On the induced decomposition of α-phenylethylhydroperoxide by peroxy radicals

Abstract

The induced decomposition of α-phenylethylhydroperoxide (HROOH) has been investigated in three different systems: hydroperoxide + cyclohexene + AIBN + O2 (I); cyclohexene substituted by isooctane (II), and cyclohexene substituted by chlorobenzene (III). The decomposition products of the HROOH were in all cases acetophenone (RO) and methylphenylcarbinol (HROH).It was established that peroxy radicals induced the decomposition. The considerable material balance deficit in I is due to the addition of the peroxy radicals to cyclohexene the rate constant of which was estimated from the experimental data. No material balance deficit was observed with II. Experiments supported the assumption that both RO and HROH were formed simultaneously in the interaction between peroxy radicals and HROOH.The rate constant of the reaction HRO2• + HROOH → HROH + O2 + HRO• was measured as k = 1.03 × 109 exp (−13 100/RT). It is suggested that in the autoxidation of ethylbenzene the induced decomposition of HROOH is fast enough to be the main source of RO and HROH.

Photochemical production of peroxy radicals and their interaction with aromatic alcohols

“…The temperature dependence of the reaction between 1-phenylethyl peroxy radicals and 1-phenyl ethanol is in very good agreement with the data of Hajdu et al [6], and they seem to be in reasonable agreement with k = 80 M--' s-' measured at T = 120°C by Danoczy et al [4] using indirect mehods. This work was supported by the OTKA grant No.…”

“…Results are given in Table 3. Taking into consideration also the data of Hajdu et al [ 6 ] , the Arrhenius plot is shown in Fig. 4…”

“…Danbczy et al [4] and Skibida et al [S] measured the relative reactivity of 1-phenyl ethanol and ethylbenzene in their reaction with I-phenylethyl peroxy radicals at T = 120°C. The rate Coefficient of the reaction between 1-phenylethyl peroxy radicals and l-phenylethanol was determined by Hajdu et al [ 6 ] . These latter authors published values between 32.2 and 47.4 M-' s-' in the temperature range of 70-90°C.…”

Autoxidation of nonane and decane: a product study

“…(lo)] or via reactions [eqns. (12), ( 13) and ( 14)]. A less likely process for ketone formation would be the heterolytic decomposition of alkyl hydroperoxides [eqn.…”

Liquid phase oxidation of α‐pinene initiated by ozone. 2: Formation of verbenol, verbenone and acid products

“…Dean and Skirrow I241 suggested, on the other hand, that the radical RO; triggers the decomposition of hydroperoxide, giving rise to the appearance of an alcohol through a reaction proceeding via formation of an intermediate complex[25] :…”