Halogenalkylhydroperoxide, II. Anlagerung von Halogen und Wasserstoffperoxid and Olefine

Abstract

Bei der Einwirkung von Brom bzw. Chlor und Wasserstoffperoxid auf Olefine in Dioxan bilden sich P-Brom-oder P-Chlor-alkylhydroperoxide. Die Reaktion wurde mit Methallylchlorid, Isobutylen, 2-Methyl-penten-(l), Tetramethylathylen und Cyclohexen durchgefiihrt.In der I. Mitteilung2) haben wir uber die Herstellung von P-Brom-alkylhydroperoxiden (1) durch Sauerstoffbehandlung von Olefinen in Gegenwart von Bromwasserstoff berichtet. Diese Reaktion verlauft entsprechend G1. (1).

Preparation and base-catalyzed reactions of some β-halohydroperoxides

“…Thus, cleavage of the 2,3-carbon -carbon bond was the predominant reaction. This is the same type of reaction previously reported for the l-bromoand 1-cllloro-2-methyl-2-propyl hydroperoxides (4,5). It has been suggested (4, 5) that the cleavage proceeds via a four-atom cyclic peroxide.…”

“…After work had begun there appeared several reports on the reactions of p-halo-and p-cyanohydroperoxides with base ( 4 6 ) . It is reported that l-chloro-2-methyl-2-propyl hydroperoxide is rapidly decoinposed by base to acetone and formaldehyde (4), while other workers report that upon treatment with base the brorno analogue, l-bromo-2-methyl-2-propyl hydroperoxide is converted partly to isobutylene oxide as well as to acetone and formaldehyde (5). A similar cleavage reaction was observed when 2-methyl-2-hydroperoxypropionitrile was treated with base (6).…”

“…In the present study it has been found that p-halohydroperoxides can be prepared conveniently and in good yield by the reaction belween olefins, N-haloamides, and excess 98 "/:, hydrogen peroxide in ether solution. The reaction appears to be general and gives essentially no dihnlogenated adducts, which are major by-products in Rieche's method (5,10).…”

“…The above p-halohydroperoxides have halogen on the ter~niilal carbon atom and a simple elimination route is not available to these materials. autoxidation of halogenated hydrocarbons (7,8), by the acid-catalyzed addition of hydrogen peroxide to allylic halides (4), by the reaction between olefins, hydrogen peroxide, and t-butyl hypocl~lorite (9), and by the addition of bromine or chlorine to olefins in the presence of hydrogen peroxide (5,10). In the present study it has been found that p-halohydroperoxides can be prepared conveniently and in good yield by the reaction belween olefins, N-haloamides, and excess 98 "/:, hydrogen peroxide in ether solution.…”

“…Hydroperoxide, 5 The procedure described for the preparation of 16 was used to prepare an ethe~eal solution of 5 from 10.4 g (0.1 mole) of purified styrene, 14.3 g (0.05 mole) of 1,3-dibromo-5,5-dimethylhydantoin, and 17 g (0.5 mole) of 98% hydrogen peroxide. The dried solution was concentrated to constant weight under 0.5 mm pressure on a water bath at 30" using a rotary evaporator.…”