106540-19-6Relevant articles and documents
Base-induced Thermal Decomposition of Terpenoid Tosylhydrazones: Part II - Chemistry of 8-diazoisolongifolane/9-Diazoisolongifolene
Satyanarayana, N.,Nayak, U. R.
, p. 28 - 31 (2007/10/02)
7αH-8-Oxoisolongifolane (3) on refluxing with tosylhydrazine in CHCl3 gives the tosylhydrazone (7) of the more stable epimer 7βH-8-oxoisolongifolane (6).Refluxing 7 with NaOMe in diglyme gives the disubstituted olefin (15, 31percent), isolongifolene (2, 23percent) and the unusual alcohol (16, 7percent).Two pure C-8 epimers of the 2-hydroxyethyl ether 17 (27percent)/18 (6percent) are formed in the protic Bamford-Stevens reaction (Na in ethylene glycol) on 7; isolongifolene (2, 20percent) and 15 (13percent) are the other products.Attempted preparation of the tosylhydrazone (10) from 8-oxoisolongifol-9-ene (9) generates only the saturated tosylhydrazone (7) via a concomitant reduction of the the olefinic bond in 9 during the reaction. 9-Diazoisolongifolene (14) generated from the tosylhydrazone (13) under aprotic conditions gives the vinylcarbene-derived olefinic methyl ether epimers (20/21) in a major yield (47percent) while the the diene (19, 6percent) and the crystalline azine (22, 4percent) are also formed.Refluxing 13 with Na in ethylene glycol generates the C-9 ethylene glycol substituted compound (23) (54percent) with only a trace (4percent) of 19.
