Issue 17, 2016

Centrohexaindane: six benzene rings mutually fixed in three dimensions – solid-state structure and six-fold nitration

Abstract

The solid-state molecular structure of centrohexaindane (1), a unique hydrocarbon comprising six benzene rings clamped to each other in three dimensions around a neopentane core, and the molecular packing in crystals of 1·CHCl3 are reported. The molecular Td-symmetry and the Cartesian orientation of the six indane wings of 1 in the solid state have been confirmed. The course and limitation of electrophilic aromatic substitution of 1 are demonstrated for the case of nitration. Based on nitration experiments of a lower congener of 1, tribenzotriquinacene 5, the six-fold nitrofunctionalisation of 1 has been achieved in excellent yield, giving four constitutional isomers, two nonsymmetrical (14 and 17) and two C3-symmetrical ones (15 and 16), all of which contain one single nitro group in each of the six benzene rings. The relative yields of the four isomers (∼3 : 1 : 1 : 3) point to a random electrophilic attack of the electrophiles at the twelve formally equivalent outer positions of the aromatic periphery of 1, suggesting electronic independence of its six aromatic π-electron systems. In turn, the pronounced conformational rigidity of the centrohexacyclic framework of 1 enables the unequivocal structural identification of the isomeric hexanitrocentrohexaindanes 14–17 by 1H NMR spectroscopy.

Graphical abstract: Centrohexaindane: six benzene rings mutually fixed in three dimensions – solid-state structure and six-fold nitration

Supplementary files

Article information

Article type
Paper
Submitted
15 nov 2015
Accepted
16 dez 2015
First published
16 dez 2015

Phys. Chem. Chem. Phys., 2016,18, 11722-11737

Author version available

Centrohexaindane: six benzene rings mutually fixed in three dimensions – solid-state structure and six-fold nitration

D. Kuck, J. Linke, L. C. Teichmann, D. Barth, J. Tellenbröker, D. Gestmann, B. Neumann, H. Stammler and H. Bögge, Phys. Chem. Chem. Phys., 2016, 18, 11722 DOI: 10.1039/C5CP07005H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements