103864-76-2Relevant articles and documents
Base-induced Thermal Decomposition of Terpenoid Tosylhydrazones: Part I - Chemistry of Diazolongibornanes
Satyanarayana, N.,Nayak, U. R.
, p. 22 - 27 (2007/10/02)
The elusive progenitor neolongifolene (6) of Isolongifolene (2) has been synthesized (44percent yield) from longicamphor tosylhydrazone (8) by generating the crucial longibornyl-10-cation (5) under basic conditions in a protic (sodium-ethylene glycol) Bamford-Stevens reaction; Longicyclene (13, 15percent) and the ether-carbinol(14, 16percent) are the other products.Exposure of 6 to BF3.OEt2 in benzene transforms it to 2.Under aprotic conditions (sodium methoxide-diglyme) 8 gives longicyclene (13) as the major product (41percent) with a trace (5percent) of 6.When 8 is exposed to n-butyllithium in hexane, the novel longibornylene (21) (54percent) is formed.Generation of anelectron-deficient species at the C-4 position on the longibornane skeleton via 24->25->26 has been studied: a novel transannular carbene insertion product 30 is formed from 24 under aprotic conditions only .In this reaction olefins 27 and 28 are very minor (5percent); the major crystalline compound is the 4-oxolongibornane azine (31) (ca. 30percent).Refluxing 24 in ethylene glycol with the sodium salt of ethylene glycol yields 27 (15percent) and 28 (16percent), besides the oxygenated compound 29 (19percent).
