反应 #1005935

反应方程式

ethyl acetate

lithium-aluminum hydride

2-butin-1-ol

tri(n-butyl)stannyl-methanolate

→

(Z)-3-Tributylstannanyl-but-2-en-1-ol

溶剂

water

THF

THF

methanol

反应条件

后处理

1. 1
   其他has been lowered to 0° C.
2. 2
   workup.STIRRINGStirring
3. 3
   workup.STIRRINGwhile stirring
4. 4
   其他A strongly exothermic reaction
5. 5
   workup.STIRRINGStirring
6. 6
   workup.WAITwas continued for 10 min
7. 7
   温度without cooling
8. 8
   workup.STIRRINGwhile stirring
9. 9
   workup.STIRRINGStirring
10. 10
    workup.WAITwas continued for 2 d at 4° C
11. 11
    workup.WAITwas continued for 1 h at ambient temperature
12. 12
    萃取extracted thrice with 150 ml diethyl ether each, the combined extracts
13. 13
    洗涤were washed twice with 80 ml of water each, then once with 40 ml saturated aqueous sodium chloride solution
14. 14
    干燥dried with sodium sulfate
15. 15
    浓缩concentrated in vacuo
16. 16
    其他Yield 48.6 g oil, which have been purified by chromatography on 300 g silica gel with hexane/MTBE (10:1)

实验过程

To 156.9 ml (156.9 mmol) of a 1 molar solution of lithium-aluminum-hydride in THF 0.77 g (14.3 mmol) sodium methylate have been added and the temperature has been lowered to 0° C. afterwards. Then a solution of 10.0 g (142.7 mmol) 2-butin-1-ol in 108 ml THF has been added dropwise with stirring at this temperature. Stirring was continued for 36 h at 4° C. Thereafter, at about 0° C., 28.6 ml (292.5 mmol) ethyl acetate was-added slowly while stirring. A strongly exothermic reaction was observed. Stirring was continued for 10 min without cooling. After cooling to about 0° C., 45.8 g (142.7 mmol) tri(n-butyl)stannyl-methanolate have been added dropwise while stirring. Stirring was continued for 2 d at 4° C. After addition of 112.9 g methanol stirring was continued for 1 h at ambient temperature. The reaction mixture was poured into 250 ml of water, extracted thrice with 150 ml diethyl ether each, the combined extracts were washed twice with 80 ml of water each, then once with 40 ml saturated aqueous sodium chloride solution, dried with sodium sulfate and concentrated in vacuo. Yield 48.6 g oil, which have been purified by chromatography on 300 g silica gel with hexane/MTBE (10:1). Final yield 34.6 g (67%) oil. δ=0.90 (m); 1.30 (m); 1.50 m); 1.97 (s); 4.02 (t); 6.27 (t).

来源