反应详情

A solution of 0.6 g of (3aR,7R,7aR)-4,4-diphenyl-7-fluoroperhydroisoindole hydrochloride and 0.51 cm3 of triethylamine in 10 cm3 of dry dichloromethane is added to a solution of 0.41 g of ethyl (2-methoxyphenyl)-acetimidate tetrafluoroborate in 10 cm3 of dry dichloromethane. The reaction mixture is refluxed for 3 hours. It is then treated, after re-equilibrating to room temperature, with 5 cm3 of a 10% aqueous solution of potassium carbonate; the organic phase is washed with 10 cm3 of distilled water, dried over magnesium sulphate and concentrated to dryness under reduced pressure (2.7 kPa). The residue is chromatographed on a silica gel column (particle size 0.04-0.06 mm, diameter 2 cm, height 20 cm), eluting under a nitrogen pressure of 0.6 bar with an ethyl acetate, acetic acid and water mixture (15/1/1 by volume) and collecting fractions of 25 cm3. Fractions 24 to 38 are pooled and concentrated to dryness under reduced pressure (2.7 kPa). The residue is taken up in 40 cm3 of dichloromethane, washed with 10 cm3 of a saturated aqueous solution of potassium carbonate and then with 10 cm3 of a saturated aqueous solution of sodium chloride. The organic phase is dried over magnesium sulphate and concentrated to dryness under reduced pressure (2.7 kPa). The residue is crystallized from isopropyl oxide. The crystals are drained and dried. 0.18 g of (3aR,7R,7aR)-4,4-diphenyl-7-fluoro-2-[1-imino-2-(2-methoxyphenyl)ethyl]perhydroisoindole is obtained in the form of white crystals, melting point 184° C., with decomposition.

1. temperatureThe reaction mixture is refluxed for 3 hours
2. additionIt is then treated
3. customto room temperature
4. washthe organic phase is washed with 10 cm3 of distilled water
5. dry with materialdried over magnesium sulphate
6. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
7. customThe residue is chromatographed on a silica gel column (particle size 0.04-0.06 mm, diameter 2 cm, height 20 cm)
8. washeluting under a nitrogen pressure of 0.6 bar with an ethyl acetate, acetic acid and water mixture (15/1/1 by volume)
9. customcollecting fractions of 25 cm3
10. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
11. washwashed with 10 cm3 of a saturated aqueous solution of potassium carbonate
12. dry with materialThe organic phase is dried over magnesium sulphate
13. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
14. customThe residue is crystallized from isopropyl oxide
15. customdried