反応 #2329956

反応方程式

1-chloro-6-iodohexane

thiophene

n-butyllithium

→

oil

収率 92.0%

2-(6-Chlorohexyl)thiophene

収率 92.0%

溶媒

THF

反応条件

後処理

1. 1
   workup.ADDITIONAfter complete addition
2. 2
   その他The reaction is quenched with sat. aq. ammonium chloride
3. 3
   抽出the reaction mixture is extracted with ethyl acetate (3×70 ml)
4. 4
   洗浄The combined organic extracts are washed with water, brine
5. 5
   乾燥dried over magnesium sulphate
6. 6
   その他The solvent is removed under reduced pressure
7. 7
   その他the residue is chromatographed (silica gel, petroleum ether)

実験手順

To a stirred solution of thiophene (5.0 g, 59.5 mmol) in dry THF (50 ml) is added n-butyllithium (2.5 M in hexanes, 20.0 ml, 50.0 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture is allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of 1-chloro-6-iodohexane (12.3 g, 50.0 mmol). The resultant mixture is stirred overnight at room temperature. The reaction is quenched with sat. aq. ammonium chloride, and the reaction mixture is extracted with ethyl acetate (3×70 ml). The combined organic extracts are washed with water, brine, and dried over magnesium sulphate. The solvent is removed under reduced pressure and the residue is chromatographed (silica gel, petroleum ether), to give a pale yellow oil (9.3 g, 92%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.06 (dd, J=5.1 Hz, 1.2 Hz, 1H, Ar—H), 6.87 (dd, J=5.1 Hz, 3.4 Hz, 1H, Ar—H), 6.75 (m, 1H, Ar—H), 3.48 (t, J=6.6 Hz, 2H, ClCH2), 2.80 (t, J=7.4 Hz 2H, ArCH2), 1.61-1.78 (m, 4H, CH2), 1.29-1.50 (m, 4H, CH2); 13C NMR (75 MHz, CDCl3): δ (ppm) 145.5 (quat.), 126.7 (CH), 124.1 (CH), 122.9 (CH), 45.1 (CH2), 32.6 (CH2), 31.7 (CH2), 29.9 (CH2), 28.4 (CH2) 26.7 (CH2); MS (m/e) 204 (M+, 9%), 202 (M+, 3%), 97 (100).

出典