反応 #2146735

反応方程式

ethyl bromide

magnesium

(5Z)-3-methylnon-5-en-1-ol

2-methylbut-3-yn-2-ol

→

(9Z)-2,7-dimethyltridec-9-en-3-yne-2,5-diol

収率 77.1%

溶媒

tetrahydrofuran

tetrahydrofuran

tetrahydrofuran

tetrahydrofuran

反応条件

後処理

1. 1
   温度by occasional heating with a heat gun
2. 2
   温度under reflux
3. 3
   温度to cool down to room temp.
4. 4
   workup.STIRRINGwith stirring
5. 5
   温度The reaction mixture was then again refluxed for 3 h
6. 6
   その他the heating bath removed
7. 7
   workup.STIRRINGwith stirring over a period of 30 min
8. 8
   温度The reaction mixture was refluxed
9. 9
   workup.STIRRINGwith stirring overnight
10. 10
    温度to cool to room temp.
11. 11
    その他quenched
12. 12
    workup.ADDITIONby pouring into 100 mL of an aqueous satd
13. 13
    その他The organic layer was separated
14. 14
    抽出the aqueous one extracted three times with 500 mL of ether each
15. 15
    乾燥The combined organic extracts were dried with sodium sulphate
16. 16
    濃縮concentrated to dryness in a rotary evaporator
17. 17
    その他The resulting residue (10.8 g) was purified by flash chromatography (200 g of silica gel, pentane/ether, 1:1, Rf=0.22)

実験手順

A solution of 10.4 g (95.6 mmol) of ethyl bromide in 40 mL of dry tetrahydrofuran was added dropwise over a period of 30 min to a vigorously stirred suspension of 2.32 g (95.6 mmol) of magnesium turnings in 15 mL of dry tetrahydrofuran, with the reaction being initiated by occasional heating with a heat gun. After stirring the reaction mixture for 90 min under reflux, it was allowed to cool down to room temp., and a solution of 3.54 g (42.2 mmol) of 2-methylbut-3-yn-2-ol in 40 mL of dry tetrahydrofuran was added dropwise with stirring. The reaction mixture was then again refluxed for 3 h, the heating bath removed and a solution of 6.50 g (42.2 mmol) of (5Z)-3-methylnon-5-en-1-ol in 40 mL of dry tetrahydrofuran added at room temp. with stirring over a period of 30 min. The reaction mixture was refluxed with stirring overnight, allowed to cool to room temp., and quenched by pouring into 100 mL of an aqueous satd. NH4Cl solution. The organic layer was separated, and the aqueous one extracted three times with 500 mL of ether each. The combined organic extracts were dried with sodium sulphate, and concentrated to dryness in a rotary evaporator. The resulting residue (10.8 g) was purified by flash chromatography (200 g of silica gel, pentane/ether, 1:1, Rf=0.22) to furnish 7.76 g (77%) of (9Z)-2,7-dimethyltridec-9-en-3-yne-2,5-diol as a colourless oil.

出典