Lactones in the bicyclo[2.2.2]octane series

Smith, Stephanie Sue (1981). Lactones in the bicyclo[2.2.2]octane series PhD Thesis, School of Molecular and Microbial Sciences, The University of Queensland. doi:10.14264/uql.2014.528

       
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Author Smith, Stephanie Sue
Thesis Title Lactones in the bicyclo[2.2.2]octane series
School, Centre or Institute School of Molecular and Microbial Sciences
Institution The University of Queensland
DOI 10.14264/uql.2014.528
Publication date 1981-01-01
Thesis type PhD Thesis
Supervisor Ray Carman
Total pages 121
Language eng
Subjects 0601 Biochemistry and Cell Biology
Formatted abstract
Several γ-lactones in the bicyclo[2.2.2]octane series have been prepared. The Diels-Alder adduct of cyclohexadiene and maleic anhydride gave an iodo-γ-lactone acid on iodination. Derivatives of this compound underwent reactions which clearly demonstrate the thermodynamic stability of the γ-lactone rather than the δ-lactone in this system. This result is contrary to a recent literature claim.

The known dilactone prepared from the iodolactone acid underwent reactions which not only confirmed the stability of the γ-lactone, but also indicated the unstable character of molecules with bulky unattached endo groups. The strain engendered by these proximal groups is relieved by epimerization of acid or ester groups to an exo position, or cyclization of two of the endo groups to give either an imide or a γ-lactone endo to the ring system.

The assignment of the structure of lactones in the bicyclo[2.2.2]-octane as either γ- or δ-lactones has been a problem in the past. The position of the carbonyl stretch frequency in the infrared has been found to be an unreliable indication of ring size. Proton nmr coupling constants for the γ-lactones synthesized in this project are consistent and compare favourably with reported values of similar γ-lactones. Carbon-13 nmr chemical shifts for the γ-lactones differ markedly from those reported for δ-lactones in this system and provide a convenient method of identification.
Keyword Lactones

Document type: Thesis
Collection: UQ Theses (RHD) - UQ staff and students only
 
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