Cumyl hydroperoxide hydrogen bonding

The analysis of the IR spectrum of hydrogen peroxide and cumyl hydroperoxide gave the following values of frequencies (cm-1) of valence and bond angle vibrations [60]. 

If cyclohexanecarboxaldehyde is incubated with CYP2B4, NADPH, and cytochrome P450 reductase, the aldehyde-cyclohexyl ring carbon-carbon bond is cleaved generating cyclohexene and formic acid (150) (Fig. 4.81). The reaction is supported if hydrogen peroxide replaces NADPH and cytochrome P450 reductase but is not supported if other oxidants at the same oxidation equivalent as peroxide but bypass the peroxy form of P450 such as iodosobenzene, m-chloroperbenzoic acid, or cumyl hydroperoxide are used. These... 

Disproportionation reaction 7 might be expected to be thermoneutral in the gas phase and perhaps less so in the liquid phase where there is the possibility of hydrogen-bonding. Only for gas phase dimethyl peroxide is the prediction true, where the reaction enthalpy is —0.2 kJmoD. The liquid phase enthalpy of reaction is the incredible —61.5 kJmoD. Of course, we have expressed some doubt about the accuracy of the enthalpy of formation of methyl hydroperoxide. For teri-butyl cumyl peroxide, the prediction for thermoneutrality is in error by about 6 kJmor in the gas phase and by ca 9 kJmoD for the liquid. The enthalpy of reaction deviation from prediction increases slightly for tert-butyl peroxide — 14kJmol for the gas phase, which is virtually the same result as in the liquid phase, — 19kJmol . The reaction enthalpy is calculated to be far from neutrality for 2-fert-butylperoxy-2-methylhex-5-en-3-yne. The enthalpies of reaction are —86.1 kJmoD (g) and —91.5 kJmol (Iq). This same species showed discrepant behavior for reaction 6. Nevertheless, still assuming thermoneutrality for conversion of diethyl peroxide to ethyl hydroperoxide in reaction 7, the derived enthalpies of formation for ethyl hydroperoxide are —206 kJmoD (Iq) and —164 kJmoD (g). The liquid phase estimated value for ethyl hydroperoxide is much more reasonable than the experimentally determined value and is consistent with the other n-alkyl hydroperoxide values, either derived or accurately determined experimentally. 

Cumyl aUyl peroxide, determination, 708 Cumyl free radical, 697 Cumyl hydroperoxide (CHP) hydrogen bonding, 103-4 hydrogen peroxide determination, 629, 637, 643, 680, 682-3... 

Tertiary alcohols are resistant to oxidation. rcr -Butyl alcohol is frequently used as a solvent in oxidations. However, some tertiary alcohols are converted into tertiary hydroperoxides on treatment with hydrogen peroxide in sulfuric acid [177, 179]. Dimethylphenylcarbinol added to a mixture of 87% hydrogen peroxide and sulfuric acid at a temperature below 0 °C gives a 94% yield of cumyl hydroperoxide after 3.5 h [777]. Similarly, acetylenic alcohols with the tertiary hydroxyl group adjacent to the triple bonds are converted into the corresponding hydroperoxides in high yields [179] (equation 272). 

Molecular complexes between substituted anilines and some hydroperoxides are mainly due to the OOH N hydrogen bonding interaction, as tested by infrared absorption spectral data121. In CCI4 solution there is evidence for the presence of both O—H N and O H—N interactions. The predominance of one of these types of interaction is affected by the structure of the hydroperoxide and by the substituent bonded to the phenyl ring of aniline. The high acidity of some hydroperoxides, such as 1,1-diphenylhydroperoxide and a-cumyl hydroperoxide, is responsible for the salt character of the formed N+—H O ion pair. 

Hydroperoxides (/-butyl hydroperoxide, cumyl hydroperoxide, and hydrogen peroxide) add to the azomethine bond of pyridine iV-aryl-imines.138 The primary addition product reacts as indicated in Eq. (13) and leads to 1,6-dihydropyridazine derivatives (97). Unsymmetrically substituted iV-arylimines furnish two products the structure of the hydroperoxide has no influence upon the nature of the final product. 

Not only oxone bnt also other oxidants can be used in the preparation of hydroxy carbonyl derivatives. So, terf-butyl hydroperoxide has been used in the enantioselective oxidation of 2-alkoxycarbonyl indanone derivatives of type 33 catalyzed by cinchonine 35 to give the expected compound with moderated enantiomeric excess (50%). This chiral compound serves as the starting material for the synthesis of pyrazoline-type insecticide indoxacarb [102]. The use of chiral dihydroquinine (double bond hydrogenated compound 11) in combination with cumyl hydroperoxide at room temperature seems to be a more promising protocol, since the expected hydroxy carbonyl compounds could be obtained with excellent chemical yields and good enantiomeric excess [103]. 

---