The cyclization in a basic medium of 2 (or 4)-chloroalkyl-4 (or 2) -hydroxyalkyl-1,3-dioxolanes leads to bicyclic acetals, the 3,6,8-trioxabicyclo[3.2.1]octanes, which are useful intermediates for synthesis, yielding notably functionalized 1,4-dioxanes. The nmr spectra of these heterobicyclics were studied. The geminal proton coupling constants permit oneto distinguish between five- and six-membered rings and the determination of couplings over several bonds (4J and 5J) yields information concerning the conformation of the model bicyclics.Two isomeric series of alkylated bicyclic acetals (3,7,9- and 4,7,9-trioxabicyclo[4.2.1]nonanes) are accessible by the following routes: (a) the intramolecular addition of a 4-hydroxy-alkyl group to the ethylenic double bond on the carbon atom a to C-2 in the 1,3-dioxolanes; (b) the dechlorohydration of 2-chloromethyl-4-hydroxyalkyl-1,3-dioxolanes; (c) the dehydration of dioxolane-diols. The main interest in these heterobicyclics is to prepare a seven-membered ring and to be able to prepare functionalized 1,4-dioxepanes. [Journal translation]