Oxidation of Adamantane to Adamantanols

The unique structure of adamantane justifies the interest for selective functionalization of this molecule in order to develop enhanced functional materials. In particular, selective synthesis of monoalcohols or diols represents the first step for the production of photoresist materials via esterification of the hydroxyl groups with acryUc and methacrylic acids [7]. 

Claimed conversion is higher than 90%, with a selectivity for alcohols depending on the cocatalyst of choice. Adamantanol production using this technology is commercialized at Daicel Arai plant in Japan. 

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The selective oxidation of adamantane to adamantanols with molecular oxygen has found practical application by using NHPI catalysis. The reaction has been proposed and patented by Ishii in collaboration with Daicel Chemical Company [8] and consists of the aerobic oxidation of adamantane in chlorobenzene or acetic acid at temperatures ranging from 75 to 85 °C for 7 h in the presence of 10% mol of NHPI and 0.5% mol of different metal salts, including Co(acac)2, Co(OAc)2, VO(acac)2, and V2O5 (Scheme 16.5). 

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