On the Mechanism of the Ozonation of Isopropyl Alcohol:  An Experimental and Density Functional Theoretical Investigation. <sup>17</sup>O NMR Spectra of Hydrogen Trioxide (HOOOH) and the Hydrotrioxide of Isopropyl Alcohol

Plesničar, Božo; Cerkovnik, Janez; Tekavec, and Tomaž; Koller, J.

doi:10.1021/ja981568z

Cited by 51 publications

(76 citation statements)

References 12 publications

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“…The ozonization of the C-H bond, which is a controversial reaction leading, at low temperature, to the formation of alkyl hydrotrioxides ROOOH and hydrogen trioxide HOOOH, was investigated in an important series of papers [520][521][522][523]. Through the use of 17 O enriched ozone, the Plesničar group [520] studied the ozonization of isopropyl alcohol, observing the formation of both the isopropyl alcohol trioxide and the hydrogen trioxide. This was confirmed by the 17 O NMR chemical shift assignments which are in excellent agreement with the calculated shifts at the GIAO/ MP2/6-311++G ** level.…”

Section: Pomentioning

confidence: 99%

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Gerothanassis

2010

Progress in Nuclear Magnetic Resonance Spectroscopy

121

107

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Section: Pomentioning

confidence: 99%

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Gerothanassis

2010

Progress in Nuclear Magnetic Resonance Spectroscopy

121

107

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“…2 The abstraction of the hydrogen atom from the RÀ ÀH bond was proposed to be formed in the first step of the ozonolysis of hydrocarbons. 14 To evaluate the activity of the H atom in different reactive sites of the acetaldehyde (CH 3 and CHO groups), we take the H abstraction from acetaldehyde by ozone as our basis study. To acquire accurate rate constants over a wide temperature range, both high-level ab initio calculation and rate constants calculation are required.…”

Section: Introductionmentioning

confidence: 99%

Direct dynamics study on the reaction of acetaldehyde with ozone

Yang

Zhang

2007

J Comput Chem

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The hydrogen abstraction reaction of ozone with acetaldehyde has been studied theoretically over the temperature range 250-2500 K. Two different reactive sites of acetaldehyde molecule, CH(3) and CHO groups have been investigated, and results confirm that the CHO group is a highly reactive site. In this study, the geometries and harmonic vibrational frequencies of all stationary points are calculated at the MPW1K, BHandHLYP, and MPWB1K levels of theory. The minimum energy paths (MEPs) were obtained at the MPW1K/6-31+G(d,p) level of theory. To refine the energies along the MEPs of each channel, single-point energy calculations were performed by a higher-level energy calculation method (denoted as HL). The rate constants were evaluated based on the MEPs from the HL method in the temperature range 250-2500 K by using the conventional transition state theory (TST), the canonical variational transition state theory (CVT), the microcanonical variational transition state theory (muVT), the CVT coupled with small-curvature tunneling (SCT) correction (CVT/SCT), and the muVT coupled with Eckart tunneling correction (muVT/Eckart). The fitted three-parameter Arrhenius expressions of the calculated CVT/SCT and muVT/Eckart rate constants of the H abstraction from CHO group are k CVT/SCT(T) = 4.92 x 10(-27).T 3.77.e(-7867.0/T) and k muVT/Eckart(T) = 2.10 x 10(-27).T(3.90).e(-7706.2/T), respectively. The fitted three-parameter Arrhenius expressions of the calculated CVT/SCT and muVT/Eckart rate constants of the H abstraction from CH3 group are k(CVT/SCT)(T) = 1.27 x 10(-27).T(3.94).e(-14554.1/T) and k muVT/Eckart(T) = 1.62 x 10(-26).T(3.66).e(-15459.8/T), respectively.

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“…1). Recently, Plesničar et al 37 showed that low-temperature ozonation of isopropyl alcohol affords significant amounts of hydrogen trioxide in addition to hydrotrioxide ROOOH (H 2 O 3 :ROOOH = 0.6:1). The following scheme was proposed to explain H 2 O 3 formation:…”

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Formation of hydrotrioxides during ozonation of hydrocarbons on silica gel. Decomposition of hydrotrioxides

Avzyanova

Timerghazin

Khalizov

et al. 2000

J. Phys. Org. Chem.

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Hydrotrioxides (HT), ROOOH, from isopentane, 1,4-dimethylcyclohexane, 1,3-dimethylcyclohexane, decalin and triphenylmethane were synthesized for the first time by low-temperature ozonation of the corresponding hydrocarbons on a silica surface. Thermal decomposition of hydrotrioxides is accompanied by the formation of radicals and by infrared and visible chemiluminescence (CL). In solution the HTs form self-associates and react reversibly with the solvent (acetone) producing Bayer-Villiger type intermediates (unsymmetrical dialkyl trioxides). These reactions cause a complex character of the decomposition kinetics of HTs, as evidenced by monitoring the dependence of CL intensity on time. Activation parameters of thermal decomposition of HTs show a compensation effect (logA vs E A ) which describes well the available experimental and theoretical data for the homolysis of organic trioxides.

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On the Mechanism of the Ozonation of Isopropyl Alcohol: An Experimental and Density Functional Theoretical Investigation. ¹⁷O NMR Spectra of Hydrogen Trioxide (HOOOH) and the Hydrotrioxide of Isopropyl Alcohol

Cited by 51 publications

References 12 publications

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Direct dynamics study on the reaction of acetaldehyde with ozone

Formation of hydrotrioxides during ozonation of hydrocarbons on silica gel. Decomposition of hydrotrioxides

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On the Mechanism of the Ozonation of Isopropyl Alcohol: An Experimental and Density Functional Theoretical Investigation. 17O NMR Spectra of Hydrogen Trioxide (HOOOH) and the Hydrotrioxide of Isopropyl Alcohol

Cited by 51 publications

References 12 publications

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Oxygen-17 NMR spectroscopy: Basic principles and applications (Part I)

Direct dynamics study on the reaction of acetaldehyde with ozone

Formation of hydrotrioxides during ozonation of hydrocarbons on silica gel. Decomposition of hydrotrioxides

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On the Mechanism of the Ozonation of Isopropyl Alcohol: An Experimental and Density Functional Theoretical Investigation. ¹⁷O NMR Spectra of Hydrogen Trioxide (HOOOH) and the Hydrotrioxide of Isopropyl Alcohol