反応 #833533

反応方程式

norbornene-5-carbonylchloride

1,1,1-trifluoro-2-trifluoromethyl-2,4-pentanediol

N-butyllithium

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title compound

収率 87.3%

1,1,1-trifluoro-2-hydroxy-2-trifluoromethyl-4-pentyl norbornene-5-carboxylate

収率 87.3%

溶媒

THF

THF

THF

反応条件

後処理

1. 1
   その他equipped with an overhead stirrer
2. 2
   温度The flask was cooled in ice
3. 3
   温度while maintaining a temperature below 10° C
4. 4
   workup.ADDITIONOnce the addition
5. 5
   workup.ADDITIONwas then slowly added over about 1.5 hours
6. 6
   温度while maintaining a temperature below 10° C
7. 7
   その他to reach room temperature
8. 8
   その他The resulting suspension was transferred to a 4-L separatory funnel
9. 9
   洗浄washed once with water (1 L)
10. 10
    その他The organic layer was separated
11. 11
    洗浄the aqueous wash
12. 12
    抽出extracted twice with ether (1 L)
13. 13
    洗浄The combined organic solutions were washed once with water and once with brine
14. 14
    乾燥dried over anhydrous magnesium sulfate
15. 15
    ろ過The suspension was filtered
16. 16
    その他the solvent removed on a rotary evaporator
17. 17
    workup.DISTILLATIONthe resulting oil distilled twice at 120° C.

実験手順

N-butyllithium (1600 ml) (2.56 mol, 1.6M solution in hexanes) was added to a 3-L, three-necked round bottomed flask equipped with an overhead stirrer, a digital thermometer, a 500-mL capacity constant-pressure dropping funnel and a nitrogen inlet. The dropping funnel was charged with a solution of 1,1,1-trifluoro-2-trifluoromethyl-2,4-pentanediol (289 g, 1.28 mol) in anhydrous THF (250 ml). The flask was cooled in ice and the THF solution was slowly added over about 2 hours, while maintaining a temperature below 10° C. Once the addition was complete, the dropping funnel was recharged with a solution of norbornene-5-carbonylchloride (201 g, 1.28 mol) in anhydrous THF (250 ml), which was then slowly added over about 1.5 hours, while maintaining a temperature below 10° C. The solution was allowed to reach room temperature with stirring overnight. The resulting suspension was transferred to a 4-L separatory funnel and washed once with water (1 L). The organic layer was separated and the aqueous wash was adjusted to pH 6 (litmus) with concentrated HCl and extracted twice with ether (1 L). The combined organic solutions were washed once with water and once with brine and dried over anhydrous magnesium sulfate. The suspension was filtered, the solvent removed on a rotary evaporator and the resulting oil distilled twice at 120° C. and 0.5 mm Hg to yield 387 g of the title compound as an oil.

出典