反应详情

Sodium metal (0.28 g, 12.6 mmoles) is dissolved in 50 mL of freshly distilled ammonia at reflux under argon. The reaction mixture is stirred at reflux until the solution turns light gray. 4,6-Bis(1,1-dimethylethyl)-5-[(2-methoxyethoxy)methoxy]-2-methylpyrimidine (3.0 g, 9.7 mmoles) is dissolved in 20 mL of tetrahydrofuran and added to the reaction. After 10 minutes, isoamyl nitrite (2.3 g, 19.3 mmoles) is added, and the reaction mixture is stirred at reflux for 2 hours. It is quenched by the addition of ammonium chloride (1.0 g, 18.7 mmoles) and the ammonia is allowed to evaporate at room temperature. The remaining oil is partitioned between 50 mL of ethyl acetate and 50 mL of water. The organic layer is washed with water (3×50 mL) and brine (50 mL), dried over magnesium sulfate, and the solvent is evaporated. The crude product is adsorbed onto a silica gel plug which is eluted with 300 mL of 5% ether in chloroform, followed by 300 mL of ether. Evaporation of the ether eluant gives 4,6-bis(1,1-dimethylethyl)-5-[(2-methoxyethoxy)methoxy]-2-pyrimidinecarboxaldehyde oxime (0.7 g, 21%), mp 90°-97° C. H1 -NMR (CDCl3) δ 10.40 (s, 1H=NOH), 8.17 (s, 1H, HON=CH<bs>--- -),5.00 (s, 2H, O--CH2 --O) , 3.97 (m, 2H) , 3.64 (m, 2H), 3.42 (s, 1H, OCH3), 1.45 (s, 18H, C. (CH3)3). C13 -NMR (CDCl3) δ 170, 155, 148, 147, 102, 72, 70, 60, 39, 30.

1. temperatureat reflux under argon
2. temperatureat reflux until the solution
3. additionadded to the reaction
4. stirringthe reaction mixture is stirred
5. temperatureat reflux for 2 hours
6. customto evaporate at room temperature
7. customThe remaining oil is partitioned between 50 mL of ethyl acetate and 50 mL of water
8. washThe organic layer is washed with water (3×50 mL) and brine (50 mL)
9. dry with materialdried over magnesium sulfate
10. customthe solvent is evaporated
11. washis eluted with 300 mL of 5% ether in chloroform
12. customEvaporation of the ether eluant