The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole

Nassim Zeinali; Jomana Al-Nu’airat; Zhe Zeng; Mohammednoor Altarawneh; Dan Li; Jakub Skut; Bogdan Z. Dlugogorski

The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole

Nassim Zeinali, Jomana Al-Nu’airat, Zhe Zeng, Mohammednoor Altarawneh, Dan Li, Jakub Skut, Bogdan Z. Dlugogorski

Research output: Contribution to conference › Paper › peer-review

Abstract

The essential role of pyrrole in comprehending the chemistry of living organisms, coal surrogates and novel drugs is indisputable. However, literature reports a few studies on its reactivity toward prominent oxidizing agents. Herein we present a comprehensive mechanistic study of oxidation of unsubstituted pyrrole with singlet oxygen (O₂¹∆_g) by deploying a quantum chemical framework leading to the production of succinimide, as the major products, through a Diels-Alder addition of O₂¹∆_g to the aromatic ring. Other products, comprising maleimide, hydroperoxide, formamide or epoxide adducts, appear to form via rather minor channels. Additionally, we determined that, the primary Diels-Alder channel encompasses a barrier of 41 kJ/mol with a fitted rate constant of k(T)=1.87×10^-13 exp(-48 000/RT) cm³ molecule^-1 s^-1

Original language	English
Publication status	Published - 2017
Externally published	Yes
Event	11th Asia-Pacific Conference on Combustion, ASPACC 2017 - Sydney, Australia Duration: Dec 10 2017 → Dec 14 2017

Conference

Conference	11th Asia-Pacific Conference on Combustion, ASPACC 2017
Country/Territory	Australia
City	Sydney
Period	12/10/17 → 12/14/17

ASJC Scopus subject areas

Condensed Matter Physics
Energy Engineering and Power Technology
Fuel Technology
Chemical Engineering(all)

Cite this

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title = "The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole",

abstract = "The essential role of pyrrole in comprehending the chemistry of living organisms, coal surrogates and novel drugs is indisputable. However, literature reports a few studies on its reactivity toward prominent oxidizing agents. Herein we present a comprehensive mechanistic study of oxidation of unsubstituted pyrrole with singlet oxygen (O21∆g) by deploying a quantum chemical framework leading to the production of succinimide, as the major products, through a Diels-Alder addition of O21∆g to the aromatic ring. Other products, comprising maleimide, hydroperoxide, formamide or epoxide adducts, appear to form via rather minor channels. Additionally, we determined that, the primary Diels-Alder channel encompasses a barrier of 41 kJ/mol with a fitted rate constant of k(T)=1.87×10-13 exp(-48 000/RT) cm3 molecule-1 s-1",

author = "Nassim Zeinali and Jomana Al-Nu{\textquoteright}airat and Zhe Zeng and Mohammednoor Altarawneh and Dan Li and Jakub Skut and Dlugogorski, {Bogdan Z.}",

note = "Funding Information: This study has been supported by grants of computing time from the National Computational Infrastructure (NCI) and from the Pawsey Supercomputing Centre, Australia as well as funds from the Australian Research Council (ARC). N.Z., J.N. and Zh.Z. thank Murdoch University for the award of postgraduate scholarships. Publisher Copyright: {\textcopyright} 2018 Combustion Institute. All Rights Reserved.; 11th Asia-Pacific Conference on Combustion, ASPACC 2017 ; Conference date: 10-12-2017 Through 14-12-2017",

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T1 - The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole

AU - Zeinali, Nassim

AU - Al-Nu’airat, Jomana

AU - Zeng, Zhe

AU - Altarawneh, Mohammednoor

AU - Li, Dan

AU - Skut, Jakub

AU - Dlugogorski, Bogdan Z.

N1 - Funding Information: This study has been supported by grants of computing time from the National Computational Infrastructure (NCI) and from the Pawsey Supercomputing Centre, Australia as well as funds from the Australian Research Council (ARC). N.Z., J.N. and Zh.Z. thank Murdoch University for the award of postgraduate scholarships. Publisher Copyright: © 2018 Combustion Institute. All Rights Reserved.

PY - 2017

Y1 - 2017

N2 - The essential role of pyrrole in comprehending the chemistry of living organisms, coal surrogates and novel drugs is indisputable. However, literature reports a few studies on its reactivity toward prominent oxidizing agents. Herein we present a comprehensive mechanistic study of oxidation of unsubstituted pyrrole with singlet oxygen (O21∆g) by deploying a quantum chemical framework leading to the production of succinimide, as the major products, through a Diels-Alder addition of O21∆g to the aromatic ring. Other products, comprising maleimide, hydroperoxide, formamide or epoxide adducts, appear to form via rather minor channels. Additionally, we determined that, the primary Diels-Alder channel encompasses a barrier of 41 kJ/mol with a fitted rate constant of k(T)=1.87×10-13 exp(-48 000/RT) cm3 molecule-1 s-1

AB - The essential role of pyrrole in comprehending the chemistry of living organisms, coal surrogates and novel drugs is indisputable. However, literature reports a few studies on its reactivity toward prominent oxidizing agents. Herein we present a comprehensive mechanistic study of oxidation of unsubstituted pyrrole with singlet oxygen (O21∆g) by deploying a quantum chemical framework leading to the production of succinimide, as the major products, through a Diels-Alder addition of O21∆g to the aromatic ring. Other products, comprising maleimide, hydroperoxide, formamide or epoxide adducts, appear to form via rather minor channels. Additionally, we determined that, the primary Diels-Alder channel encompasses a barrier of 41 kJ/mol with a fitted rate constant of k(T)=1.87×10-13 exp(-48 000/RT) cm3 molecule-1 s-1

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M3 - Paper

AN - SCOPUS:85046439509

T2 - 11th Asia-Pacific Conference on Combustion, ASPACC 2017

Y2 - 10 December 2017 through 14 December 2017

ER -

The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole

Abstract

Conference

ASJC Scopus subject areas

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