A kind of synthetic method for preparing marine alkaloid baculiferin-1 intermediate
A technology for intermediates and substances is applied in the field of preparation of natural marine alkaloids BaculiferinL intermediates, and can solve the problems of using expensive catalysts, low yield, increased cost and the like
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Embodiment 1
[0052] Embodiment 1, the synthesis of the Baculiferin L intermediate shown in formula (a):
[0053]
[0054] (1) Put nitrilotriacetic acid (10g, 52.3mmol) in 50mL of methanol solvent, stir at room temperature, add 2.78ml of concentrated sulfuric acid solution, heat up to 65°C after the addition, reflux for 18h, and TLC detects that the reaction is complete. The methanol in the reaction solution was concentrated under reduced pressure, the residue was dissolved in dichloromethane, washed successively with saturated sodium bicarbonate solution (50 mL×2) and saturated sodium chloride (50 mL×2), and the organic layer was dried over anhydrous sodium sulfate , filtered with suction, and the filtrate was concentrated to obtain the compound represented by formula (I), with a yield of 81.14%.
[0055] (2) Compound (2.5g, 10.7mmol) shown in formula (I) and dimethyl oxalate (1.266g, 10.7mmol) were dissolved in sodium methylate solution (from sodium block (1.331g, 0.058mol) and methano...
Embodiment 2
[0078] Embodiment 2, the synthesis of the Baculiferin-L intermediate shown in formula (b):
[0079]
[0080] (1) Put benzyliminodiacetic acid (11.7g, 52.4mmol) in 50mL of methanol solvent, stir at room temperature, add 2.79mL of concentrated sulfuric acid solution, heat up to 65°C after the addition, reflux for 18h, and detect the reaction by TLC After completion, the methanol in the reaction solution was concentrated under reduced pressure, the residue was dissolved in dichloromethane, washed with saturated sodium bicarbonate solution (50mL×2) and saturated sodium chloride (50mL×2) successively, and the organic layer was washed with anhydrous Dry over sodium sulfate, filter with suction, and concentrate the filtrate to obtain the compound shown in formula (I);
[0081] (2) The compound represented by formula (I) (4.3g, 17.1mmol) and dimethyl oxalate (2.01g, 17.1mmol) were dissolved in sodium methoxide solution (from sodium block (1.96g, 0.085mol) and methanol (25mL ), aft...
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