Method for preparing aliskiren intermediate
A technology for intermediates and compounds, which is applied in the field of preparation of aliskiren intermediate compounds, can solve the problems of long reaction time, increased cost, environmental impact, etc., and achieves the effects of long reaction time, reduced impact and easy operation.
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Embodiment 1
[0037] Add 4-methoxy-3-hydroxy-benzaldehyde (50g, 0.33mol), 3-methoxy-1-bromopropane (75g, 0.49mol), potassium carbonate (67g, 0.485mol) into a 500mL three-necked flask ) and 250mL ethanol, heated to reflux for 4 hours, then cooled to 20°C, added sodium borohydride (6.0g, 0.16mol), reacted for 10 minutes, concentrated under reduced pressure and distilled ethanol, then added 250mL water, 150mL dichloromethane, Stand to separate layers, extract the water phase with 50ml of dichloromethane for 2 times, combine the dichloromethane layers, wash 3 times with 150ml of water each time, dry and filter with anhydrous sodium sulfate, concentrate to obtain the aliskiren intermediate compound 4- Methoxy-3-(3-methoxypropoxy)-benzyl alcohol 71.68 g. (Molar yield: 96%)
[0038] H-NMR (CDCl 3 ): 6.80-6.95 (m, 3H), 4.58 (d, 2H), 4.11 (t, 2H), 3.84 (s, 3H), 3.56 (t, 2H), 2.33 (s, 3H), 2.11 (m, 2H), 1.95(t, 1H).
Embodiment 2
[0040] Add 4-methoxy-3-hydroxy-benzaldehyde (50g, 0.33mol), 3-methoxy-1-bromopropane (60g, 0.39mol), potassium carbonate (45g, 0.33mol) into a 500mL three-necked flask ) and 250mL ethanol, heated to reflux for 9 hours, then cooled to 5°C, added sodium borohydride (4.5g, 0.12mol), reacted for 45 minutes, concentrated under reduced pressure and evaporated ethanol, then added 250mL water, 150mL dichloromethane, Stand and separate layers, extract the water phase with 50 mL of dichloromethane for 2 times, combine the dichloromethane layers, wash 3 times with 100 mL of water each time, dry and filter with anhydrous sodium sulfate, concentrate to obtain the aliskiren intermediate compound 4- Methoxy-3-(3-methoxypropoxy)-benzyl alcohol 69.8 g. (Molar yield: 93.5%)
[0041] H-NMR (CDCl 3 ): 6.80-6.96 (m, 3H), 4.59 (d, 2H), 4.15 (t, 2H), 3.84 (s, 3H), 3.60 (t, 2H), 2.35 (s, 3H), 2.12 (m, 2H), 1.93(t, 1H).
Embodiment 3
[0043] Add 4-methoxy-3-hydroxy-benzaldehyde (40g, 0.26mol), 3-methoxy-1-bromopropane (43.8g, 0.286mol), potassium carbonate (44g, 0.32 mol) and 200mL ethanol, heated to reflux for 7 hours, then cooled to 10°C, added sodium borohydride (2.9g, 0.078mol), reacted for 30 minutes, concentrated under reduced pressure and evaporated ethanol, then added 200mL water, 120mL dichloromethane , standing and layering, the aqueous phase was extracted twice with 50 mL of dichloromethane, the combined dichloromethane layers were washed with 100 mL of water three times each time, dried and filtered over anhydrous sodium sulfate, and then concentrated to obtain the aliskiren intermediate compound 4 - Methoxy-3-(3-methoxypropoxy)-benzyl alcohol 55.9 g. (Molar yield: 95%)
[0044] H-NMR (CDCl 3 ): 6.80-6.90 (m, 3H), 4.55 (d, 2H), 4.15 (t, 2H), 3.85 (s, 3H), 3.60 (t, 2H), 3.35 (s, 3H), 2.10 (m, 2H), 1.90(t, 1H).
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