Steric and conformational control of the regioselectivities in the ene reaction with trisubstituted cycloalkenes: comparison of the enophiles singlet oxygen, triazolinedione, and nitrosoarene
The nitrosoarene ene reaction with the cycloalkenes 1-3 and E-4 proceeds in high twix regioselectivity to afford the hydroxylamine ene products 1a-4a (twix) and 1b-4b (twin, except far E-4 twix). Steric interactions in the enophile attack are responsible for the skew trajectory of the nitrosoarene enophile. For Z-1-methylcyclooctene (Z-4), twin abstraction dominates, caused by conformational constraints (transannular interactions) in the hydrgogen-atom abstraction. The balance between these steric and conformational factors dictates the regioselectivity in the ene reaction
Reaction profile of the photooxygenation of trisubstituted alkenes
Abstract Photooxygenation of a series of isotopically-labeled trimethylethylenes shows that formation of the perepoxide intermediate is rate-determining.
Modeling of chemical reactors—XXIX mixing-cell model for packed bed reactors. Steady state considerations. Problems of multiplicity
Abstract The axial heat and mass transfer in tubular catalytic reactors may be described by mixing-cell model and diffusion model as well. The diffusion description yields for a strong exothermic reaction and adiabatic conditions three steady state profiles, on the other hand the mixing-cell model gives rise to more than three steady states. A simple numerical and graphical analysis for mixing-cell model is presented.