3050-62-2Relevant academic research and scientific papers
Reactions of Saturated and Unsaturated Tertiary Alkyl Halides and Saturated Secondary Alkyl Iodides with Lithium Aluminum Deuteride. Convincing Evidence for a Single-Electron-Transfer Pathway
Ashby, E. C.,Welder, Catherine O.
, p. 7707 - 7714 (1998)
Reactions of saturated secondary and tertiary alkyl halides with LiAlH4 (LAH) and LiAlD4 (LAD) have been carried out, and convincing evidence for a single-electron-transfer (SET) pathway has been obtained. Reactions involving saturated alkyl halides with LAD provide a model system in which a halogen-atom radical chain process is not possible, and therefore, the observation of large quantities (in some cases >90 percent) of protium in the reduction product provides strong evidence for a radical intermediate and a SET pathway. Specifically, the reaction of 2-iodooctane (10) with LAD produced octane with a deuterium content as low as 21 percent. Also, the reaction of the tertiary halide 2-iodo-2-methylheptane (15) with LAD produced 2-methylheptane (16) with a deuterium content as low as 8 percent. The effect of stoichiometry, halogen type, and reaction vessel surface on these reactions was studied. Reaction of the unsaturated tertiary halide 6-iodo-6-methyl-1-heptene (25) with LAD was also studied and was found to proceed predominantly by a SET process involving a halogen-atom radical chain process. The possibility of a carbocation intermediate in all of these reactions is discussed.
Photochemistry of racemic and resolved 2-iodooctane. Effect of solvent polarity and viscosity on the chemistry
Gao, Fang,Boyles, David,Sullivan, Rodney,Compton, Robert N.,Pagni, Richard M.
, p. 9361 - 9367 (2007/10/03)
The photochemistry of racemic and resolved 2-iodooctane was examined in cyclopentane, methanol, and 2-methyl-2-propanol, media with differing polarities and viscosities. The photochemistry of racemic 2-iodooctane was also examined in the gas phase. The photochemistry of 2-deuterio- and 1,1,1-trideuterio-2-iodooctane in cyclopentane and methanol was also studied. The photoreactions in cyclopentane, 2-methyl-2-propanol, and the gas phase occurred exclusively through homolytic reactions, while in methanol, they occurred predominantly (> 53%) through heterolytic reactions. By comparing the disappearance of the optically active substrate with its loss of optical activity, F, the fraction of the initially formed radical pair (RP) or ion pair (IP) resulting in product was determined for the three solvents. Because F contains contributions of both escape of the partners in the RP or IP into the bulk of the solvent and reaction within the RP or IP to yield products other than the substrate, there was no correlation between F and solvent viscosity. The F values will be valuable in assessing the photochemistry of 2-iodooctane in the same media with circularly polarized light.
