反応 #1137869

反応方程式

n-BuLi

hexane

2,3-dihydrothieno[3,4-b][1,4]dioxine

tetramethylethylenediamine

Tributylstannyl chloride

→

tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane

収率 40.0%

溶媒

tetrahydrofuran

反応条件

後処理

1. 1
   温度cooled in a dry ice/acetone bath
2. 2
   workup.STIRRINGstirred at this temperature for 1 hour
3. 3
   温度cooled in a dry ice/acetone bath
4. 4
   温度to warm up
5. 5
   その他The volatiles were removed under reduced pressure
6. 6
   workup.ADDITIONThe residue was diluted with toluene (100 mL)
7. 7
   その他chromatographed
8. 8
   workup.ADDITIONfilled with silica gel (500 mL)
9. 9
   洗浄washed with 2% triethylamine in hexane (500 mL)

実験手順

1.5M n-BuLi in hexane (53 mL, 80 mmol) was added in small portions to a solution of 2,3-dihydrothieno[3,4-b][1,4]dioxine (10.00 g, 80 mmol) and tetramethylethylenediamine (12.0 mL, 80 mmol) in tetrahydrofuran (100 mL) stirred under argon and cooled in a dry ice/acetone bath. The reaction mixture was heated to 35° C., stirred at this temperature for 1 hour, and then cooled in a dry ice/acetone bath. Tributylstannyl chloride (20.3 mL), 75 mmol was then added, the mixture was allowed to warm up, and it was left at room temperature for 16 hours. The volatiles were removed under reduced pressure. The residue was diluted with toluene (100 mL) and chromatographed using a column filled with silica gel (500 mL) washed with 2% triethylamine in hexane (500 mL) to give tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane (12.17 g, 40%) of high purity. 1H NMR (400 MHz, CDCl3): δ 6.57 (s, 1H, thiophene), 4.15 (m, 4H, OCH2CH2O), 1.53 (m, 6H, Bu), 1.32 (quintet, J=7.3 Hz, 6H, Bu), 1.09 (m, 6H, Bu), 0.88 (t, J=7.3 Hz, 9H, Bu).

出典