A Facile Synthetic Method for Anhydride from Carboxylic Acid with the Promotion of Triphenylphosphine Oxide and Oxaloyl Chloride

Abstract

A highly efficient synthesis reaction of carboxylic anhydrides catalyzed by triphenylphosphine oxide is described for the quick synthesis of a range of symmetric carboxylic anhydrides and cyclic anhydrides under mild and neutral conditions with a high yield. The system adopts the strong reactive intermediate Ph 3 PCl 2 as the catalyst of carboxylic acid salt; driven by catalytic reaction, the synthesis takes a relatively short time to complete.

Base-Mediated Synthesis of Anhydrides from Activated Amides

“…. 12 According to the general procedure, the reaction of 2-(4-methylbenzoyl) benzo [d]isothiazol-3(2H)-one 1,1-dioxide (301 mg, 1.0 mmol) afforded 4-methylbenzoic anhydride (2d) (99 mg, 0.39 mmol, 78%) as yellow solid after column chromatography with hexane/EtOAc (3:1). mp 88−90 °C; 1 H NMR (500 MHz, CDCl 3 ) δ 8.04 (d, J = 8.2 Hz, 4H), 7.31 (d, J = 7.9 Hz, 4H), 2.46 (s, 6H); 13 C{ 1 H} NMR (126 MHz, CDCl 3 ) δ 162.…”

Facile Cleavage of Activated Ketones: An Access to Thioethers via In Situ Generation of Anhydrides by Pummerer-Type Rearrangement

“…Therefore, tremendous efforts have been invested in developing synthetic methods for the preparation of aromatic anhydrides. These compounds are traditionally prepared from acids, acid chlorides, and esters . Moreover, Pd-catalyzed carbonylation and cross-dehydrogenative coupling of aldehydes with carboxylic acid have also been reported .…”

Response surface methodology based on the Box‐Behnken design for optimizing the synthesis of symmetrical anhydrides from acid chlorides using cerium (III) as a homogeneous catalyst

“…The importance of this family on an industrial scale has contributed to the development of several synthesis protocols, [10–11] the recovery of carboxylic acid anhydrides can be done through different access routes that we can cite for example the dehydration reactions of acids, the reaction of an acyl halide with a carboxy ion, [12] the use of strong coupling agents such as thionyl chloride, [13–15] phosgene, [16] phosphoranes [17] or isocyanate [18] . Although the yields are high, the above reactions require a strong source of energy or the use of reagents that are harmful and very dangerous to human health and the environment; hence the need to develop environmentally friendly processes.…”

“…Carboxylic anhydrides represent an important class of highly electrophilic reagents whose roles not only as acylating agents but also as key intermediates for the synthesis of many target molecules, particularly for the preparation of high added-value products, are of great interest for fundamental research involving drug, flavor and food industry. [1][2][3][4][5][6][7][8][9] The importance of this family on an industrial scale has contributed to the development of several synthesis protocols, [10][11] the recovery of carboxylic acid anhydrides can be done through different access routes that we can cite for example the dehydration reactions of acids, the reaction of an acyl halide with a carboxy ion, [12] the use of strong coupling agents such as thionyl chloride, [13][14][15] phosgene, [16] phosphoranes [17] or isocyanate. [18] Although the yields are high, the above reactions require a strong source of energy or the use of reagents that are harmful and very dangerous to human health and the environment; hence the need to develop environmentally friendly processes.…”