Renewable solvents for Diels–Alder/cheletropic reaction sequences: preparation of pentaphenylbenzene and 1,2,4-triphenyltriphenylene

Sara Ahmed; Harry Burrows; Brian A. Chalmers; David B. Cordes; Ruairidh M. Davidson; Lauren Emmens; Theodore V. Fulton; Daniel Kleinjan; Iain L. J. Patterson; Iain A. Smellie

doi:10.3390/reactions6030041

Renewable solvents for Diels–Alder/cheletropic reaction sequences: preparation of pentaphenylbenzene and 1,2,4-triphenyltriphenylene

Sara Ahmed, Harry Burrows, Brian A. Chalmers, David B. Cordes, Ruairidh M. Davidson, Lauren Emmens, Theodore V. Fulton, Daniel Kleinjan, Iain L. J. Patterson, Iain A. Smellie^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Polycyclic aromatic compounds can often be made by a sequence featuring an initial Diels–Alder [4 + 2] cycloaddition reaction, followed by cheletropic extrusion of carbon monoxide. These reactions normally require heating the diene and dieneophile in petrochemical-derived aromatic hydrocarbon solvents, such as xylenes or diphenyl ether. This article summarizes the results of attempts to use renewable solvents in place of those currently in use to prepare pentaphenylbenzene and 1,2,4-triphenyltriphenylene. Dihydrolevoglucosenone, p-cymene, ethyl lactate, diethyl carbonate, and cyclopentyl methyl ether have all been successfully evaluated as renewable solvent alternatives in Diels–Alder/cheletropic reaction sequences. An analysis of the products from the reactions investigated did not show evidence of oxidative degradation of the diene reactants. Furthermore, norbornadien-7-one intermediates were not isolated from any of the reactions tested.

Original language	English
Article number	41
Pages (from-to)	1-13
Number of pages	13
Journal	Reactions
Volume	6
Issue number	3
DOIs	https://doi.org/10.3390/reactions6030041
Publication status	Published - 30 Jul 2025

Keywords

Diels-Alder reaction
Cheletropic reaction
Pericyclic chemistry
Polycyclic aromatic compounds
Green solvents

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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Ahmed-et-al-2025-Renewable-solvents-Reactions-06-00041-CCBY
Copyright: © 2025 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Final published version, 1.08 MBLicence: CC BY

CCDC 2465931: Experimental Crystal Structure Determination
Chalmers, B. (Creator), Cordes, D. (Creator), Patterson, I. (Creator) & Smellie, I. (Creator), Cambridge Crystallographic Data Centre, 2025
DOI: 10.5517/ccdc.csd.cc2ns05n
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Ahmed, S., Burrows, H., Chalmers, B. A., Cordes, D. B., Davidson, R. M., Emmens, L., Fulton, T. V., Kleinjan, D., Patterson, I. L. J., & Smellie, I. A. (2025). Renewable solvents for Diels–Alder/cheletropic reaction sequences: preparation of pentaphenylbenzene and 1,2,4-triphenyltriphenylene. Reactions, 6(3), 1-13. Article 41. https://doi.org/10.3390/reactions6030041

@article{31be29febbea472289f132b268409132,

title = "Renewable solvents for Diels–Alder/cheletropic reaction sequences: preparation of pentaphenylbenzene and 1,2,4-triphenyltriphenylene",

abstract = "Polycyclic aromatic compounds can often be made by a sequence featuring an initial Diels–Alder [4 + 2] cycloaddition reaction, followed by cheletropic extrusion of carbon monoxide. These reactions normally require heating the diene and dieneophile in petrochemical-derived aromatic hydrocarbon solvents, such as xylenes or diphenyl ether. This article summarizes the results of attempts to use renewable solvents in place of those currently in use to prepare pentaphenylbenzene and 1,2,4-triphenyltriphenylene. Dihydrolevoglucosenone, p-cymene, ethyl lactate, diethyl carbonate, and cyclopentyl methyl ether have all been successfully evaluated as renewable solvent alternatives in Diels–Alder/cheletropic reaction sequences. An analysis of the products from the reactions investigated did not show evidence of oxidative degradation of the diene reactants. Furthermore, norbornadien-7-one intermediates were not isolated from any of the reactions tested.",

keywords = "Diels-Alder reaction, Cheletropic reaction, Pericyclic chemistry, Polycyclic aromatic compounds, Green solvents",

author = "Sara Ahmed and Harry Burrows and Chalmers, {Brian A.} and Cordes, {David B.} and Davidson, {Ruairidh M.} and Lauren Emmens and Fulton, {Theodore V.} and Daniel Kleinjan and Patterson, {Iain L. J.} and Smellie, {Iain A.}",

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T2 - preparation of pentaphenylbenzene and 1,2,4-triphenyltriphenylene

AU - Ahmed, Sara

AU - Burrows, Harry

AU - Chalmers, Brian A.

AU - Cordes, David B.

AU - Davidson, Ruairidh M.

AU - Emmens, Lauren

AU - Fulton, Theodore V.

AU - Kleinjan, Daniel

AU - Patterson, Iain L. J.

AU - Smellie, Iain A.

PY - 2025/7/30

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N2 - Polycyclic aromatic compounds can often be made by a sequence featuring an initial Diels–Alder [4 + 2] cycloaddition reaction, followed by cheletropic extrusion of carbon monoxide. These reactions normally require heating the diene and dieneophile in petrochemical-derived aromatic hydrocarbon solvents, such as xylenes or diphenyl ether. This article summarizes the results of attempts to use renewable solvents in place of those currently in use to prepare pentaphenylbenzene and 1,2,4-triphenyltriphenylene. Dihydrolevoglucosenone, p-cymene, ethyl lactate, diethyl carbonate, and cyclopentyl methyl ether have all been successfully evaluated as renewable solvent alternatives in Diels–Alder/cheletropic reaction sequences. An analysis of the products from the reactions investigated did not show evidence of oxidative degradation of the diene reactants. Furthermore, norbornadien-7-one intermediates were not isolated from any of the reactions tested.

AB - Polycyclic aromatic compounds can often be made by a sequence featuring an initial Diels–Alder [4 + 2] cycloaddition reaction, followed by cheletropic extrusion of carbon monoxide. These reactions normally require heating the diene and dieneophile in petrochemical-derived aromatic hydrocarbon solvents, such as xylenes or diphenyl ether. This article summarizes the results of attempts to use renewable solvents in place of those currently in use to prepare pentaphenylbenzene and 1,2,4-triphenyltriphenylene. Dihydrolevoglucosenone, p-cymene, ethyl lactate, diethyl carbonate, and cyclopentyl methyl ether have all been successfully evaluated as renewable solvent alternatives in Diels–Alder/cheletropic reaction sequences. An analysis of the products from the reactions investigated did not show evidence of oxidative degradation of the diene reactants. Furthermore, norbornadien-7-one intermediates were not isolated from any of the reactions tested.

KW - Diels-Alder reaction

KW - Cheletropic reaction

KW - Pericyclic chemistry

KW - Polycyclic aromatic compounds

KW - Green solvents

U2 - 10.3390/reactions6030041

DO - 10.3390/reactions6030041

M3 - Article

SN - 2624-781X

VL - 6

SP - 1

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JO - Reactions

JF - Reactions

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M1 - 41

ER -

Renewable solvents for Diels–Alder/cheletropic reaction sequences: preparation of pentaphenylbenzene and 1,2,4-triphenyltriphenylene

Abstract

Keywords

UN SDGs

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Datasets

CCDC 2465931: Experimental Crystal Structure Determination

Cite this