Reacción #833533

Ecuación de reacción

norbornene-5-carbonylchloride

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

N-butyllithium

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title compound

Rendimiento 87.3%

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

Rendimiento 87.3%

Disolventes

THF

THF

THF

Condiciones de reacción

Tratamiento posterior

1. 1
   Otroequipped with an overhead stirrer
2. 2
   TemperaturaThe flask was cooled in ice
3. 3
   Temperaturawhile 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
   Temperaturawhile maintaining a temperature below 10° C
7. 7
   Otroto reach room temperature
8. 8
   OtroThe resulting suspension was transferred to a 4-L separatory funnel
9. 9
   Lavadowashed once with water (1 L)
10. 10
    OtroThe organic layer was separated
11. 11
    Lavadothe aqueous wash
12. 12
    Extracciónextracted twice with ether (1 L)
13. 13
    LavadoThe combined organic solutions were washed once with water and once with brine
14. 14
    Secadodried over anhydrous magnesium sulfate
15. 15
    FiltraciónThe suspension was filtered
16. 16
    Otrothe solvent removed on a rotary evaporator
17. 17
    workup.DISTILLATIONthe resulting oil distilled twice at 120° C.

Procedimiento

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.

Fuente