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Synlett 2022; 33(03): 269-272
DOI: 10.1055/a-1707-0965
DOI: 10.1055/a-1707-0965
letter
Synthesis of 1,3,4-Oxadiazoles by Iodine-Mediated Oxidative Cyclization of Methyl Ketones with 4-Phenylsemicarbazide
We gratefully acknowledge the financial support for this research provided by the National Science Foundation of China (51603192, 21172200) and the Natural Science Foundation of Henan Province (182300410211).
Abstract
An efficient one-pot method has been developed to access 5-amino-2-(het)aroyl-1,3,4-oxadiazoles through I2/DMSO-promoted oxidative cyclization of 4-phenylsemicarbazide with (het)aryl methyl ketones under mild conditions. This reaction proceeds smoothly with a wide range of methyl ketones containing various functional groups to give the corresponding products in moderate yields under mild conditions.
Keywords
one-pot reaction - oxadiazoles - oxidative cyclization - phenylsemicarbazide - methyl ketonesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1707-0965.
- Supporting Information
Publication History
Received: 16 October 2021
Accepted after revision: 25 November 2021
Accepted Manuscript online:
25 November 2021
Article published online:
20 December 2021
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- 19 1,3,4-Oxadiazoles 3aa–ka; General Procedure A 25 mL Schlenk-flask equipped with a magnetic stirrer bar was charged with the appropriate methyl ketone 1 (0.2 mmol, 1.0 equiv.), I2 (0.5 mmol), and DMSO (1.0 mL), and the mixture was heated at 110 °C for 1 h. 4-Phenylsemicarbazide (2; 0.24 mmol), K2CO3 (0.6 mmol), and DMSO (1.0 mL) were added, and the resulting mixture was stirred at 110 °C for 15 h. The reaction was then quenched with 5% aq Na2S2O3 (20 mL), and the mixture was extracted with CH2Cl2 (3 × 20 mL). The organic layer was dried (Na2SO4) and concentrated, and the residue was purified by chromatography (silica gel). [5-(Phenylamino)-1,3,4-oxadiazol-2-yl](4-tolyl)methanone (3aa) Yellow solid; yield: 44.5 mg (80%); mp 201–203 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 11.13 (s, 1 H), 8.23 (d, J = 8.4 Hz, 2 H), 7.58 (d, J = 8.0 Hz, 2 H), 7.37–7.32 (m, 4 H), 7.01 (t, J = 7.2 Hz, 1 H), 2.36 (s, 3 H). 13C NMR (100 MHz, DMSO-d 6): δ = 176.6, 161.3, 156.6, 145.5, 138.3, 132.4, 130.8, 129.8, 129.7, 123.2, 118.0, 21.8. HRMS (ESI-TOF): m/z [M + H]+ calcd for C16H14N3O2: 280.1081; found: 280.1081. [5-(Phenylamino)-1,3,4-oxadiazol-2-yl](2-thienyl)methanone (3ca) Yellow solid; yield: 28.5 mg (53%); mp 199–202 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 11.20 (s, 1 H), 8.54 (dd, J = 4.0, 1.2 Hz, 1 H), 8.24 (dd, J = 4.8, 1.2 Hz, 1 H), 7.66–7.63 (m, 2 H), 7.44–7.37 (m, 3 H), 7.09 (tt, J = 7.6, 1.2 Hz, 1 H). 13C NMR (100 MHz, DMSO-d 6): δ = 169.0, 161.5, 156.0, 140.1, 138.3, 138.2, 137.1, 129.7, 129.6, 123.3, 118.1. HRMS (ESI-TOF) m/z [M + H]+ calcd for C13H10N3O2S: 272.0488; found: 272.0491. (3,4-Difluorophenyl)[5-(phenylamino)-1,3,4-oxadiazol-2-yl]methanone (3ka) Yellow solid; yield: 37.3 mg (62%); mp 199–202 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 11.25 (s, 1 H), 8.39–8.34 (m, 1 H), 8.32–8.28 (m, 1 H), 7.76–7.69 (m, 1 H), 7.65–7.62 (m, 2 H), 7.43–7.39 (m, 2 H), 7.12–7.07 (m, 1 H). 13C NMR (100 MHz, DMSO-d 6): δ = 174.5 (d, J C–F = 1.4 Hz), 161.5, 156.4, 152.4 (d, J C-F = 12.4 Hz), 148.4 (d, J C-F = 13.0 Hz), 138.2, 132.3 (dd, J C–F = 5.5, 3.3 Hz), 129.7, 128.7 (dd, J C–F = 8.1, 3.3 Hz), 123.4, 119.8 (d, J C–F = 18.8 Hz), 118.6 (d, J C–F = 17.7 Hz), 118.1. 19F NMR (376 MHz, DMSO-d 6): δ = –129.4 (d, J F–F = 22.56 Hz), –137.1 (d, J F–F = 22.18 Hz). HRMS (ESI-TOF): m/z [M + H]+ calcd for C15H10F2N3O2: 302.0736; found: 302.0737.