Synthesis of tert-butyl hydroperoxide and tert-butyl peroxide and their optical investigation in relation to the problem of the structure of hydrogen peroxide

Abstract

1. It is shown that test-butyl hydroperoxide and tert-butyl peroxide can be prepared from isobutene. 2. It is shown that in previous investigations insufficient account has been taken of the part played by hydrogen bonding in hydrogen peroxide, of which tert-butyl hydroperoxide is a derivative (a fact that is amply confirmed by the presence in the Raman spectrum of the frequencies associated with all of the analogous vibrations of the molecules of the two substances). A study of the Raman spectrum of tert-butyl hydroperoxide shows that hydrogen bonding occurs in this substance. The optical characteristics of the hydroxyl group have been found for complexes formed from many molecules associated through hydrogen bonds (band with a maximum at 3403 cm−1), for the dimer ring (line at 3456 cm−1), and for the monomeric molecule (line at 3622 cm−1), This optical characterization was confirmed by a cryoscopic investigation. The degree of acidity of tert-butyl hydroperoxide was determined optically. It was shown that the optical characteristcs of quaternary branching at the ends of the chains of tert-butyl hydroperoxide, tert-butyl peroxide, and the corresponding hydrocarbons were almost identical. li]3.The stability of the investigated peroxide is explained by its structural characteristics.