18931-59-4Relevant articles and documents
A Contribution to the Bisnorcaradiene Problem. Synthesis, Properties, and Structural Parameters of Bicycloundecapentaene - the Valence Isomer of Bisnorcaradiene
Duerr, Heinz,Pauly, Karl-Heinz,Fischer, Karl
, p. 2855 - 2871 (2007/10/02)
The problem of the existence of bisnorcaradiene (2) is discussed.MINDO/3 calculations show that the equilibrium of 2 (bearing substituents) with its valence isomers 5 and 21 is shifted towards 5 and 21 with about 11 kcal/mol.The photolysis of the spironorcaradiene/spirotropylidene equilibrium mixtures (78) followed by NMR-spectroscopy allowed the detection of the valence isomer 5.Irradiations of (78) on a preparative scale gave mixtures of hydrocarbons 5, 16, 17, 18, 19, and 20.In the case of the dibenzo derivative, the bicycloundecapentaene 5e could be isolated.NMR and CMR spectra as well as an X-ray analysis clearly established the structure to be 5e.Even at low temperature the bisnorcaradiene (2) could not be detected by NMR spectroscopy.Thermolysis of 5a - e giving 16 and 17 can be explained via an equilibrium 5221, i.e. a bisnorcaradiene must be involved as an unstable intermediate.The photorearrangement of (78) producing 5 (221) has most probably to be regarded as a di-?-methane rearrangement.