15352-94-0Relevant academic research and scientific papers
Kinetics of Reactions of Cyclic Secondary Amines with 2,4-Dinitro-1-naphthyl Ethyl Ether in Dimethyl Sulfoxide Solution. Spectacular Difference between the Behavior of Pyrrolidine and Piperidine
Bunnett, Joseph F.,Sekiguchi, Shizen,Smith, Lewis A.
, p. 4865 - 4871 (2007/10/02)
The reactions named in the title, which form N-(2,4-dinitro-1-naphthyl) derivatives of these heterocyclic amines, occur in two distinct stages.In stage I, the spectrum of a ?-adduct intermediate develops at a rate which is measurable in a stopped flow apparatus; in stage II, it decays at a slower and easily measurable rate.The kinetics of both stage I and stage II have been studied.Pyrrolidine and piperidine are similar in their stage I behavior, but reactivity in stage II is about 11000 times greater in the pyrrolidine system.This huge difference between systems apparently so similar is judged to arise from steric interactions forced by differences in conformation between the amino moieties in the intermediate ? adducts as they release the nucleofuge.It calls into question the rate-limiting proton transfer interpretation of base catalysis in analogous aminodephenoxylation reactions in protic solvents.
