A kind of solvent-free preparation method of cyclopentylpyrimidine compound
A cyclopentyl pyrimidine and solvent-free technology is applied in the field of chemical preparation and solvent-free preparation of cyclopentyl pyrimidine compounds, which can solve problems such as difficulty in removing high-boiling organic solvents, and achieve the improvement of equipment production capacity, reaction rate improvement, The effect of increasing the concentration of reactants
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Embodiment 1
[0023] Take a 500ml three-neck flask equipped with a condensing reflux tube and nitrogen balloon protection, add 2-[[(3AR,4S,6R,6AS)-6-aminotetrahydro-2,2-dimethyl-4H-cyclopentenene -1,3-dioxolan-4-yl]oxy]ethanol (88.7g, 408.3mmol, 1.0eq), 4,6-dichloro-2-(propylthio)-5-aminopyrimidine (98.0g, 408.3mmol, 1.0eq), N,N-diisopropylethylamine (79.1g, 612.5mmol, 1.5eq), heated and stirred at 120-125°C for 10 hours (HPLC detection, peak area percentage 4,6 -Dichloro-2-(propylthio)-5-aminopyrimidine <1.0%), stop heating and cool down to <60°C, add ethyl acetate and water to wash and extract. Concentrate under reduced pressure until 200 ml of ethyl acetate remains, add petroleum ether for recrystallization, and obtain 160 g of off-white solid, yield 93.5%, HPLC peak area percentage SM-C ≥ 98.5%.
Embodiment 2
[0025] Take a 500ml three-neck flask equipped with a condensing reflux tube and nitrogen balloon protection, add 2-[[(3AR,4S,6R,6AS)-6-aminotetrahydro-2,2-dimethyl-4H-cyclopentenene -1,3-dioxolan-4-yl]oxy]ethanol (88.7g, 408.3mmol, 1.0eq), 4,6-dichloro-2-(propylthio)-5-aminopyrimidine (98.0g, 408.3mmol, 1.0eq), N,N-diisopropylethylamine (105.5g, 816.6mmol, 2.0eq), heated and stirred at 120-125°C for 10 hours (HPLC detection, peak area percentage 4,6 -Dichloro-2-(propylthio)-5-aminopyrimidine <1.0%), stop heating and cool down to <60°C, add ethyl acetate and water to wash and extract. Concentrate under reduced pressure until 200 ml of ethyl acetate remains, add petroleum ether for recrystallization, and obtain 152.7 g of off-white solid, yield 89%, HPLC peak area percentage SM-C ≥ 98.5%.
Embodiment 3
[0027] Take a 500ml three-neck flask equipped with a condensing reflux tube and nitrogen balloon protection, add 2-[[(3AR,4S,6R,6AS)-6-aminotetrahydro-2,2-dimethyl-4H-cyclopentenene -1,3-dioxolan-4-yl]oxy]ethanol (88.7g, 408.3mmol, 1.0eq), 4,6-dichloro-2-(propylthio)-5-aminopyrimidine (98.0g, 408.3mmol, 1.0eq), N,N-diisopropylethylamine (131.9g, 1020.75mmol, 2.5eq), heated and stirred at 125-130°C for 8 hours (HPLC detection, peak area percentage 4,6 -Dichloro-2-(propylthio)-5-aminopyrimidine <1.0%), stop heating and cool down to <60°C, add ethyl acetate and water to wash and extract. Concentrate under reduced pressure until 200 ml of ethyl acetate remains, add petroleum ether for recrystallization, and obtain 150.5 g of off-white solid, yield 88%, HPLC peak area percentage SM-C ≥ 98.5%.
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