosated using a standardized solution of N2O4 in CDCl3 at -40°C. The reactions, which produced the corresponding N-4-R-benzyl-
Reaction of essentially free benzyl cations with acetonitrile; synthesis of ethanimidic carboxylic anhydrides and unsymmetrical diacylamines
Darbeau, Ron W.,White, Emil H.,Nunez, Nicholas,Coit, Brian,Daigle, Mark
, p. 1115 - 1120 (2000)
Benzyl cations were generated via the thermal decomposition of N-benzyl- N-nitrosopivalamide in acetonitrile and acetonitrile-water mixtures at 25 °C. The first-formed (primary) benzylating agent, the benzyl cation, was scavenged competitively by pivalate (trimethyl acetate) ion to yield benzyl pivalate, by acetonitrile to yield the corresponding N-benzylnitrilium ion, and by water (when present) to yield benzyl alcohol. The nitrilium ion underwent a cascade of reactions to yield an array of products whose identities and relative yields as a function of time were used to elucidate the mechanistic paths involved. Thus, the N-benzylnitrilium ion reacted with pivalate ion to yield the Z-isomer of N-benzylethanimidic pivalic anhydride, followed by its conversion into the E-isomer. This article appears to be the first to document compounds of this type. The E-isomer is labile under the reaction conditions, rearranging into N-acetyl-N-pivalylbenzylamine. In the presence of water as a diluent, a significant fraction of the nitrosoamide was hydrolyzed to benzyl alcohol; hydrolysis of the nitrilium ion yielded N- benzyl acetamide. The yield of hydrosylates was directly proportional to the mole fraction of water in the medium.
