Collect. Czech. Chem. Commun. 1979, 44, 2230-2237

13C NMR spectra of hydroxy adamantanes additivity in 13C NMR spectra of dihydroxyadamantanes

Jan Schramla, Harald Janckeb, Günter Engelhardtb, Luděk Vodičkac and Josef Hlavatýc

a Institute of Chemical Process Fundamentals, Czechoslovak Academy of Sciences, 165 02 Prague 6-Suchdol
b Central Institute of Physical Chemistry, Academy of Sciences of GDR, 1199 Berlin-Adlershof, G.D.R.
c Laboratory of Synthetic Fuels, Prague Institute of Chemical Technology, 166 28 Prague 6


The 13C NMR spectra of all monohydroxy and ditopic dihydroxy adamantane isomers were measured and the lines assigned. The numbers of the isomers and of the non-equivalent carbon atoms permitted a verification of the simple additivity of the shielding contributions of two hydroxyl groups on the rigid adamantane skeleton in the isomers without a possibility of a direct OH-OH interaction. If such interactions occur, deviations are found. The direction and magnitude of the deviations is in agreement with the current interpretation of 13C chemical shifts in other classes of cyclic compounds. It is concluded that the deviations are not caused by intramolecular hydrogen bonds. The deviations and the values of substituent chemical shifts offer some limited information about the origin of the shielding effects, especially of those dependent on stereochemistry and degree of substitution (γanti effect).