Oxidation of adamantanols

The oxidation of adamantan-2-ol, 2-methyladamantan-2-ol, adamantan-2-methanol and 2-butyladamantan-2-ol was studied using silver salts and bromine. Oxidation of 2-methyladamantan-2-ol was also studied using iodine and silver acetate. The products of the reaction have been reported. The reaction conditions were optimized and a free radical scavenger, thiophenol, was used to investigate the presence of any free radicals in the reaction solution. The results suggest the formation of adamantan-2-one from the reaction of adamantan-2-ol with silver carbonate and bromine. Adamantan-2-one and 2-oxa-adamantane were produced when silver acetate and bromine were used. No free radicals were detected in the reaction of the alcohol with silver carbonate and bromine. Free radicals were detected in the reaction of the alcohol with silver acetate and bromine. The reaction of 2-methyladamantan-2-ol with silver salts and bromine produced only minor quantities of methyl-tricyclo (3,3,1,0$\sp{3,7}$) non-3-yl ketone which was derivatized by 2,4-dinitrophenylhydrazine to yield ethanone, 1-(hexahydro-2,5-methanopentalen-3a(1H)-yl)-(2,4-dinitrophenyl) hydrazone. The reaction of the alcohol with iodine and silver acetate produced 3-di-iodomethylene-2-oxatricyclo (4,3,1,1$\sp{4,8}$) undecane. No free radicals were detected in this reaction. Reaction of 2-butyladamantan-2-ol with silver salts and bromine yielded the following compounds: cis and trans isomers of 2-oxa-3-(1-bromo butylidene) tricyclo (4,3,1,1$\sp{4,8}$) undecane, spiro (furan-2(3H),2$\sp\prime$-tricyclo (3,3,1,1$\sp{3,7}$) decane), dihydro-5-methyl, 2-butylidene tricyclo (3,3,1,1$\sp{3,7}$) decane and butyl tricyclo (3,3,1,0$\sp{3,7}$) non-3-yl ketone. No free radicals were detected in the reaction. The reaction of adamantan-1-methanol with silver acetate and bromine in carbon tetrachloride produced 1-acetoxyadamantane and undesired side products 1-chloroadamantane and 1-bromo-3-chloroadamantane. No free radicals were detected in the reaction. The reaction of adamantan-1-methanol with silver carbonate and bromine was conducted in hexane and the mass spectral analysis of the compound obtained in the reaction suggests that adamantan-1-methyl formate may have formed. Free radicals were detected in the reaction.