72569-85-8Relevant academic research and scientific papers
THERMOLYSIS OF THE PROPELLANES. MECHANISM FOR THE THERMOLYSIS OF BICYCLOHEXANES.
Wiberg, Kenneth B.,Matturro, Michael G.
, p. 3481 - 3484 (1981)
The thermolysis of the propellene proceeds with good first order kinetics and gives Ea = 46 kcal/mole.The increase in Ea over that for bicycloyhexane and the propellane provides evidence for the mechanism of these thermolyses.
Kinetics of the thermolysis of [n.2.2]propellanes and related compounds. Mechanism of the thermolysis of bicyclo[2.2.0] hexanes
Wiberg, Kenneth B.,Caringi, Joseph J.,Matturro, Michael G.
, p. 5854 - 5861 (2007/10/02)
The thermolyses of a series of 1,4-bridged bicyclo[2.2.0]hexanes have been studied. With bridges having three or more carbons, the compounds have higher activation energies than for bicyclo[2.2.0]hexane, indicating that the bridge prevents the formation of a chair cyclohexane-1,4-diyl, forcing the reaction to proceed via an orbital symmetry disallowed process. It appears likely that [2.2.2]propellane and its derivatives react via the same mechanism, and the driving force from strain relief appears to be the major factor in reducing its activation energy. The thermolysis of the relatively unstrained [3.3.2]propellane occurs at a significantly higher temperature and leads to a mixture of products which also were found in the thermolysis of 1,5-dimethylenecyclooctane. The thermolysis of the latter at 420°C formed the propellane. The strain relief in the cleavage of the central bond in this group of propellanes were estimated via a combination of ab initio and molecular mechanics calculations and was found to be correlated with the changes in activation energy. The thermolyses of [3.2.1]- and [4.2.1]propellanes also are reported and were found to be less reactive than expected on the basis of strain energy relief.
Synthesis of Bicyclic Non-conjugated Polyenes. Stereochemistry and Transanular Interactions
Martin, Hans-Dieter,Heller, Constanze,Mayer, Bernhard,Beckhaus, Hans-Dieter
, p. 2589 - 2600 (2007/10/02)
The synthesis of the bicyclic polyenes 8 - 11 has been achieved by cleavage of the strained ?-bonds of suitable cyclopropanedimethanols 14b/15b and cyclobutanedimethanol-bis(methanesulfonates) 16c/17c using P2I4 (14b/15b) or Zn/KBr (16c/17c), respectively.From an inspection of the 1H NMR spectra a preferred endo-conformation (chair) for 8 and a twisted structure (twist-chair) for 10 is proposed.The predicted extent of transanular conjugation for these geometries is in accordance with the photoelectron spectroscopic measurements.
