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Synlett 2020; 31(18): 1795-1799
DOI: 10.1055/s-0040-1707248
DOI: 10.1055/s-0040-1707248
letter
Electrochemical Synthesis of Quinazolinones by the Metal-Free and Acceptor-Free Dehydrogenation of 2-Aminobenzamides
We thank the National Natural Science Foundation of China (21861006), Ministry of Education of the People’s Republic of China (IRT_16R15), Natural Science Foundation of Guangxi Province (2016GXNSFEA380001, 2016GXNSFGA380005, 2018GXNSFBA281151), Guangxi Key R&D Program (No. AB18221005), Science and Technology Major Project of Guangxi (AA17204058-21), Guangxi Science and Technology Base and Special Talents (guike AD19110027), Guangxi Funds for Distinguished Experts and State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (CMEMR2019-A03), and Guangxi Science and Technology Base and Talents Program (AD18281035, AD18281028) for financial support.Weitere Informationen
Publikationsverlauf
Received: 02. Juni 2020
Accepted after revision: 26. Juli 2020
Publikationsdatum:
19. August 2020 (online)
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-freeSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707248.
- Supporting Information
-
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.