反応 #8633

反応方程式

magnesium

iodine

4-bromo-1-butene

24

Difluorodiphenylsilane

iodine

→

31

収率 83.1%

(3-Buten-1-yl)diphenylfluorosilane

収率 83.1%

溶媒

ether

ether

反応条件

後処理

1. 1
   その他In a two-neck flask equipped with a condenser
2. 2
   温度The flask was warmed
3. 3
   温度the resulting mixture refluxed for 2 h
4. 4
   workup.ADDITIONadded over 30 min via cannula to a second flask
5. 5
   その他the reaction mixture was quenched with water (20 mL)
6. 6
   その他the organic layer isolated
7. 7
   抽出The aqueous layer was extracted twice with 50-mL portions of ether
8. 8
   洗浄The combined organic extracts were washed with saturated aqueous NaCl
9. 9
   乾燥dried over Na2SO4
10. 10
    濃縮concentrated
11. 11
    workup.DISTILLATIONDistillation (134° C., 1.5 mm Hg)

実験手順

In a two-neck flask equipped with a condenser was placed magnesium (3.46 g, 142 mmol) and a crystal of iodine. The flask was warmed with heat gun until iodine had sublimed. A solution of 4-bromo-1-butene (9.62 g, 71.3 mmol) in ether (100 mL) was added dropwise in 30 min and the resulting mixture refluxed for 2 h. This Grignard solution was cooled to rt and added over 30 min via cannula to a second flask containing 24 (15.7 g, 71.3 mmol) in ether (100 mL) at rt. After stirring overnight at rt under argon, the reaction mixture was quenched with water (20 mL) and the organic layer isolated. The aqueous layer was extracted twice with 50-mL portions of ether. The combined organic extracts were washed with saturated aqueous NaCl, dried over Na2SO4, and concentrated. Distillation (134° C., 1.5 mm Hg) provided pure 31 as a colorless oil (15.2 g, 83%): 1H NMR (300 MHz, CDCl3) δ 7.62 (d, J=7.8 Hz, 4H), 7.50–7.39 (m, 6H), 5.97–5.83 (m, 1H), 5.02 (dd, J=17.1, 1.7 Hz, 1H), 4.94 (dd, J=10.2, 1.7 Hz, 1H), 2.28–2.20 (m, 2H), 1.38–1.30 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 140.9, 135.9, 134.1, 129.7, 127.8, 113.1, 26.9, 14.0.

出典