A kind of preparation method of quinoxaline compounds
A compound, the technology of quinoxaline, which is applied in the field of preparation of quinoxaline compounds, can solve the problems such as the limitation of synthetic molecular structure diversity, and achieve the effect of diverse structure of target products, simple and easy synthesis process
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Embodiment 1
[0018] Dissolve 1.0 mmol of 1,3-dicarbonyl compound and 1.0 mmol of 2,2,6,6-tetramethylpiperidine oxide in 20 mL of ethyl acetate, add 0.2 mmol of cerium ammonium nitrate and heat to 60 °C and stir for 30 Minutes, after the reaction is complete, filter to remove insoluble inorganic salts, remove ethyl acetate by rotary evaporation, and separate by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1) to obtain α-position 2,2,6,6-tetramethyl 1,3-dicarbonyl compounds substituted by base piperidine oxides, the 1,3-dicarbonyl compounds substituted by α-position 2,2,6,6-tetramethylpiperidinium oxides are used for quinoxaline compounds synthesis.
Embodiment 2
[0020]
[0021] Dissolve 108 mg (1.0 mmol) of the raw material compound o-phenylenediamine and 314 mg (1.1 mmol) of ethyl acetoacetate substituted by α-position TEMPO in 5.0 mL of glacial acetic acid, stir the reaction system at room temperature for 10 minutes, evaporate the acetic acid, add The residue was dissolved in ethyl acetate, washed twice with saturated sodium bicarbonate solution (30mL×2), the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation, column chromatography (eluent: petroleum ether: acetic acid Ethyl ester = 5:1) isolated to obtain 212 mg (98%) of pure compound 3-1.
[0022] 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (dd, J = 8.3, 1.2 Hz, 1H), 8.05 (d, J =8.3 Hz, 1H), 7.83 (ddt, J = 8.7, 7.0, 1.7 Hz, 1H), 7.77 (ddd, J = 8.7, 3.3,1.7 Hz, 1H), 4.57 (qd, J = 7.1, 1.4 Hz, 2H), 2.96 (d, J = 1.5 Hz, 3H), 1.50 (td, J = 7.1, 1.5 Hz, 3H).
Embodiment 3
[0024]
[0025] Compound 3-2 was prepared in the same manner as Compound 3-1, except that α-TEMPO-substituted methyl acetoacetate was used instead of α-TEMPO-substituted ethyl acetoacetate.
[0026] 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (dd, J = 8.4, 1.1 Hz, 1H), 8.05 (dd, J = 8.4, 1.0 Hz, 1H), 7.87-7.81 (m, 1H), 7.80-7.73 (m, 1H), 4.09 (s, 3H), 2.98(s, 3H).
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