Collect. Czech. Chem. Commun. 1990, 55, 2475-2480

Reactions of isomeric oxo-2(3)-oxahomodiamantanes. Dehydration of tetracyclic diols with concentrated phosphoric acid

Josef Jankůa, Sergei D. Isaevb, Leonid V. Cybulskiib, Luděk Vodičkaa and Alexander G. Yurchenkob

a Laboratory of Synthetic Fuels, Prague Institute of Chemical Technology, 166 28 Prague 6, Czechoslovakia
b Department of Organic Chemistry, Kiev Polytechnical Institute, 252056, Kiev, U.S.S.R.


Reduction of 11-oxo-10-oxapentacyclo[,13.02,7.06,12]pentadecane (lactone I) and 10-oxo-11-oxapentacyclo[,13.02,7.06,12]pentadecane (lactone II) with lithium aluminium hydride afforded 4-hydroxymethyl-12-hydroxytetracyclo[,7.06,11]tridecane (diol III) and 4-hydroxy-12-hydroxymethyltetracyclo[,7.06,11]tridecane (diol IV). Diol III reacted with concentrated phosphoric acid to give 3-methyltetracyclo[,6.05,10]tridecanone-9 (V) as practically the sole product. Diol IV afforded a complex mixture of products in which were identified 2-methyl-3-oxadiadamantane (VI; 57%), 10-oxa-2(3)-homodiadamantane (VII; 20%), 3-hydroxydiadamantane (VIII; 3%), diadamantane (X; 7%) and diadamantanone (IX; 2%).