反应详情

In an argon stream, 3-benzyloxybenzaldehyde (21.3 g) and diethylphosphonoethyl acetate (23.6 g) were suspended in dry DMF (250 ml). Under ice cooling and stirring, 65% oily sodium hydride (3.88 g) was added little by little; after completion of this addition, the mixture was stirred at room temperature for 2 hours. After the solvent was distilled off, the residue was dissolved in ethyl acetate and washed with water and saturated saline, after which it was dried over anhydrous sodium sulfate. Under reduced pressure, the solvent was distilled off to yield 33.15 g of a crude product of ethyl (E)-3-[3-(benzyloxy)phenyl]-2-propenate as an oily substance. This product was dissolved in ethanol (406 ml); ethylenediamine-treated 5% palladium carbon [Pd—C (en), 2.7 g] was added, followed by vigorous stirring in a hydrogen atmosphere. Hydrogen (1.75 L) was consumed to complete hydrogenation, and the catalyst was filtered off. Under reduced pressure, the solvent was distilled off; the residue was dissolved in dehydrated THF (120 ml). This solution was added drop by drop to a mixture of lithium aluminum hydride (4.61 g) suspended in dehydrated THF (120 ml) under ice cooling. The reaction mixture was stirred under ice cooling for 1.5 hours and at room temperature for 1 hour. The reaction mixture was added to ice water and acidified, after which it was extracted with ethyl acetate, washed with water and saturated saline, after which it was dried over anhydrous sodium sulfate. Under reduced pressure, the solvent was distilled off; the residue was purified by silica gel column chromatography to yield the titled compound (14.39 g) as a colorless oily substance.

1. additionafter completion of this addition
2. stirringthe mixture was stirred at room temperature for 2 hours
3. distillationAfter the solvent was distilled off
4. dissolutionthe residue was dissolved in ethyl acetate
5. washwashed with water and saturated saline
6. dry with materialafter which it was dried over anhydrous sodium sulfate
7. distillationUnder reduced pressure, the solvent was distilled off
8. customto yield 33.15 g of a crude product of ethyl (E)-3-[3-(benzyloxy)phenyl]-2-propenate as an oily substance
9. additionwas added
10. customHydrogen (1.75 L) was consumed
11. filtrationthe catalyst was filtered off
12. distillationUnder reduced pressure, the solvent was distilled off
13. dissolutionthe residue was dissolved in dehydrated THF (120 ml)
14. additionThis solution was added drop by drop
15. additionto a mixture of lithium aluminum hydride (4.61 g)
16. stirringThe reaction mixture was stirred under ice cooling for 1.5 hours and at room temperature for 1 hour
17. additionThe reaction mixture was added to ice water
18. extractionafter which it was extracted with ethyl acetate
19. washwashed with water and saturated saline
20. dry with materialafter which it was dried over anhydrous sodium sulfate
21. distillationUnder reduced pressure, the solvent was distilled off
22. customthe residue was purified by silica gel column chromatography