反应详情

To a solution of 3,4-dichloroacetophenone (2 mmol) in ethanol was added dimethylamine (5 equiv.), paraformaldehyde (5 equiv.) and aq. HCl. After 12 h, the solvent was removed and ethyl acetate and 1N NaOH were added and organic layer was extracted 3 times. It was dried over MgSO4, filtered, evaporated and the filtrate was concentrated at reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate and hexane. The product was dissolved in methanol and added NaBH4 (2 equiv.). After 2 h, sat. NaHCO3 and ethyl acetate were added and the organic layer was extracted 3 times with ethyl acetate. It was dried over MgSO4, filtered, evaporated and the filtrate was concentrated at reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate and methanol. The resulting residue was dissolved in THF and was added 1H-tetrazole (1.5 equiv.), triphenylphosphine (1.5 equiv.) and diisopropyl azodicarboxylate (1.5 equiv.) dropwise at 0□ and warmed to room temperature. After 2 h, the solvent was removed and the residue was purified by column chromatography eluting with ethyl acetate and methanol: Yield 35% 1H-NMR (CDCl3, 200 MHz) d 2.2 (m, 7H), 2.6 (m, 2H), 6.0 (t, 1H), 7.2 (dd, 1H), 7.4 (dd, 1H), 7.5 (d, 1H), 8.5 (s, 1H)

1. customthe solvent was removed
2. additionethyl acetate and 1N NaOH were added
3. extractionorganic layer was extracted 3 times
4. dry with materialIt was dried over MgSO4
5. filtrationfiltered
6. customevaporated
7. concentrationthe filtrate was concentrated at reduced pressure
8. customThe residue was purified by column chromatography
9. washeluting with ethyl acetate and hexane
10. dissolutionThe product was dissolved in methanol
11. waitAfter 2 h
12. extractionthe organic layer was extracted 3 times with ethyl acetate
13. dry with materialIt was dried over MgSO4
14. filtrationfiltered
15. customevaporated
16. concentrationthe filtrate was concentrated at reduced pressure
17. customThe residue was purified by column chromatography
18. washeluting with ethyl acetate and methanol
19. dissolutionThe resulting residue was dissolved in THF
20. waitAfter 2 h
21. customthe solvent was removed
22. customthe residue was purified by column chromatography
23. washeluting with ethyl acetate and methanol