Substituent Effects on the Nature of Hydrogen Bonding in Organic Hydroperoxides and the Structure of Triphenylmethyl Hydroperoxide

It has been found that in the crystalline state in triphenylmethyl hydroperoxide the hydroperoxy group is involved in intermolecular hydrogen-bond formation of the type O-h...π, with one C...C π-bond in a benzene ring. Conformational analysis and comparison with the results of x-ray structural analysis leads us to conclude that there are very narrow limits on the possible conformations of the COOH group in tert-butyl, cumyl, 1,1-diphenylethyl, and triphenylmethyl hydroperoxides, independent of their aggregation state or the nature of the substituent attached to the COOH group

Molecular Structure of Dicumyl Peroxide

Conclusions It has been shown by x-ray diffraction analysis that the peroxide group in. dicumyl peroxide has a planar transoid conformation as in the crystals of its analogs (bis(triphen-ylmethyl) peroxide and di-tert-butyl peroxide); and so this conformation is the preferred one for peroxides with two tertiary hydrocarbon substituents. This conclusion is supported by the results of conformational calculations carried out using MNDO and molecular mechanics