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Current Organic Synthesis

Author(s): Diparjun Das, Kalyani Rajkumari and Lalthazuala Rokhum*

DOI: 10.2174/1570179416666190919152424

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Polymer-Bound Triphenylphosphine and 4,4′-Dinitroazobenzene as a Coupling Reagents for Chromatography-Free Esterification Reaction

Page: [1024 - 1031] Pages: 8

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Abstract

Aim and Objective: Sustainable production of fine chemicals both in industries and pharmaceuticals heavily depends on the application of solid-phase synthesis route coupled with microwave technologies due to their environmentally benign nature. In this report, a microwave-assisted esterification reaction using polymer-bound triphenylphosphine and 4,4′-dinitroazobenzene reagent system was investigated.

Materials and Methods: The solvents were obtained from Merck India. Polymer-bound triphenylphosphine (~3 mmol triphenylphosphine moiety/g) was acquired from Sigma-Aldrich. The progress of the reaction was observed by thin-layer chromatography. All the reactions were performed in Milestones StartSYNTH microwave. The NMR spectra were recorded on Bruker Avance III 300, 400, and 500 MHz FT NMR Spectrometers. Using azo compound and polymer-bound triphenyl phosphine as a coupling reagent, esterification of different carboxylic acids with alcohols was performed under microwave irradiation.

Results: Esterification of benzoic acid with 1-propanol under microwave irradiation gave a high yield of 92% propyl benzoate in 60 minutes only. Isolation of the ester products was relatively simple as both the byproducts polymer-bound triphenylphosphine oxide and hydrazine could be removed by simple filtration. The rates of reactions were found to be directly proportional to the pKa of the benzoic acids.

Conclusion: 4,4′-Dinitroazobenzene was introduced as a novel coupling reagent, in conjugation with polymer-bound triphenylphosphine, for esterification reactions under microwave irradiation. The low moisture sensitivity of the reaction system, easy separation of the byproducts, and column chromatographyfree isolation of esters help our methods with application significance, particularly from the ‘Sustainable Chemistry’ perspective.

Keywords: Esterification reaction, chemoselective, retention, chromatography-free, microwave irradiation, simple filtration.

Graphical Abstract

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