Nuclear Magnetic Resonance Studies of Bicyclic Thiophene Derivatives. II. Through Space H–F Coupling in o-Fluorophenyl Derivatives of Benzoylthiophene, Thienopyrimidine and Thienodiazepine Derivatives

Abstract
Proton–fluorine coupling over six bonds has been observed between fluorine and Hβ of the thiophene ring in ortho fluorophenyl derivatives of 4-phenylthienopyrimidines (1), 2-acetylamino-3-benzoylthiophenes (2), 5-phenyl-1,4-thienodiazepines (3) and 5-phenyl-1,4-thienodiazepine-4-oxides (4). The solvent effect and the N-methylation effect on the coupling constant can be explained by considering that the H–F coupling is a through space coupling. The value of coupling constant (JHF: 0.5 Hz to 4.1 Hz) depends upon the geometry of the ring system condensed at 2-C and 3-C of thiophene ring, decreasing in the order of 1>2>3>4. A discussion is given on the manner of steric repulsion between the benzene ring and some atoms on the other moiety of these compounds.

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