74693-82-6Relevant academic research and scientific papers
Adamantane Chemistry. Part 3. Abnormal Hypoiodite Reactions of 2-Substituted Adamantan-2-ols; Synthetic Routes to 4-Oxahomo- and 2-Oxa-adamantanes, and 7-Substituted-bicyclononan-3-ols
Black, Robin M.,Gill, G. Bryon
, p. 410 - 418 (2007/10/02)
Reaction of 2-methyladamantan-2-ol (1a) with lead tetra-acetate and iodine in boiling benzene did not yield the expected radical fragmentation product (3a), but rather a yellow, crystalline di-iodo-ether which was previously assigned structure (4) on the basis of chemical degradative evidence and on an apparent m/e 418 molecular ion (electron impact).Structure (4) is not supported by the spectroscopic data, and 13C n.m.r. studies on an isotopically enriched sample of the di-iodo-ether indicate the structure to be (5b).Re-investigation of the mass spectrum has revealed that the (fairly intense) molecular ion has m/e 416; previous assignment of the molecular ion to the m/e 418 peak (i.e.M+2) arose largely through the absence at that time of mass-marking facilities and the large interval between M.+ and the highest mass fragment ion.Similar hypoiodite reaction of 2-ethyl- (1b) and of 2-phenyl-adamantan-2-ol (1c) gave, respectively, the products (5a) and (7b), the latter arising from the hydrolysis during isolation of the iodo-ether (6c).Investigation of the chemistry of (5b) and (7b) has revealed useful preparative routes to substituted 4-oxahomo- and 2-oxa-adamantanes as well as 7-substituted-bicyclononan-3-ols.Several unusual reactions have been discovered, and reaction mechanisms are suggested.
