Ethylhydroperoxide

Fig. 8. Structure of the product obtained in the HO-l-catalyzed oxidation of heme supported by ethylhydroperoxide.

A bottle that you thought contained ethanol had oxidized to 10% ethylhydroperoxide. If the contents of this bottle suddenly went to ehemical equilibrium, estimate the temperature and pressure in the bottle (for a short time). The heat of formationof ethylhydroperoxide is -41 kcal/tnole and the heat of carbon oxidation to CO2 is -67 kcal/mole. 

Ethyl Peroxyacetate, CH8C0-00-C2H6, mw 104.11, oil Believed to have been prepd from acetic anhydride and a dilute soln of ethylhydroperoxide (Ref 2) but not further examined... 

Ethylhydroperoxide and derivs 6 E300—E301 ethylhydroperoxide salts 6 E300—E301... 

Ethylhydroperoxide Salts. Several salts are known,some of them explosive. Its Barium Sa//,Ba(00. C2H5)2 2H20,consists of prisms... 

On the basis of kinetic stndies the presence of a peroxo-intermediate was postdated and spectroscopic evidence for such an intermediate has been obtained. Brs", Br2, or HOBr appear to be the primary reaction prodncts of the enzyme-mediated peroxidation of bromide. The vanadium enzyme also nses phenylperacetic acid, m-chloroperoxybenzoic acid, and jo-nitroperoxybenzoic acid as oxidants, but alkyl peroxides such as ethylhydroperoxide, tert-butyl hydroperoxide, and cuminyl hydroperoxide are not substrates for the enzyme in the oxidation of bromide. The enzyme from the brown seaweed Ascophyllum nodosum does not display any specificity with regard to bromination of various organic nucleophilic acceptors which suggests a mechanism in which the oxidized bromine species are released into solution by the enzyme. Figure 1 gives a simple model for the reaction mechanism of the enzyme. 

Jonsson and co-workers [90, 91] have also reported enthalpy values from semiempirical and a number of higher level ab initio calculations. Sheng et al. [10, 92] report data on the ethyl peroxy and 2-hydroperoxide ethyl radicals and on the stable ethylhydroperoxide. Schaefer and co-workers [93, 94] have reported results on the ethyl peroxy and 2-hydroperoxide ethyl radicals. Sumathi and Green [95] have reported results from ab initio molecular orbital calculations at the Hartree-Fock level for S and Q (7) and complete basis set (CBS-Q atomization reaction) level for enthalpies on methyl, ethyl, isopropyl, and tertbutyl hydroperoxides and their corresponding methylperoxides. 

Before moving to unsaturated species we use the value of methyl hydroperoxide to test our calculation method on ethylhydroperoxide (CH3CH2OOH) and provide some comparison of our results with available data. The calculated ethylhydroperoxide value is included in Table 3.7 and is found to be within 0.3 kcal mof of the selected literature value of 39.52 kcal mof, given in Appendix A (Table A.3). 

Yields have been determined for hydroperoxide formation from the alkyl side-groups ethylbenzene-2-hydroperoxide, 17 % C from OH + ethylbenzene benzyl-hydroperoxide, 5 % C from OH + toluene (Bachmann). Low yields of methylhydroperoxide are reported for both systems, and ethylhydroperoxide was also observed in the reaction of OH with ethylbenzene. 

We photolysed 2 and 3-pentanone. We found ethylhydroperoxide in the experiment with 3-pentanone and methylhydroperoxide and propylhydroperoxide in the oxidation of 2-pentanone as product of the Norrish reaction. Other products were diketones and organic acids. Some main products at late retention time could not be identified. Tests with HPLC/fluorescence detection indicate that they are hydroperoxides. 

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