36639-40-4Relevant academic research and scientific papers
Experimental/computational study of the electrochemical oxidation of cyclooctatetraene in protic media. Solvent effects
Connors, Grayson,Wu, Xin,Fry, Albert J.
, p. 1671 - 1674 (2008/02/02)
Electrochemical oxidation of cyclooctatetraene (COT) in methanol affords a ring-contracted acetal in high yield. Ring contraction is only a minor process in acetic acid. Ab initio computational methods were applied to understand and explain the effect of solvent. The computations show considerable differences between the thermodynamic and kinetic preferences for ring contraction vs bicyclo[4.2.0] product formation.
Influence of XCH2 and X2CH Rests upon Equilibrium Compositions Among Monosubstituted Bullvalenes and Cycloheptatrienes
Zeiger, Roland,Sarma, Keshab,Schroeder, Gerhard
, p. 2889 - 2894 (2007/10/02)
Cycloheptatrienylmethyl methyl ethers (5) and cycloheptatriene-carboxaldehyde dimethyl acetals (7) were equilibrated at 160-180 degC (1,5-H shift).While 7 approaches a statistical ("hydrogen-like") distribution of the CHX2 group, the methoxymethyl group of 5 strongly prefers position 1.In contrast, the NMR spectra of the analogous bullvalenes (2 and 9) indicate a nearly statistical distribution of CH2X, but not of CHX2.We conclude that electronic substituent effects on sigmatropic equilibria should not be generalized.
