1- ADAMANTANOL Adamantanone

Tnfluoroacetic anhydnde in a mixture with sulfuric acid is an efficient reagent for the sulfonylation of aromatic compounds [44] The reaction of benzene with this system in nitromethane at room temperature gives diphenyl sulfone in 61% yield Alkyl and alkoxy benzenes under similar conditions form the corresponding diaryl sulfones in almost quantitative yield, whereas yields of sulfones from deactivated arenes such as chlorobenzene are substantially lower [44] The same reagent (tnfluoroacetic anhydride-sulfunc acid) reacts with adamantane and its derivatives with formation of isomeric adamantanols, adamantanones, and cyclic sultones [45]... 

The preparative method presented is a slight modification of that reported by Geluk and co-workers.3-4 These authors also give a detailed account of the several reactions of adamantane, 1-adamantanol, and 2-adamantanol that take place in sulfuric acid.3-5 Adamantanone can be prepared essentially as herein described starting with 1-adamantanol instead of adamantane3—the yield is better (70%) and the reaction time is shorter, but adamantane is a more suitable starting material. 

Heteropolyanions have been shown to effectively catalyze the oxidation of alkanes into the corresponding alcohols and ketones [32], Thus, the compound [PW9037][Fe2Ni(0Ac)3] catalyzes [32b] the transformation ofadamantane into 1-adamantanol (76%), 2-adamantanol (12%) and 2-adamantanone (12%) with a total turnover number of 25 and a 29% conversion. The mixed-addenda hetero-... 

In a typical GLC scale experiment, adamantane (100 mg.) was added in excess to a CCI3F solution of ozone, and the mixture was set aside at —78°C. for 6 days. After removing residual ozone, the solvent was evaporated using a 30-inch Vigreux column. GLC of an ethereal solution of the residue on diglycerol (15% 2 meters 100°C.) demonstrated two main products, adamantanone (relative retention time t = 22) and 1-adamantanol (t = 48). In a similar experiment in which the solvent was a mixture of bromotrichloromethane (13 ml.) and CCI3F (21 ml.) (this mixture precipitated some solid CClsBr at — 78°C.), GLC analysis demonstrated the presence in the product of 1-chloroadamantane (t = 2.5), 1-bromoadamantane (r = 4), adamantanone (low yield), and 1-adamantanol. Five other components (t = 6, 12, 17, 23, 62) were not investigated. 

In a typical preparative scale experiment adamantane (1 gram) was oxidized with a CCbF solution of ozone at —78°C. for 8 days. After working up by the usual method, the residue was dissolved in ether and washed with aqueous sodium hydroxide. The ether layer on evaporation yielded a white crystalline solid (870 mg.). Elution with light petroleum (b.p., 30-40°C.) from neutral alumina (175 grams) gave unchanged adamantane (505 mg.), and 30% diethyl ether in petroleum eluted a ketonic fraction (63 mg.). Finally, pure ether eluted 1-adamantanol (227 mg.). TLC of the ketonic fraction separated the major component—adamantanone— from a minor unidentified component. 

At —40°C and under Ar, (43c) reacts with adamantane to afford 1-adamantanol (56%) and 2-adamantanone (20%). With H2O2 as a terminal oxidant, however, (43a) and its sterically more demanding analogue [Fe(6-Me2-BPMCN)(OTf)2] (44a) catalyzes enantioselective epoxidation and ci5-dihydroxylation of alkene substrates, demonstrating the metal-based nature of this transformation. Apparently, the use of HOOH vs. ROOH significantly alters the pathways adopted by the Fe —OOR (R = alkyl or H) adduct. The origin of such a functional shift needs further clarification. 

Kinetic isotope effect of cyclohexanol formation. l-adamantanol/(2-adamantanol + 2-adamantanone) corrected for the number of C-H bonds in a group. 

Catalyst 1-adamantanol /% 2-adamantanol 1% 2-adamantanone 1% terttary/secondary selectivity... 

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