反应详情

A solution of the title compound of Example 3 (37.1 g, 164 mmol) in a mixture of MeOH (100 mL) and acetic acid (25 mL) was added 10% Pd-C (3.7 g) and the reaction mixture was hydrogenated (50. psi) for 24 h at rt in a Parr apparatus. Analysis of the reaction by TLC (solvent system A) and IR (to look for presence or absence of N3 str peak at 2100 cm31 1) indicated the reaction to be complete. The solution was filtered through celite to remove catalyst and the filtrate was evaporated in vacuo to give the crude product as an oily residue. The residue was dissolved in 500 mL of 10% aqueous acetic acid and the solution was extracted with Et2O (3×200 mL). The combined ethereal extract was discarded and the aqueous solution was basified by addition of excess concentrated aqueous NH3 solution. The basified mixture was extracted with Et2O (3×200 mL) and the combined organic extract was dried (Na2SO4) and evaporated to give the product (22.8 g, 69%) as a pale yellow oil. The hemifumarate of the title compound crystallized from 2-propanol: mp 197°-198° C., 1H-NMR (CDCl3) ∂3.93 (br s, 1H), 3.82 (dm, Jgem =13 Hz, 1H), 2.70-2.87 (complex m, 2H), 2.56 (m, 1H), 1.93 (dm, Jgem =13 Hz, 1H), 1.68 (m, 1H), 1.46 (s, 9H), 1.29-1.41 (complex m, 3H), 1.24 (m, 1H); CIMS (MH+ calcd for C10H20N2O2): 201. Found (MH+): 201; Anal. (calc'd for C10H20N2O2 ·0.5C4H4O4):C,H,N.

1. customfor 24 h
2. customat rt
3. customAnalysis of the reaction by TLC (solvent system A) and IR (
4. customthe reaction
5. filtrationThe solution was filtered through celite
6. customto remove catalyst
7. customthe filtrate was evaporated in vacuo
8. customto give the crude product as an oily residue
9. extractionthe solution was extracted with Et2O (3×200 mL)
10. extractionThe combined ethereal extract
11. additionthe aqueous solution was basified by addition of excess concentrated aqueous NH3 solution
12. extractionThe basified mixture was extracted with Et2O (3×200 mL)
13. extractionthe combined organic extract
14. dry with materialwas dried (Na2SO4)
15. customevaporated