反応 #70996

反応方程式

isocyanatotrimethylsilane

3,4-dichloropyridine

2,2,6,6-tetramethylpiperidine

n-BuLi

hexane

acetic acid

isocyanatotrimethylsilane

→

3,4-dichloropicolinamide

収率 39.0%

溶媒

diethyl ether

diethyl ether

water

反応条件

後処理

1. 1
   workup.ADDITIONAfter the addition
2. 2
   その他the cooling bath was removed
3. 3
   温度to warm to room temperature over 1 h
4. 4
   workup.STIRRINGto stir overnight
5. 5
   その他the white solid that formed
6. 6
   ろ過was collected through filtration
7. 7
   洗浄washed with water
8. 8
   抽出The filtrate was extracted with ethyl acetate (3×300 mL)
9. 9
   その他The solid that was collected previously
10. 10
    workup.DISSOLUTIONwas dissolved in the combined organic layers
11. 11
    洗浄the resulting solution was washed with brine (2×200 mL)
12. 12
    乾燥dried over MgSO4
13. 13
    濃縮concentrated in vacuo
14. 14
    その他sonicated
15. 15
    ろ過The remaining solid was collected through filtration
16. 16
    洗浄washed with minimum amount of diethyl ether

実験手順

To a solution of 2,2,6,6-tetramethylpiperidine (31.1 g, 0.22 mol) in diethyl ether (400 mL) at 0° C. was added n-BuLi in hexane (1.6 M, 138.0 mL, 0.22 mol) via syringe over 15 min. The resulting solution was stirred at 0° C. for 0.5 h and at −78° C. for 0.5 h. To this mixture was then slowly added a solution of 3,4-dichloropyridine (29.6 g, 0.20 mol) in diethyl ether (20 mL) via syringe over 15 min. The resulting mixture was stirred at −78° C. for 2 h before the addition of isocyanatotrimethylsilane (85% pure, 40.0 mL, 0.30 mol). The source for isocyanatotrimethylsilane is TCI. After the addition, the cooling bath was removed and the reaction mixture was allowed to warm to room temperature over 1 h. The reaction mixture was quenched with acetic acid (40 g, 0.67 mol) and 200 mL of water. The mixture was allowed to stir overnight and the white solid that formed was collected through filtration and washed with water. The filtrate was extracted with ethyl acetate (3×300 mL). The solid that was collected previously was dissolved in the combined organic layers, and the resulting solution was washed with brine (2×200 mL), dried over MgSO4 and concentrated in vacuo. The residue was suspended in 200 mL of diethyl ether and sonicated. The remaining solid was collected through filtration and washed with minimum amount of diethyl ether to provide 3,4-dichloropicolinamide (14.8 g, 39%).

出典