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: Chapter in Book/Report/Conference proceeding › Conference Paper published in Proceedings › peer-review

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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
Title of host publication	11th Asia-Pacific Conference on Combustion 2017
Editors	A.R. Masri, M. Cleary, M. Dunn, A. Kourmatzis, E. Hawkes, S. Kook, Q.N. Chan
Place of Publication	United States
Publisher	Combustion Institute China Section
Pages	1215-1218
Number of pages	4
Volume	2017-December
ISBN (Print)	9781510856462
Publication status	Published - 2017
Externally published	Yes
Event	11th Asia-Pacific Conference on Combustion, ASPACC 2017 - Sydney, Australia Duration: 10 Dec 2017 → 14 Dec 2017

Conference

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

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Zeinali, N., Al-Nu’airat, J., Zeng, Z., Altarawneh, M., Li, D., Skut, J., & Dlugogorski, B. Z. (2017). The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole. In A. R. Masri, M. Cleary, M. Dunn, A. Kourmatzis, E. Hawkes, S. Kook, & Q. N. Chan (Eds.), 11th Asia-Pacific Conference on Combustion 2017 (Vol. 2017-December, pp. 1215-1218). Combustion Institute China Section.

Zeinali, Nassim ; Al-Nu’airat, Jomana ; Zeng, Zhe et al. / The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole. 11th Asia-Pacific Conference on Combustion 2017 . editor / A.R. Masri ; M. Cleary ; M. Dunn ; A. Kourmatzis ; E. Hawkes ; S. Kook ; Q.N. Chan. Vol. 2017-December United States : Combustion Institute China Section, 2017. pp. 1215-1218

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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.}",

year = "2017",

language = "English",

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booktitle = "11th Asia-Pacific Conference on Combustion 2017",

publisher = "Combustion Institute China Section",

note = "11th Asia-Pacific Conference on Combustion, ASPACC 2017 ; Conference date: 10-12-2017 Through 14-12-2017",

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Zeinali, N, Al-Nu’airat, J, Zeng, Z, Altarawneh, M, Li, D, Skut, J & Dlugogorski, BZ 2017, The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole. in AR Masri, M Cleary, M Dunn, A Kourmatzis, E Hawkes, S Kook & QN Chan (eds), 11th Asia-Pacific Conference on Combustion 2017 . vol. 2017-December, Combustion Institute China Section, United States, pp. 1215-1218, 11th Asia-Pacific Conference on Combustion, ASPACC 2017, Sydney, Australia, 10/12/17.

The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole. / Zeinali, Nassim; Al-Nu’airat, Jomana; Zeng, Zhe et al.
11th Asia-Pacific Conference on Combustion 2017 . ed. / A.R. Masri; M. Cleary; M. Dunn; A. Kourmatzis; E. Hawkes; S. Kook; Q.N. Chan. Vol. 2017-December United States: Combustion Institute China Section, 2017. p. 1215-1218.

Research output: Chapter in Book/Report/Conference proceeding › Conference Paper published in Proceedings › peer-review

TY - GEN

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 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 - Conference Paper published in Proceedings

AN - SCOPUS:85046439509

SN - 9781510856462

VL - 2017-December

SP - 1215

EP - 1218

BT - 11th Asia-Pacific Conference on Combustion 2017

A2 - Masri, A.R.

A2 - Cleary, M.

A2 - Dunn, M.

A2 - Kourmatzis, A.

A2 - Hawkes, E.

A2 - Kook, S.

A2 - Chan, Q.N.

PB - Combustion Institute China Section

CY - United States

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

Y2 - 10 December 2017 through 14 December 2017

ER -

Zeinali N, Al-Nu’airat J, Zeng Z, Altarawneh M, Li D, Skut J et al. The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole. In Masri AR, Cleary M, Dunn M, Kourmatzis A, Hawkes E, Kook S, Chan QN, editors, 11th Asia-Pacific Conference on Combustion 2017 . Vol. 2017-December. United States: Combustion Institute China Section. 2017. p. 1215-1218

The mechanism of electrophilic addition of singlet oxygen to unsubstituted pyrrole

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