Restricted rotation involving the tetrahedral carbon. XXXIII. Restricted rotation about a Csp3-Csp2 bond in 10,10-disubstituted 9-(2,6-xylyl)-9,10-dihydroanthracene derivatives.

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概要

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• A series of 10,10-disubstituted 9-(2,6-xylyl)-9,10-dihydroanthracene derivatives have been prepared and their conformations and barriers to internal rotation about the C<SUB>xylyl</SUB>–C<SUB>9</SUB> bond have been examined. These compounds exist predominantly as a pseudo-equatorial form in the ground state for rotation. A large effect is inserted by the substituents in 10 position on barriers to rotation and is interpreted in terms of a rotation-inversion mechanism rather than a simple rotation mechanism for the methyl-exchange process which is observed by <SUP>1</SUP>H NMR spectra. The highest barrier to rotation has been found in the compound having two peri-chloro groups and a hydroxyl group in 9-position. The high barrier is ascribed to destabilization of the transition state, where 9-aryl group takes axial conformation, due to the three electronegative groups which are forced to be arranged parallelly in quite a near region. The change of 9-OH to 9-H thus decreases the barrier to rotation when peri-chlorines are present, while the increase in barrier is observed as in the case of 9-arylfluorenes and 9-arylxanthenes when they are absent.

• 公益社団法人 日本化学会の論文

著者

• Oki Michinori

  Department Of Chemistry Faculty Of Science Okawama University Of Science

• Nakamura Mikio

  Department Of Anatomy Jikei-kai School Of Medicine

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