Effect of substituents and promoters on the Diels–Alder cycloaddition reaction in the biorenewable synthesis of trimellitic acid

Khan, Tuhin Suvra and Gupta, Shelaka and Ahmad, Maaz and et al, . (2020) Effect of substituents and promoters on the Diels–Alder cycloaddition reaction in the biorenewable synthesis of trimellitic acid. RSC Advances, 10 (51). pp. 30656-30670. ISSN 2046-2069

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Abstract

An efficient route to produce oxanorbornene, a precursor for the production of bio-based trimellitic acid (TMLA) via the Diels-Alder (DA) reaction of biomass-derived dienes and dienophiles has been proposed by utilizing density functional theory (DFT) simulations. It has been suggested that DA reaction of dienes such as 5-hydroxymethyl furfural (HMF), 2,5-dimethylfuran (DMF), furan dicarboxylic acid (FDCA) and biomass-derived dienophiles (ethylene derivatives e.g., acrolein, acrylic acid, etc.) leads to the formation of an intermediate product oxanorbornene, a precursor for the production of TMLA. The activation barriers for the DA reaction were correlated to the type of substituent present on the dienes and dienophiles. Among the dienophiles, acrolein was found to be the best candidate showing a low activation energy (<40 kJ mol-1) for the cycloaddition reaction with dienes DMF, HMF and hydroxy methyl furoic acid (HMFA). The FMO gap and (IPdiene + EAdienophile)/2 were both suggested to be suitable descriptors for the DA reaction of electron-rich diene and electron-deficient dienophile. Further solvents did not have a significant effect on the activation barrier for DA reaction. In contrast, the presence of a Lewis acid was seen to lower the activation barrier due to the reduction in the FMO gap. © The Royal Society of Chemistry.

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IITH Creators:

IITH Creators	ORCiD
Gupta, Shelaka	UNSPECIFIED

Item Type:

Article

Additional Information:

Authors would like to acknowledge nancial assistance from the Department of Science and Technology (Government of India, Grant No. CRG/2019/006176). Initial seed grant from ICAR-IITD joint MFIRP project (MI02031G) is appreciated to pursue this research. Computational resources are provided by the high performance computing (HPC) facility of IIT Delhi.

Uncontrolled Keywords:

Activation barriers; Cycloaddition reaction; Dicarboxylic acid; Diels-Alder cycloadditions; Diels-Alder reaction; Electron-deficient; Intermediate product; Low-activation energy

Subjects:

Chemical Engineering

Divisions:

Department of Chemical Engineering

Depositing User:

. LibTrainee 2021

Date Deposited:

02 Nov 2022 07:44

Last Modified:

02 Nov 2022 07:44

URI:

http://raiithold.iith.ac.in/id/eprint/11128