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Heterodiamantanes and Structurally Related Compounds. Part II: The Pentacyclic C 10 ‐Diethers 5,12‐Dioxapentacyclo [6.4.0.0 2,6 .0 3,11 .0 4,9 ]dodecane and 4,12‐Dioxapentacyclo[6.3.1.0 2,7 .0 3,10 .0 5,9 ]dodecane
Author(s) -
Ammann Willi,
Jäggi Franz Josef,
Ganter Camille
Publication year - 1980
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19800630730
Subject(s) - chemistry , intramolecular force , diol , benzene , stereochemistry , dimer , alkyl , sulfuric acid , epoxide , medicinal chemistry , ring (chemistry) , acid catalysis , organic chemistry , catalysis
In connection with studies on heterodiamantanes and structurally related compounds the two novel pentacyclic diethers 9 and 10 were prepared starting from the photo‐dimer 8 of cyclopentadienone. All three compounds have as common features a central carbocyclic 6membered ring with four axial alkyl substituents and two oxygen function in 1,4‐position. The diether 9 was obtained on the one hand from the intermediate tetracyclic unsaturated alcohol 23 by intramolecular addition, catalyzed either by acid or base (scheme 3) , and on the other hand from the tetracyclic diol 32 or the dibromoketones 34 ( via 38 ) and 35 ( via 39 ) by intramolecular substitution (schemes 4 and 5). The synthesis of the isomeric diether 10 was achieved by intramolecular substitution of the tetracyclic diol 33 (scheme 4). Diether 9 is thermodynamically more stable than 10 . The latter was easily isomerized to the former on treatment with concentrated sulfuric acid in benzene.