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

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
General Chemical Engineering

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",

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 = "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",

year = "2017",

language = "English",

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TY - CONF

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.

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

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

UR - https://www.scopus.com/pages/publications/85046439509

UR - https://www.scopus.com/pages/publications/85046439509#tab=citedBy

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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