Decomposition of multifunctionalized α-alkoxyalkyl-hydroperoxides derived from the reactions of Criegee intermediates with diols in liquid phases

Abstract

The ozonolysis of alpha-terpineol with C3–C5 diols produced multifunctionalized ROOHs that decomposed into hemiacetals and H2O2 in acidic aqueous organic media.

Proton-Catalyzed Decomposition of Multifunctionalized Organic Hydroperoxides Derived from the Reactions of Criegee Intermediates with Ethylene Glycol in Aqueous Organic Media

“…This result was in agreement with previous reports about α-AHs derived from the reaction of α-Tp CIs with 1-propanol 23 and 1,5-pentanediol. 27 Temporal profiles of hemiacetals (m/z 283) showed a rise-and-decay behavior at pH 5.1, but the increase of the rate of decay as the pH decreased (Figure S3) was consistent with previous results with hemiacetals produced from the decomposition of α-AHs. 23,27 The formation and decay of the hemiacetals are acid-catalyzed.…”

“…These results were in agreement with the mechanism by which α-AHs are derived from α-Tp CIs +1-propanol 17 and α-Tp CIs +1,5-pentanediol. 27 Scheme 2. Decomposition of C 12 α-AHs Derived from Ozonolysis of α-Terpineol in W/EG Solutions Therefore, we concluded the presence of an additional −OH group and the size difference did not change the decomposition product of the α-AHs.…”

“…27 Temporal profiles of hemiacetals (m/z 283) showed a rise-and-decay behavior at pH 5.1, but the increase of the rate of decay as the pH decreased (Figure S3) was consistent with previous results with hemiacetals produced from the decomposition of α-AHs. 23,27 The formation and decay of the hemiacetals are acid-catalyzed. 23,27 The observed nonzero baselines of the profiles of α-AH signals at m/z 299 were attributable to the limited presence of an R 1 C(−H)(−OOH)(−OR′) and/or cyclic peroxyhemiacetal isomers 51,52 that did not decompose via the H + -catalyzed mechanism within the duration of the experiments (vide supra).…”

“…We have investigated the fates of α-AHs derived from the reaction of α-terpineol (α-Tp) CIs with alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol). 23,27 Our discovery that these α-AHs decompose into the corresponding hemiacetals faster at lower pH led us to hypothesize that the decompositions proceeded via an acid-catalyzed mechanism. Theoretical calculations have revealed that the proton (H + ) plays the key role in the decomposition of C 13 α-AHs derived from α-Tp CIs + 1propanol/2-propanol.…”

Stability of Terpenoid-Derived Secondary Ozonides in Aqueous Organic Media

“…The mechanism in which a water molecule is incorporated into the α-Tp CIs to form α-HHs, followed by rapid decomposition into the corresponding aldehyde and isomerization into lactols is in agreement with our previous results obtained from negative-ion mass spectrometry. , The fact that the signals attributed to lactols kept increasing even after that of α-HH-Na + had disappeared (Figure A) implies that the aldehyde was MS-silent and acted as a reservoir that slowly isomerized into the lactols (Scheme ). Furthermore, we note the possibility that these lactols were also produced from the decomposition of HP-THP/THF (the conversion of ROOH to ROH) as observed in the cases of α-alkoxyalkyl hydroperoxides ,− and other ROOH . Based on the fact that the ion signals at m / z 267;269 also appeared in water:CD 3 COCD 3 solvent (see below) and the increase of the signals as a function of time was not correlated with the decay of m / z 283, we concluded that these lactols were not a decomposition product of C 13 SOZs.…”