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Synlett 2019; 30(05): 630-634
DOI: 10.1055/s-0037-1612080
DOI: 10.1055/s-0037-1612080
letter
A Copper Halide Promoted Regioselective Halogenation of Coumarins Using N-Halosuccinimide as Halide Source
We thank the financial support from the National Natural Science Foundation of China (No. 21462003), Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry ([2013]1792), the Key Scientific Research Projects of Guangxi Department of Education (2011ZD003), the Scientific Research Foundation of Guangxi University (No. XGZ111491), and the Guangxi Undergraduate Student Innovation Training Project (No. 201710593193).Further Information
Publication History
Received: 04 December 2018
Accepted after revision: 07 January 2019
Publication Date:
30 January 2019 (online)
Abstract
A safe, convenient, and regioselective synthesis of 3-halo coumarins using a metal halide (CuX2 alone or with ZnX2) promoted halogenation with N-halosuccinimide (NXS) as halide source is reported. The synthesis involved the steady in situ generation of highly reactive positive halogen (X+) by the coordination of copper or zinc with the N-halosuccinimide and subsequent electrophilic aromatic substitution of the electron-deficient coumarins. This procedure works well also for the halogenation of less electron-rich naphthoquinones, flavones, and methoxypsoralen in moderate to quantitative yields. This protocol features simple experimental conditions using readily available inexpensive reagents and provides a convenient approach to the chlorination or bromination of some useful heteroaromatic compounds.
Key words
coumarin - halogenation - aryl halide - electrophilic aromatic substitution - N-halosuccinimideSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1612080.
- Supporting Information
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References and Notes
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- 26 3,7-Dichloro-2H-chromen-2-one (2b) – Typical Procedure To a 50 mL round-bottom flask, 7-chloro coumarin (180.6 mg, 1 mmol), NCS (935.2 mg, 7 mmol), CuCl2·2H2O (2387 mg, 14 mmol), and 20 mL anhydrous MeCN were added and refluxed until the reaction completed. The cooled mixture was concentrated in vacuum, dispensed in 25 mL 5% NaHSO3 aqueous solution and extracted with 25 mL EtOAc for three times. The organic layer was combined, washed with 10 mL water and dried over anhydrous Na2SO4. After the solvent was removed, the crude product was purified by silica gel column chromatography to afford 96.2 mg 2b (44.9%). 3,7-Dichloro-2H-chromen-2-one (2b) White solid, mp 123–124 ℃ (acetone/PE, 2:1, V/V). 1H NMR (600 MHz, CDCl3): δ = 7.84 (s, 1 H), 7.40 (d, J = 8.3 Hz, 1 H), 7.38 (d, J = 1.9 Hz, 1 H), 7.30 (dd, J = 8.3, 1.9 Hz, 1 H). 13C NMR (151 MHz, CDCl3): δ = 156.6, 152.9, 139.3, 137.9, 128.0, 125.7, 122.5, 117.4, 117.2, 100.0. IR (KBr): νmax = 3103, 3061, 3040, 1736, 1720, 1702, 1604, 1484, 1403, 1348, 1318, 1245, 1206, 1144, 1123, 1077, 998, 969, 939, 916, 865, 825, 752, 681, 617, 595, 462 cm–1. HRMS (ESI): m/z calcd for C9H5Cl2O2 [M + H] (35Cl): 214.9661; found: 214.9661.