Electronic structure investigations of 4-methyl-3-penten-2-one by UV–Visible and NMR spectral studies and natural bond orbital analysis by DFT calculations

Arjunan, V.; Jayaprakash, Anitha; Santhanam, R.; Govindaraja, S. Thillai; Mohan, S.

doi:10.1016/j.molstruc.2012.04.076

Cited by 5 publications

(5 citation statements)

References 33 publications

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“…4M3P2O has two conformers corresponding to Z (A) and E (B) orientation of the C(CH 3 ) 2 group with respect to carbonyl O atom (see Figure ). The E -conformer (B) is 12.31 kJ/mol higher in energy than the Z -one (A), which is in good agreement with the reported literature . Consequently, the Z -conformer (A) is chosen for the following discussions unless otherwise specified.…”

Section: Resultsmentioning

confidence: 99%

“…The E-conformer (B) is 12.31 kJ/mol higher in energy than the Z-one (A), which is in good agreement with the reported literature. 7 Consequently, the Zconformer (A) is chosen for the following discussions unless otherwise specified.…”

Section: Initial Reactions Of 4m3p2o With Oh Radicalsmentioning

confidence: 99%

“…6 Large quantities of 4M3P2O are used extensively in vinyl resins, insect repellents, paints and varnish removers, rollcoating inks, and methyl isobutyl ketones. 7 In addition, it finds wide application as chemical intermediates in the synthesis of organometallic compounds and undergoes evaporative losses to the atmosphere. 8 It has been reported that the production rate of 4M3P2O is as high as 0.1 Tg yr −1 in the US.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigations of the OH-Initialized Oxidation of 4-Methyl-3-Penten-2-One in the Atmosphere

Zhang

2022

ACS Earth Space Chem.

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The present work represents the reaction mechanism and kinetics study of the 4-methyl-3-penten-2-one initiated by OH radicals. The geometries of all stationary points are optimized at the M06-2X/6-311+ +G(d,p) level of theory, and the energy values are refined by making single point energy calculation at the CCSD(T)/6-311++G(d,p) level of theory to construct an energy-level diagram. By employing conventional transition state theory along with a tunneling coefficient, the overall rate constants are calculated in the temperature range of 180−360 K and can be summarized by a modified Arrhenius three-parameter fit expression: k (T) = 6.72 × 10 −20 × T 2.5 × exp (2056.4/T) cm 3 molecule −1 s −1 . The rate constant obtained at 298 K is found to be 1.02 × 10 −10 cm 3 molecule −1 s −1 , which is in good agreement with the experimental data. In the atmosphere, the major oxidation products of the title reaction are acetone, methyl glyoxal, (CH 3 ) 2 COHC(O)H, CO 2 , and formaldehyde, which are in accordance with experimental detection. The atmospheric lifetime of 4-methyl-3-penten-2-one initiated by OH radicals and the impact of products on tropospheric chemistry have been provided in the paper.

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Section: Resultsmentioning

confidence: 99%

Section: Initial Reactions Of 4m3p2o With Oh Radicalsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigations of the OH-Initialized Oxidation of 4-Methyl-3-Penten-2-One in the Atmosphere

Zhang

2022

ACS Earth Space Chem.

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“…As illustrated in Figure , there are conjugated double bonds (CO and CC) in the MPO molecule. In Arjunan’s study, three different conformers of MPO were considered due to the rotation of O 1 –C 2 –C 3 –C 4 dihedral and the cis configuration has the lowest energy . Therefore, the s -cis conformer was chosen for the following discussions.…”

Section: Resultsmentioning

confidence: 99%

“…The compound 4-methyl-3-penten-2-one (MPO, CH 3 C(O)CHC(CH 3 ) 2 ), also known as mesityl oxide, is an important α,β-unsaturated ketone and has been identified in biogenic emissions to the atmosphere. , MPO is emitted by Cardamine pratensis involved in plant growth and productivity . In addition, as a key intermediate in the synthesis of organometallic compounds, MPO is widely used in the manufacture of vinyl resins, insect repellents, paint and varnish removers, roll-coating inks, and methyl isobutyl ketones . It has a wide range of potential applications owing to its excellent optical clarity combined with a high melting point, electrical properties, low bulk density, high chemical resistance, and high permeability to gases. , MPO is toxic by ingestion, inhalation, or skin absorption, which can irritate eyes, skin, and the mucous membrane and even cause severe damage to the liver, kidneys, and the central nervous system .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of the Atmospheric Cl Oxidation Chemistry of 4-Methyl-3-penten-2-one

Zhao

Han

2020

ACS Earth Space Chem.

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The reaction mechanisms and kinetics of 4-methyl-3-penten-2-one (MPO) with atomic Cl have been studied using second-order Møller−Plesset perturbation theory (MP2) and canonical variational transition-state (CVT) theory with smallcurvature tunneling (SCT) correction methods. Eight different reaction paths are considered: two possible Cl addition reactions and six possible hydrogen abstraction reactions. The results of the theoretical investigation indicate that Cl addition dominates the initial reactions of MPO with Cl atoms, and the most energetically favorable pathway is the Cl addition to the double bond carbon adjacent to the carbonyl in the molecule. Among all of the six Habstraction paths, the H abstraction from the two methyl groups linked to the double bond is predicted to occur readily according to the calculated data. In addition, the 1,5-H shift isomerization process, involving the Cl addition mechanism, was proposed and found to be feasible. The major possible products that were detected in experiment and derived from our theoretical study have been identified. The rate constants and branching ratios of the main reaction paths have been obtained over the temperature range of 180−380 K. The total rate constants are dependent on temperature and the Arrhenius equation is fitted as k total = (2.99 × 10 −13 )exp(1795.60/T). The atmospheric lifetime is also estimated and shows a positive temperature dependence.

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The gas-phase reaction kinetics of different structure of unsaturated alcohols and ketones with O3

Dan

Chen

et al. 2021

Atmospheric Environment

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Electronic structure investigations of 4-methyl-3-penten-2-one by UV–Visible and NMR spectral studies and natural bond orbital analysis by DFT calculations

Cited by 5 publications

References 33 publications

Theoretical Investigations of the OH-Initialized Oxidation of 4-Methyl-3-Penten-2-One in the Atmosphere

Theoretical Investigations of the OH-Initialized Oxidation of 4-Methyl-3-Penten-2-One in the Atmosphere

Theoretical Investigation of the Atmospheric Cl Oxidation Chemistry of 4-Methyl-3-penten-2-one

The gas-phase reaction kinetics of different structure of unsaturated alcohols and ketones with O3

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