Functionalization and kinetic stabilization of the [4]paracyclophane system and aromaticity of its extremely bent benzene ring.

Kinetic stabilization of the [4]paracyclophane skeleton by the introduction of substituents, which serve to sterically hinder reactions at the reactive bridgehead sites, and properties of the resultant [4]paracyclophanes are investigated in this study. Modification of the property of [4]paracyclophane by functionalization is also intended. [4]Paracyclophanes are designed to be derived from the corresponding Dewar benzene isomers via their photochemical aromatization, and the requisite 1,4-bridged Dewar benzenes bearing sterically demanding functional groups are prepared. Irradiation of these precursors under matrix isolation at 77 K leads to the formation of [4]paracyclophanes, which exhibit characteristic electronic absorption spectra. The half-lives of the generated species vary widely from less than 1 min at -90 degrees C to 0.5 h at -20 degrees C, depending on the type of substituents and the pattern of substitution. One of the derivatives, 24, is stable enough and its content in the irradiated mixture is high enough to permit the measurement of the (1)H NMR spectrum. The recorded spectrum, which is reproduced very well by theoretical calculations using the GIAO method at the hybrid HF-DFT (B3LYP/6-31+G*) level, suggests the sustenance of rather strong diatropicity in its severely bent benzene moiety. Calculations on the bent benzene whose geometry is constrained to that calculated for 24 support that aromaticity is retained to a significant extent as compared to that of planar benzene, as judged by the magnetic criteria of aromaticity, that is, diamagnetic susceptibility exaltation and nucleus-independent chemical shift. The reason for the retention of aromaticity despite the severe bending of the benzene ring is discussed. Cyclophane 24 is so strained that it exceeds the corresponding Dewar benzene precursor in energy and thermally reverts to the latter with a half-life of 15 +/- 5 min at -20 degrees C (DeltaG++ = 18.3 +/- 0.3 kcal mol(-1)).