反応 #1859303

反応方程式

116b

Methyl 3-Methylthiophene-2-carboxylate

N-bromosuccinimide

2,2′-azobisisobutyronitrile

→

116c

収率 99.7%

Methyl 3-(Bromomethyl)thiophene-2-carboxylate

収率 99.7%

溶媒

carbon tetra-chloride

反応条件

後処理

1. 1
   その他A 1-L single-neck round-bottomed flask equipped with a magnetic stirrer
2. 2
   温度reflux condenser and nitrogen inlet
3. 3
   その他was purged with nitrogen
4. 4
   workup.ADDITIONwas added
5. 5
   温度The resulting mixture was refluxed for 3 h
6. 6
   ろ過filtered
7. 7
   洗浄The filter cake was washed with carbon tetrachloride (2×50 mL)
8. 8
   workup.ADDITIONThe filtrate was diluted with ethyl acetate (300 mL)
9. 9
   洗浄washed with water (40 mL), saturated aqueous sodium bicarbonate (40 mL) and brine (40 mL)
10. 10
    乾燥The organic layer was dried over sodium sulfate
11. 11
    濃縮concentrated under reduced pressure

実験手順

A 1-L single-neck round-bottomed flask equipped with a magnetic stirrer, reflux condenser and nitrogen inlet was purged with nitrogen and charged with 116b (5.00 g, 32.0 mmol), N-bromosuccinimide (5.70 g, 32.0 mmol) and carbon tetra-chloride (300 mL). The solution was heated to 70° C. (oil bath temperature), and 2,2′-azobisisobutyronitrile (526 mg, 3.20 mmol) was added. The resulting mixture was refluxed for 3 h. After that time, the mixture was cooled to room temperature and filtered. The filter cake was washed with carbon tetrachloride (2×50 mL). The filtrate was diluted with ethyl acetate (300 mL) and washed with water (40 mL), saturated aqueous sodium bicarbonate (40 mL) and brine (40 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure to afford a quantitative yield (7.50 g) of 116c as a colorless oil: 1H NMR (300 MHz, CDCl3) δ 7.39 (d, 1H, J=5.0 Hz), 7.11 (d, 1H, J=5.1 Hz), 4.85 (s, 2H), 3.83 (s, 3H).

出典