Some oxidations of hydrocarbons

Jones, Stephen Ronald (1976) Some oxidations of hydrocarbons. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The products of the oxidation of adamar_tane, bicyclo[3,3,1]nonane and diamantane by the oxidants cobalt(III) acetate, manganese(III) acetate dihydrate''and lead tetra acetate/chloride' ion in trifluoroacetic acid/dichloromethane have been investigated. In every case the predominant products are the monosubstituted bridgehead trifluoroacetates. Oxidation of 1-t-butytadamantane and a 1,1°-biadamantane' leads to products derived from substitution of a bridgehead hydrogen, rather than fragmentation of the carbon-carbon bond at the bridgehead position, which is the major pathway when these compounds are oxidized electrochemically in acetonitri7.e. The synthetic application of the le:,3(IV) oxidations in trifluoroacetic acid/dichloromethane have been investigated. High yields of the bridgehead mono-alcohols are obtained o oxidation with excess lead(IV) from a series of 1-alkyladamantar_esdiamantane and bicyclo[3,3,1] nonane after hydrolysis of the intermediate trifluoroacetates. 1-Substituted adartiantanes where the substituent is electron withdrawwing are less reactive and give either poorer coersions to products or do not react. The use of the intermediate trifluoroacctate to prepare a number of bridgehead substituted products is also described. Controlled- potential electrolyses of 1-alkyladomantanes in dryacetonitrile give N(3-alkyl-1 -adamantyl)acetamides by anodic substitution and N(1-adamantyl)acetamide by anodic fragmentation. When the alkyl group is ethyl, substitution is the only pathway and with isopropyl substitution is the preferred pathway, whereas with t-butyl fragmentation is predominant.Oxidation of adamantane in acetonitrile or trifluoroacetic acid at higher anodic potentials, as indicated from linear sweep vo1 tammetry, gives disbstituted products. Thus the major product from the anodic oxidation in acetonitrile is N,N'-(1,3-adamantyl)bisacetamide;`while in trifluoroacetic acid the major product after hydrolysis is 1,3-adamantanediol.

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