CONFORMATIONAL BEHAVIOR OF CYCLOBUTYL MONOHALIDES

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1966

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Ohio State University

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The results of a study of the conformational behavior of the monosubstituted cyclobutane ring by far-infrared, microwave, infrared, and Raman spectroscopy are presented. The data were evaluated with the help of (1) calculations of the dipole moment as a function of the ring conformation, (2) computer calculations of vapor band envelops, including vibration-rotation interaction, (3) quantum-mechanical computer calculations of the energy levels, probability distribution, transition moments, infrared intensities, and average dihedral angles of the ring puckering mode, and (4) some semi-quantitative considerations of non-bonded interactions. It is concluded that cyclobutyl-X exists in two conformations which have no common energy levels. The more stable conformer possesses a strongly bent carbon ring, whereas the carbon ring of the less stable conformer is nearly planar. The energy difference between the two conformations is about 1 kcal mole. The two conformations cause the appearance of two widely spaced carbon-halogen stretching modes in bromocyclobutane and chlorocyclobutane.

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Author Institution: Scientific Laboratory, Ford Motor Company

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