3450-15-5Relevant articles and documents
Maitlis,McVey
, p. 254 (1965)
Control of functional group proximity and direction by conformational networks: Synthesis and stereodynamics of persubstituted arenes
Kilway, Kathleen V,Siegel, Jay S
, p. 3615 - 3627 (2007/10/03)
The cooperative nonbonded interactions present in hexaethylbenzene result in an arrangement of alkyl groups such that the 1,3,5 and 2,4,6 substituents point to opposite faces of the benzene ring. Correspondingly, derivatives of hexaethylbenzene have their functional groups convergent (meta as in 1,3,5-trisubstituted-2,4,6-triethylbenzene) or divergent (ortho, para as in 1,2-disubstituted-3,4,5,6-tetraethylbenzenes or 1,4-disubstituted-2,3,5,6-tetraethylbenzenes) due to this cooperative conformational network. To illustrate this structural feature and probe its dynamics, 1,4-di-X-2,3,5,6-tetraethylbenzenes have been synthesized. The dynamic stereochemistry of the disubstituted compounds has been studied by variable temperature 1H NMR spectroscopy. Using the same strategy, the 1,3,5-tris(CH2Y)-2,4,6-triethylbenzenes have also been prepared. The steric bulk of the substituent in the disubstituted compounds has been found to influence the barrier height. The trends found are applicable for the use of these compounds as angular building blocks for the design of ligands, polymers, and supramolecular architectures.
Novel Catalysis of Hydroquinone Autoxidation with Nitrogen Oxides
Bosch, E.,Rathore, R.,Kochi, J. K.
, p. 2529 - 2536 (2007/10/02)
An efficient catalytic method is described for the preparative conversion of hydroquinones to quinones with dioxygen under mild conditions.The use of the gaseous nitrogen oxide (NOx) catalyst allows a simple workup procedure for the isolation of quinones in essentially quantitative yields by merely removing the low-boiling solvent dichloromethane in vacuo.The mechanism of the catalytic autoxidation of hydroquinones is ascribed to the critical role of nitrosonium (NO(+)) in the one-electron oxidation of hydroquinone, followed by the reoxidation of the reduced nitric oxide (NO) with dioxygen.An extensive series of complex interchanges among various NOx species in nitrogen-(V), -(IV), -(III), and -(II) oxidation states, coupled with stepwise oxidation of hydroquinone via a successive series of one-electron/proton transfer, from the critical components of the catalytic cycle.