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Determination of ring inversion barriers for 1H,3H-naphtho[1,8-cd]-pyran and its methyl substituted derivatives by molecular mechanics calculations and dynamic nuclear magnetic resonance spectroscopy

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Molecular mechanics calculations with Allinger's MMPI program indicate that substitution of the methylene hydrogens in 1H,3H-naphtho[1,8-cd]pyran with methyl groups lowers the barrier to ring inversion. This seems to arise from increasing steric interactions in the ground state, whereas the energy of the transition state is less affected. The transition state for the inversion process has been calculated to possess C, symmetry. Increased steric interactions on the introduction of methyl groups result in a more planar (i.e less puckered) ground state with an increased C-O-C bond angle. Dynamic 1H n.m.r. spectroscopy of 2,2-dimethyl-1H,3H-naphtho[1,8-cd]pyran reveals a △G value for ring inversion of 6.9 kcal mol-1 at -133°. For the four other naphthopyrans studied by dynamic n.m.r. only upper limits for the inversion barrier are obtained.

OriginalsprogEngelsk
TidsskriftJournal of the Chemical Society, Perkin Transactions 2
Udgave nummer4
Sider (fra-til)741-746
Antal sider6
ISSN1472-779X
DOI
StatusUdgivet - 1 jan. 1981

ID: 218714752