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Synlett 2018; 29(10): 1395-1399
DOI: 10.1055/s-0036-1591565
DOI: 10.1055/s-0036-1591565
letter
Copper-Catalyzed Cascade Synthesis of [1,2,4]-Triazoloquinazolinones
Financial support from the National Natural Science Foundation of China (Grant No. 21772108) is gratefully acknowledged.
Weitere Informationen
Publikationsverlauf
Received: 04. Februar 2018
Accepted after revision: 12. März 2018
Publikationsdatum:
20. April 2018 (online)
Abstract
An efficient and practical method for the synthesis of 1,2,4-triazolo[5,1-b]quinazolin-9(3H)-ones has been developed via the copper-catalyzed domino reactions of readily available substituted N′-acetyl-2-bromobenzohydrazides with cyanamide. The protocol uses inexpensive CuI as the catalyst, and no other ligand or additive was required. The target products were prepared in good to excellent yields with tolerance of various functional groups.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591565.
- Supporting Information
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- 15 General Procedures for the Preparation of Compounds 3a–w: A Schlenk tube was charged with a mixture of CuI (0.03 mmol, 5.7 mg), Cs2CO3 (0.3 mmol, 98 mg), substituted N′-acetyl-2-bromobenzohydrazide 1 (0.3 mmol), cyanamide (2; 0.45 mmol, 19 mg) and anhyd DMF (3.0 mL). After being evacuated and recharged with Ar for three times, the tube was sealed and the mixture was allowed to stir at 120 °C for 10–15 h. After completion of the reaction, the mixture was cooled to r.t., and H2O (20 mL) was added to the mixture. The solution was extracted with CH2Cl2–MeOH (10:1; 3 × 10 mL), and the combined organic layers were dried over anhyd Na2SO4. The solution was concentrated, and the residue was purified by silica gel column chromatography (CH2Cl2–MeOH = 30:1 or 20:1) providing the target product (3a–x). Three representative examples are shown as follows: 6-Methyl-2-phenyl-[1,2,4]triazolo[5,1-b]quinazolin-9(3H)-one (3e): eluent: CH2Cl2–MeOH = 30:1. Isolated yield: 85% (70.4 mg); white solid; mp 352–353 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 8.16 (d, J = 6.5 Hz, 2 H), 8.11 (d, J = 8.2 Hz, 1 H), 7.54 (q, J = 6.4 Hz, 3 H), 7.27 (s, 1 H), 7.21 (d, J = 8.2 Hz, 1 H), 2.47 (s, 3 H). 13C NMR (151 MHz, DMSO-d6 ): δ = 161.6, 155.4, 151.5, 145.9, 139.5, 130.4, 130.1, 128.9 (2 × CH), 127.4, 126.7 (2 × CH), 124.4, 116.3, 111.3, 21.6. ESI–HRMS: m/z [M + Na]+ calcd for C16H12N4NaO: 299.0903; found: 299.0906. 7-Chloro-2-phenyl-[1,2,4]triazolo[5,1-b]quinazolin-9(3H)-one (3r): eluent: CH2Cl2–MeOH = 30:1. Isolated yield: 68% (60.4 mg); white solid; mp 281–283 °C. 1H NMR (600 MHz, DMSO-d 6): δ = 8.14–8.19 (m, 3 H), 7.88 (dd, J = 8.8, 2.4 Hz, 1 H), 7.51–7.58 (m, 4 H). 13C NMR (151 MHz, DMSO-d 6): δ = 161.6, 155.0, 151.3, 139.1, 134.5, 131.1, 129.9, 128.3 (2 × CH), 127.9, 127.1, 126.5 (2 × CH), 122.4, 116.6. ESI–HRMS: m/z [M + H]+ calcd for C15H10ClN4O: 297.0538; found: 297.0540. 2-Methyl-[1,2,4]triazolo[5,1-b]quinazolin-9(3H)-one (3w): eluent: CH2Cl2–MeOH = 30:1. Reaction time: 15 h. Isolated yield: 67% (40.3 mg); white solid; mp 312–314 °C. 1H NMR (600 MHz, DMSO-d 6): δ = 8.16 (d, J = 7.7 Hz, 1 H), 7.78 (t, J = 7.4 Hz, 1 H), 7.50 (d, J = 7.9 Hz, 1 H), 7.33 (t, J = 7.5 Hz, 1 H), 2.36 (s, 3 H). 13C NMR (151 MHz, DMSO-d 6): δ = 161.9, 155.2, 151.0, 139.7, 134.8, 127.3, 122.6, 117.2, 113.3, 14.4. ESI–HRMS: m/z [M + H]+ calcd for C10H9N4O: 201.0771; found: 201.0770.
For selected papers, see:
For selected reviews on copper-catalyzed cross-couplings, see: