Method for preparing poly-substituted quinoline compound
A multi-substitution and compound technology, which is applied in the field of preparation of multi-substituted quinoline compounds, can solve problems such as lack of flexibility in substitution forms
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Embodiment 1
[0022] The preparation of embodiment 1 6-quinoline acetic acid (R 4 for methylene carboxyl)
[0023] 4.8 mol of acrolein, 1.37 mol of p-aminophenylacetic acid, and 0.68 mol of ferrous sulfate heptahydrate were successively put into the reactor, stirred evenly, and 4.5 mol of concentrated sulfuric acid was slowly added dropwise. After the dropwise addition, heat to reflux, and after the reflux reaction for about 20 hours, the reaction system is cooled to room temperature. Add 1.15 L of 32% sodium hydroxide solution to the reaction system, adjust the pH of the system to 13, filter after stirring fully, collect the filtrate, and adjust the pH of the filtrate to 4.0 with glacial acetic acid. The precipitated solid was filtered and recrystallized with 150ml of methanol to obtain 179.6g of 6-quinolineacetic acid with a yield of 70%; colorless crystals with a melting point of 220°C-222°C. H NMR spectrum ( 1 H NMR, 200MHz, DMSO) δ8.87(dd, J=4.17, 1.64Hz, 1H), 8.33(d, J=7.58Hz, 1H),...
Embodiment 2
[0024] The preparation of embodiment 2 6-quinoline ethyl acetate (R 4 6-methylenecarbonyloxyethyl)
[0025] Put 0.96mol 6-quinolineacetic acid and 26mol absolute ethanol into the reaction kettle successively, then add 20ml concentrated sulfuric acid, heat and reflux for about 6 hours, cool to room temperature, concentrate to remove ethanol, and dissolve with 68ml 15% sodium carbonate solution After the concentrate was stirred evenly, it was extracted 4 times with 500 ml of ethyl acetate, and the extracts were combined and concentrated to obtain 134.3 g of ethyl 6-quinoline acetate with a yield of 65%. Proton nuclear magnetic resonance (1H NMR, 200MHz, DMSO) δ8.87 (dd, J=4.17, 1.64Hz, 1H), 8.33 (d, J=7.58Hz, 1H), 7.98 (d, J=8.59Hz, 1H ), 7.86(d, J=1.77Hz, 1H), 7.68(dd, J=8.59, 2.02Hz, 1H), 7.51(dd, J=8.34, 4.04Hz, 1H), 4.15(q, J=7.2Hz , 2H), 3.80(s, 2H) 1.30(t, J=7.2Hz, 3H).
Embodiment 3
[0026] The preparation of embodiment 3 6-quinoline isopropionic acid ethyl esters (R 4 6-(2-methyl)-ethoxycarbonylmethylene)
[0027]At -78°C, under the protection of argon, add dropwise 0.17mol tetrahydrofuran solution of ethyl 6-quinoline acetate to 0.221mol tetrahydrofuran solution of lithium diisopropylamide, stir for 1 hour, then add dropwise 0.179mol iodine Methane tetrahydrofuran solution, after that, react at -78°C for 3 hours, then raise the temperature naturally, stir and react for 12 hours, after the reaction is completed, quench the reaction with 20ml of 30% ammonium chloride solution for 0.5h, remove the tetrahydrofuran by rotary evaporation, add 500ml of dichloro Diluted with methane and concentrated to obtain 216.6 g of yellow liquid ethyl 6-quinoline isopropionate with a yield of 55%. H NMR spectrum ( 1 H NMR, 200MHz, DMSO) δ8.87(dd, J=4.17, 1.64Hz, 1H), 8.33(d, J=7.58Hz, 1H), 7.98(d, J=8.59Hz, 1H), 7.86(d , J=1.77Hz, 1H), 7.68 (dd, J=8.59, 2.02Hz, 1H), 7.51...
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