Direct Detection of Products from the Pyrolysis of 2-Phenethyl Phenyl Ether

Jarvis, Mark; Daily, John W.; Carstensen, Hans-Heinrich; Dean, Anthony M.; Sharma, Sanjai; Dayton, David C.; Robichaud, David J.; Nimlos, Mark R.

doi:10.1021/jp1076356

Cited by 163 publications

(150 citation statements)

References 79 publications

(95 reference statements)

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“…A similar range of values have been reported by other researchers [73][74][75]. The Nimlos's research group [72] reported the formation of degradation products from the gas-phase pyrolysis of phenethyl phenyl ether and they concluded that the C−O homolysis occurred at high temperatures (>1000 °C), whereas the concerted retro-ene and Maccoll mechanisms were significant at lower temperatures (<600 °C).…”

Section: Ether Cleavage Mechanismssupporting

confidence: 82%

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Lignin pyrolysis reactions

2017

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Section: Ether Cleavage Mechanismssupporting

confidence: 82%

“…Several concerted (heterolytic) mechanisms have been proposed for β-ether bond cleavage [42,[72][73][74][75][76]. Klein and Virk [42] proposed a six membered retro-ene mechanism based on an analysis of the kinetics for the formation of styrene and phenol from phenethyl phenyl ether.…”

Section: Ether Cleavage Mechanismsmentioning

confidence: 99%

Lignin pyrolysis reactions

2017

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“…Initial pyrolysis mechanism of the lignin model dimer According to previous studies, both homolytic cleavage and concerted decomposition may occur during the initial pyrolysis of lignin model compounds [39,40]. In order to elucidate the possible initial pyrolysis mechanism of this lignin model dimer, the BDEs for the C b -O and C a -C b homolysis and the activation energy for the C b -O concerted decomposition are calculated and illustrated in Fig.…”

Section: Resultsmentioning

confidence: 99%

Pyrolysis mechanism of a β-O-4 type lignin dimer model compound

Zhang

Jiang

et al. 2015

J Therm Anal Calorim

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To help understand the pyrolysis mechanism of lignin, a non-phenolic lignin dimer model compound with b-O-4 linkage, namely 1-methoxy-2-(4-methoxyphenethoxy) benzene, was prepared. Its pyrolysis mechanism was investigated by density functional theory calculations and confirmed by the analytical pyrolysis-gas chromatography/mass spectrometry experiments. Possible pyrolytic pathways were proposed and analyzed based on three initial pyrolysis mechanisms of the model compound, including the C b -O homolytic mechanism, the C a -C b homolytic mechanism and the C b -O concerted decomposition mechanism. The results indicate that the lignin dimer model compound is thermally stable at low pyrolysis temperature (300°C), whereas at moderate pyrolysis temperature (500°C), four major pyrolytic products will be generated via the initial C b -O concerted decomposition and C b -O homolysis, including the 1-methoxy-4-vinylbenzene, 2-hydroxybenzaldehyde, 1-ethyl-4-methoxybenzene and 2-methoxyphenol. Products from the C a -C b homolysis can hardly be formed, due to the high-energy barriers and limitation of the available free hydrogen atoms. Secondary cracking of the primary pyrolytic products will take place to form some light compounds, which will be enhanced with the increase in pyrolysis temperature.

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“…[7,8] Computational studies have begun to provide insight into individual reaction steps, as well as substituent effects, that would be challenging experimentally. [11,15,[24][25][26][27][28][29][30][31][32] FVP deuterium isotope studies of PPE found products associated with carbon-oxygen homolysis and 1,2-elimination. [7,8] At higher temperatures (above 500 8C), the carbon-carbon bond was also cleaved, but at a lower rate.…”

Section: Introductionmentioning

confidence: 99%

Computational Study of Bond Dissociation Enthalpies for Substituted β‐O‐4 Lignin Model Compounds

2011

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The biopolymer lignin is a potential source of valuable chemicals. Phenethyl phenyl ether (PPE) is representative of the dominant β-O-4 ether linkage. DFT is used to calculate the Boltzmann-weighted carbon-oxygen and carbon-carbon bond dissociation enthalpies (BDEs) of substituted PPE. These values are important for understanding lignin decomposition. Exclusion of all conformers that have distributions of less than 5% at 298 K impacts the BDE by less than 1 kcal mol(-1). We find that aliphatic hydroxyl/methylhydroxyl substituents introduce only small changes to the BDEs (0-3 kcal mol(-1)). Substitution on the phenyl ring at the ortho position substantially lowers the C-O BDE, except in combination with the hydroxyl/methylhydroxyl substituents, for which the effect of methoxy substitution is reduced by hydrogen bonding. Hydrogen bonding between the aliphatic substituents and the ether oxygen in the PPE derivatives has a significant influence on the BDE. CCSD(T)-calculated BDEs and hydrogen-bond strengths of ortho-substituted anisoles, when compared with M06-2X values, confirm that the latter method is sufficient to describe the molecules studied and provide an important benchmark for lignin model compounds.

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Direct Detection of Products from the Pyrolysis of 2-Phenethyl Phenyl Ether

Abstract: This supplemental material contains Cartesian coordinates (Angstroms) for all structures at the CBS-QB3 level of theory.

Cited by 163 publications

References 79 publications

Lignin pyrolysis reactions

Lignin pyrolysis reactions

Pyrolysis mechanism of a β-O-4 type lignin dimer model compound

Computational Study of Bond Dissociation Enthalpies for Substituted β‐O‐4 Lignin Model Compounds

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