THE PREPARATION AND PROPERTIES OF ORGANIC DERIVATIVES OF PEROXIDES OF PHOSPHORUS, TIN, BORON, SILICON, AND SULFUR.
WESTERN RESERVE UNIV CLEVELAND OH
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The first hydroperoxides of Sn, first stable hydroperoxides of Si, the first stable bisperoxides of Si, the first bis-peroxide of P, and the first stable sulfonyl peroxides were prepared. Hydroperoxides of the Group IV elements other than C tend to rearrange rather than react with other compounds. Kinetics, products, and energies of activation were determined. With an increasing atomic wt. of the peroxidic elements there is a decrease in activation energy for the rearrangement process which is much smaller than predicted in the literature. All the hydroperoxides are reasonably stable. The bisperoxide of P is of reasonable stability but tends to rearrange. Of all the sulfonyl perixides prepared, only the nitro derivatives were safe for routine use. They substitute aromatic nuclei in 70 yield and the sulfonate esters produced hydrolyze easily. Peroxidic copolymers of Sn compounds, aldehydes and ketones are very stable and may be of value as free radical catalysts which decompose by mechanical shear. Author