ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Heterodiamantanes and Structurally Related Compounds. Part III. The Pentacyclic C11-Diethers 5, 13-Dioxapentacyclo [6.5.0.02,6.03,12.04,9]tridecane, 4, 13-Dioxapentacyclo [6.4.1.02,7.03,10.05,9]tridecane, and 3, 10-Dioxapentacyclo [7.3.1.02,7.04,12.06,11]tridecaneIn connection with the studies on heterodiamantanes and structurally related compounds the three novel pentacyclic diethers 3-5 were prepared starting from the cyclopentadienone dimer 6. All four compounds have as common features a central carbocyclic 6-membered ring with four axial alkyl substituents and two oxygen functions in 1, 4 position. The required eleventh C-atom was introduced by dichlorocarbene addition either to 6 ( → 7) (Scheme 2) or to 29 ( → 28) (Scheme 4).Diether 3 was obtained by reduction of 26 (Scheme 2), a suitable precursor prepared either by intramolecular addition (24 → 26; Scheme 2) or substitution (30 → 26, 31 → 26; Scheme 4), as well as by direct substitution (44 → 3, 42 → 3; Scheme 5). Diether 4 was the product of a direct substitution (39 → 4, 36 → 4; Scheme 5). The synthesis of diether 5 was achieved from the addition product 51 (resulting from the alcohols 47 and 48; Scheme 6).Diether 4 is the thermodynamically least stable of the three diethers 3-5. It was easily isomerized to 5 on treatment with concentrated sulfuric acid in benzene whereas 3 and 5 remained unchanged under these conditions.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19810640406
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