Synthesis of 3,4-Diarylsubstituted Maleic Anhydride/Maleimide via Unusual Oxidative Cyclization of Phenacyl Ester/Amide [1]

Abstract

A simple and general method has been developed for the synthesis of 3,4-diarylsubstituted maleic anhydride and maleimide through tandem cyclization and oxidation reaction of phenacyl ester or amide. A wide variety of phenacyl esters or amides was treated with DBU under oxygen atmosphere to give the expected compounds in good to excellent yield. Mechanism of the reaction and application of the methodology have been discussed.

Key words

3,4-diarylsubstituted maleic anhydride/maleimide - oxidative cyclization - phenacyl ester/amide - oxygen

1

DRF Publication No. 185.

References

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1

DRF Publication No. 185.

21

A useful method for the synthesis of 3,4-diaryl-5-hydroxyfuranones has been developed by us and will be reported elsewhere.

23

Typical Procedure for the Synthesis of 3,4-Diaryl Substituted Maleic Anhydride: Preparation of 4: To a solution of 2-oxo-2-phenylethyl-2-phenylacetate (0.50 g, 1.968 mmol) in acetonitrile (8 mL) was added DBU (0.899 g, 5.905 mmol) slowly and dropwise at 25 °C in the presence of atmospheric oxygen. The mixture was stirred for 6 h. After completion of the reaction the mixture was poured into ice-cold 3 N HCl solution (20 mL) with stirring. The solid separated was filtered off, washed with water (2 × 10 mL) followed by petroleum ether (2 × 5 mL). Compound 4 was isolated in 77% yield as light yellow solid, mp 158-160 °C (lit [16] 159-160 °C).

24

Spectral data for 11: mp: 161.5-162 °C (1:9 EtOAc-hexane); IR _max (KBr): 1833, 1766 cm^-1; ¹H NMR (200 MHz, CDCl₃): δ = 7.31-7.54 (m, 5 H), 7.74 (d, J = 8.74 Hz, 2 H), 8.27 (d, J = 8.79 Hz, 2 H); Mass (CI method, I-butane): m/z (%) = 296(100) [MH⁺]; UV (MeOH): 268 nm. Elemental analysis found: C, 64.81; H, 3.11; N, 4.62. C₁₆H₉NO₅ requires C, 65.09; H, 3.07; N, 4.74.

25

Spectral data for 12: mp: 121-122 °C (1:9 EtOAc-hexane); IR _max (KBr): 1826, 1757 cm^-1; ¹H NMR (200 MHz, CDCl₃): δ = 2.38 (s, 3 H), 7.18-7.26 (m, 3 H), 7.39-7.56 (m, 6 H); Mass (CI method, I-butane): m/z (%) = 265(100) [MH⁺]; UV (MeOH): 355 nm. Elemental analysis found: C, 77.55; H, 4.32. C₁₇H₁₂O₃ requires C, 77.26; H, 4.58.