反应详情

In a 25 ml. round-bottomed flask equipped with a magnetic bar, water-cooled reflux condenser, and an argon filled balloon, 7-butyramido-2-methylquinoline-5,8-dione (30) (prepared as described in Example 30) (0.516 g., 2 mmol), selenium dioxide (0.255 g., 2.3 mmol), 12 ml. of dried, distilled 1,4-dioxane, and 0.25 ml. of water were stirred and slowly heated to reflux over a two-hour period. The reaction was monitored by TLC and found to be complete after 33.5 hours. The selenium metal was allowed to settle, and the supernatant solution was pipetted off and filtered. 1,4-Dioxane (10 ml.) was added to the residue, stirred and refluxed for five minutes. The entire mixture was filtered and the selenium was washed with dichloromethane (10 ml.). All filtrates were combined and stored at 4° C. overnight. This solution was diluted with 50 ml of dichloromethane and washed with a 3% sodium bicarbonate solution (2×50 ml.). The organic layer was dried with magnesium sulfate and rotoevaporated to give a pale yellow product. The solid was dried under vacuum overnight and weighed 0.356 g. (yield of 65%). The product was recrystallized from ethyl acetate: mp. 208°-210° C.; 1H NMR (CDCl3) δ 1.02 (3H, t, J=7.4 Hz, C-7NHCOCH2CH2CH3), 1.70-1.89 (2H, m, 7NHCOCH2 CH2CH3), 2.52 (2H, t, J=7.4 Hz, 7NHCOCH2CH2 CH3), 8.06 (1H, s, C-6H), 8.31 (1H, d, J=8.0 Hz, C-3H), 8.39 (1H, br. s, C-7NH), 8.61 (1H, d, J=8.0 Hz, C-4H), 10.28 (1H, s, C-2CHO); IR (KBr) vmax 3299, 3081, 2966, 2935, 2876, 1723, 1694, 1638, 1606, 1505 cm-1 ; EIMS, m/e (relative intensity) 272 (54), 202 (36), 175 (9); HRMS, m/e for C14H12N2O4 calculated 272.079707, found 272.078696; analysis for C14H12N2O4 calculated C, 61.76; H, 4.44; N, 10.29; found C, 61.31; H, 4.36; N, 9.94.

1. customround-bottomed flask equipped with a magnetic bar
2. temperaturereflux condenser
3. customof dried
4. distillationdistilled 1,4-dioxane, and 0.25 ml
5. temperatureslowly heated
6. temperatureto reflux over a two-hour period
7. filtrationfiltered
8. addition1,4-Dioxane (10 ml.) was added to the residue
9. stirringstirred
10. temperaturerefluxed for five minutes
11. filtrationThe entire mixture was filtered
12. washthe selenium was washed with dichloromethane (10 ml.)
13. waitstored at 4° C. overnight
14. additionThis solution was diluted with 50 ml of dichloromethane
15. washwashed with a 3% sodium bicarbonate solution (2×50 ml.)
16. dry with materialThe organic layer was dried with magnesium sulfate
17. customto give a pale yellow product
18. customThe solid was dried under vacuum overnight
19. customThe product was recrystallized from ethyl acetate