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 IV. The Pentacyclic C12-Diethers 5, 14-Dioxapentacyclo[7.5.0.02,6.03,13.04,10]tetradecane, 4,14-Dioxapentacyclo[7.4.1.02,8.03,11.05,10]tetradecane, 3,11-Dioxapentacyclo[8.31.02,8.04,13.07,12]tetradecane, and 3,10-Dioxapentacyclo[7.3.1.14,12.02,7.06,11]tetradecane (3,10-Dioxadiamantane)In connection with the studies on heterodiamantanes and structurally related compounds the four novel pentacyclic diethers 6-9 were prepared starting from the cyclopentadienone dimer 12, All five compounds have as common features a central carbocyclic 6-membered ring with four axial alkyl substituents and two oxygen functions in 1,4-positions. The required twelfth C- atom was introduced by dichlorocarbene addition to 11 (the rnonocarbene adduct of 12) (→ 10, Scheme 2). The two three-membered rings in 10 had to be opened step wise. Controlled thermolysis of 10 yielded the chloride 13 and the acetate 14, respectively, from which the alcohols 16, 17 and 20 as well as the acetates 22 and 23 were obtained by reduction (Scheme 2). The remaining second ring was opened again thermally either to tricyclic compounds as 22 → 25 + 26, 23 → 27 + 28 or under simultaneous ether formation to tetra-cyclic compounds as 16 → 29 + 30, 17 → 32 + 33, 20 → 34 + 35 (Scheme 3). The two compounds 29 and 30 were also obtained from 37, the dichlorocarbene adduct of the tricyclic C11-ether 36 (Scheme 4). These tri- and tetracyclic compounds 25-30 and 32-35 were suitable intermediates for the syntheses of all four pentacyclic diethers 6-9.Diether 6 was prepared from 25, 26, 29 as well as 30 via 38 (Scheme 5), and from 29 by the route depicted in Scheme 6. By a procedure analogous to the latter one, diether 7 was obtained from 30 (Scheme 6). Diether 8 was the result of transformations starting from either 27, 28, 32 or 33 (Scheme 7). The synthesis of diether 9 (3,10-dioxadiamantane), the thermodynamically most stable of the four diethers 6-9, was achieved in three different ways : ring closure starting from the highly substituted tricyclic compounds 25 and 26 (Scheme 9), skeletal rearrangement of the group-A
Additional Material:
6 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19820650331
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