A kind of statin drug intermediate and its preparation method and application
A technology for intermediates and drugs, applied in the field of organic chemical synthesis, can solve problems such as low reaction yield, and achieve the effect of cheap and easy-to-obtain raw materials
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Embodiment 1
[0037]
[0038] Dissolve 1,4-cyclohexanedione (10.0g) in 100mL of toluene, add trimethyl orthoformate (19.8g) and p-toluenesulfonic acid (0.46g) under stirring at room temperature, stir for 1 hour, add 6-chloro Methyl-4-hydroxy-tetrahydropyran-2-one (30.0 g), continued stirring for 1 hour. The reaction solution was poured into aqueous sodium bicarbonate solution, extracted twice with toluene, the combined organic phases were washed once with saturated brine, dried over sodium sulfate, concentrated to dry column chromatography to obtain 33.5 g of the target product with a molar yield of 80%.
[0039] The structure of the product was confirmed by H NMR spectroscopy and electrospray ionization mass spectrometry.
[0040] 1 H NMR (300MHz, CDCl 3 ): δ4.53-4.62(1H,m),4.31-4.40(1H,m),3.95-4.15(2H,m),3.68(3H,s),3.66(3H,s),3,44-3.56 (4H, m), 2.35-2.65 (4H, m), 1.22-2.08 (12H, m).
[0041] MS (ESI) m / z: (M+H) = 469.1.
Embodiment 2
[0043]
[0044] Dissolve 1,4-cyclohexanedione (12.0g) in 120mL of dichloromethane, add trimethyl orthoformate (23.8g) and p-toluenesulfonic acid (0.46g) under stirring at room temperature, stir for 1 hour, add 6 - Azidomethyl-4-hydroxy-tetrahydropyran-2-one (40.2 g), continue stirring for 1 hour. The reaction solution was poured into aqueous sodium bicarbonate solution, extracted twice with toluene, the combined organic phases were washed once with saturated brine, dried over sodium sulfate, concentrated to dry column chromatography to obtain 40.2 g of the target product with a molar yield of 78%.
[0045] The structure of the product was confirmed by H NMR spectroscopy and electrospray ionization mass spectrometry.
[0046] 1 H NMR (300MHz, CDCl 3 ):δ4.48-4.57(1H,m),4.30-4.43(1H,m),3.91-4.12(2H,m),3.64(3H,s),3.61(3H,s),2.32-2.64(4H ,m), 1.19-2.04(16H,m).
[0047] MS (ESI) m / z: (M+H) = 483.2.
Embodiment 3
[0049]
[0050] Dissolve 1,4-cyclohexanedione (15.0g) in 150mL tetrahydrofuran, add triethyl orthoformate (42.3g) and p-toluenesulfonic acid (0.67g) under stirring at room temperature, stir for 1 hour, add 6-cyano methyl-4-hydroxy-tetrahydropyran-2-one (44.3 g), and the stirring reaction was continued for 1 hour. The reaction solution was poured into aqueous sodium bicarbonate solution, extracted twice with toluene, the combined organic phases were washed once with saturated brine, dried over sodium sulfate, concentrated to dry column chromatography to obtain 50.9 g of the target product with a molar yield of 82%.
[0051] The structure of the product was confirmed by H NMR spectroscopy and electrospray ionization mass spectrometry.
[0052] 1 H NMR (300MHz, CDCl 3 ):δ; 4.56-4.68(1H,m),4.31-4.40(1H,m),4.13(2H,q),3.44-3.56(4H,m),2.35-2.65(8H,m),1.21-2.06 (18H,m).
[0053] MS (ESI) m / z: (M+H) = 479.2.
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