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• 281-23-2 adamantane 
• 75-05-8 acetonitrile 

Relevant academic research and scientific papers

Highly selective N- and O-functionalization of adamantane utilizing nitrogen oxides. Kyodai-nitration of aliphatic hydrocarbons

In the presence of ozone at -78°C, nitrogen dioxide selectively reacts rapidly with adamantane at the bridgehead position to give the corresponding nitration product, while in the presence of methanesulfonic acid at 0°C, dinitrogen pentoxide readily reacts with this hydrocarbon at the same position exclusively to afford the corresponding nitrooxylation product, the yields of both products being quite satisfactory.

Ozone-mediated nitration of adamantane and derivatives with nitrogen dioxide: Selectivity in the hydrogen abstraction by nitrogen trioxide and subsequent coupling of the resulting carbon radicals with nitrogen dioxide

In the presence of ozone at -78°C, nitrogen dioxide reacts rapidly and selectively with adamantane at a bridgehead position to give the corresponding nitro derivative as the sole major product. The relative reactivity has been determined for a series of 1-substituted adamantanes, which reveals that electron-withdrawing substituents exert a considerable influence on the ease of substitution at the γ-position as well as the distribution of the N- and O-functionalized products. The results may be rationalized in terms of the initial hydrogen abstraction by nitrogen trioxide, followed by rapid trapping of the resulting adamantyl radicals with nitrogen dioxide.

Oxidative functionalization of adamantane and some of its derivatives in solution

1,2,4,5-Benzenetetracarbonitrile (TCB) is irradiated in the presence of adamantane (1) and some of its derivatives. The singlet excited state of TCB is a strong oxidant, and there is various evidence, including time-resolved spectroscopy, to prove that SET from the alkane to TCB1* takes place and yields the corresponding radical ions. The adamantane radical cation deprotonates from the bridgehead position, and the resulting radical couples with TCB-*. Deprotonation via the radical cation occurs with a number of substituted adamantanes and remains the exclusive or predominating reaction also with derivatives containing a potential electrofugal group, such as one of the following carbocations: t-Bu, CH2OMe, CH2OH (notable here is that C-H deprotonation is more efficient than O-H deprotonation). A carboxy group is lost more efficiently than a proton, however. In contrast, detaching of such cations is the main process when the radical cations of substituted adamantanes is produced anodically. This different behavior is explained on the basis of thermochemical calculation and of the different environments experienced by the radical cation in the two cases, viz reaction from the solvated radical cation in the first case and from the substrate adsorbed on the anode in the latter one. 1-Methoxyadamantane deprotonates from the methyl group, a reaction explained by the different structure of the radical cation. On the other hand, the radical NO3*, conveniently produced by photolysis of cerium(IV) ammonium nitrate, reacts by hydrogen abstraction with selective attack at the bridgehead position and little interference by substituents and thus offers a useful way for the selective oxidative functionalization of adamantanes.

PHOTOCHEMICAL OXIDATION AND AUTOXIDATION OF SOME CYCLOALKANES PROMOTED BY CERIC AMMONIUM NITRATE IN ACETONITRILE

The oxidation and autoxidation of adamantane, norbornane and cyclohexane can be photochemically promoted by ceric ammonium nitrate in acetonitrile at room temperature, both processes being extremely efficient and selective with adamantane.