Electrochemical Synthesis of Quinazolinones by the Metal-Free and Acceptor-Free Dehydrogenation of 2-Aminobenzamides

Yan Yao; Xiu-Jin Meng; Qing-Hu Teng; Yan-Yan Chen

doi:10.1055/s-0040-1707248

Synlett, Inhaltsverzeichnis

Synlett 2020; 31(18): 1795-1799
DOI: 10.1055/s-0040-1707248

letter

Electrochemical Synthesis of Quinazolinones by the Metal-Free and Acceptor-Free Dehydrogenation of 2-Aminobenzamides

Yan Yao

^aState Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, P. R. of China eMail: qinghuteng@163.com

,

Xiu-Jin Meng

^aState Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, P. R. of China eMail: qinghuteng@163.com

,

Qing-Hu Teng∗

^aState Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, P. R. of China eMail: qinghuteng@163.com

^bGuangxi Key Laboratory of Electrochemical and Magnetochemical Function Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, P. R. of China

,

Yan-Yan Chen∗

^cPharmacy School, Guilin Medical University, Guilin 541004, P. R. of China eMail: chenyy269614@163.com

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Abstract

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Abstract

An efficient approach has been developed for the construction of quinazolin-4(3H)-ones by the selective anodic dehydrogenative oxidation/cyclization of benzylic chlorides and 2-aminobenzamides. The method features acceptor-free and metal-free dehydrogenation of amines to imines; a subsequent intermolecular addition provides the products in moderate to good yields.

Key words

quinazolinones - electrochemical synthesis - aminobenzamides - benzylic chlorides - metal-free

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Referenzen

References and Notes

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19 Quinazolinones 3a–q; General Procedure A mixture of the appropriate 2-aminobenzamide 1 (0.5 mmol), benzylic chloride 2 (0.6 mmol), and Bu₄NBF₄ (10 mol%) was placed in a 25 mL three-necked round-bottomed flask equipped with a condenser, an RVC (100 PPI) anode, and a Pt plate (1 × 1 cm) cathode. The flask was opened to air and MeCN (6 mL) was added. Electrolysis was carried out at 80 °C (oil-bath temperature) at a constant current of 10 mA until the substrate was completely consumed (TLC). The mixture was then cooled to rt, and the solvent was removed under reduced pressure. The residue was purified by chromatography (silica gel, EtOAc–PE). 2-Phenylquinazolin-4(3H)-one (3a) White solid; yield: 88.8 mg (80%); mp 233–235 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 12.52 (s, 1 H), 8.22–8.12 (m, 3 H), 7.84–7.77 (m, 1 H), 7.73 (d, J = 8.0 Hz, 1 H), 7.53 (qt, J = 11.0, 5.2 Hz, 4 H). ¹³C NMR (101 MHz, DMSO): δ = 162.80, 152.84, 149.28, 135.09, 133.26, 131.90, 129.12, 128.30, 128.03, 127.09, 126.39, 121.51. 2-(4-Fluorophenyl)quinazolin-4(3H)-one (3b) White solid; yield: 72.0 mg (60%); mp 240–242 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 12.57 (s, 1 H), 8.25 (dd, J = 8.8, 5.6 Hz, 2 H), 8.15 (d, J = 6.4 Hz, 1 H), 7.84 (t, J = 6.8 Hz, 1 H), 7.73 (d, J = 8.1 Hz, 1 H), 7.55–7.50 (m, 1 H), 7.39 (t, J = 8.8 Hz, 2 H). ¹³C NMR (100 MHz, DMSO): δ = 162.69, 151.86, 149.11, 135.15, 130.85 (d, J = 9.3 Hz), 130.10, 129.66 (d, J = 3.2 Hz), 127.92, 127.11, 126.32, 121.32, 116.11 (d, J = 22.0 Hz). 2-(4-Chlorophenyl)quinazolin-4(3H)-one (3c) White solid; yield: 81.9 mg (64%); mp 295.5–298 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 12.61 (s, 1 H), 8.21 (d, J = 8.7 Hz, 2 H), 8.16 (d, J = 7.9 Hz, 1 H), 7.85 (t, J = 6.9 Hz, 1 H), 7.75 (d, J = 8.0 Hz, 1 H), 7.64 (d, J = 8.6 Hz, 2 H), 7.54 (t, J = 7.5 Hz, 1 H). ¹³C NMR (100 MHz, DMSO): δ = 163.04, 152.10, 149.31, 137.04, 135.45, 132.29, 130.37, 129.44, 128.27, 127.55, 126.62, 121.72.

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