n-Butyl lithium → 1,1,1-Trifluoro-2-hydroxy-2-trifluoromethyl-4-pentyl norbornene-5-carboxylate

HRID 1593921

Reaktionsgleichung

Reaktionsgleichung von HRID 1593921
[Li+].CCC[CH2-].[F:6][C:7]([F:19])([F:18])[C:8]([C:14]([F:17])([F:16])[F:15])([OH:13])[CH2:9][CH:10]([OH:12])[CH3:11].[CH:20]12[CH2:29][CH:23]([CH:24]([C:26](Cl)=[O:27])[CH2:25]1)[CH:22]=[CH:21]2>C1COCC1>[CH:20]12[CH2:29][CH:23]([CH:24]([C:26]([O:12][CH:10]([CH3:11])[CH2:9][C:8]([OH:13])([C:14]([F:15])([F:16])[F:17])[C:7]([F:18])([F:19])[F:6])=[O:27])[CH2:25]1)[CH:22]=[CH:21]2

Komponenten

5

Edukt 3

HCID 61028n-Butyl lithiumHCID 98233Bicyclo(2.2.1)hept-5-ene-2-carbonyl chlorideHCID 1181911,1,1-Trifluoro-2-(trifluoromethyl)-2,4-pentanediol

Produkt 1

HCID 576290111,1,1-Trifluoro-2-hydroxy-2-trifluoromethyl-4-pentyl norbornene-5-carboxylateAusbeute 87,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

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 100 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 HCI 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 1200 C. and 0.5 mm Hg to yield 387 g of the title compound as an oil.

Aufarbeitung

  1. customequipped with an overhead stirrer
  2. temperatureThe flask was cooled in ice
  3. temperaturewhile maintaining a temperature below 100 C
  4. additionOnce the addition
  5. additionwas then slowly added over about 1.5 hours
  6. temperaturewhile maintaining a temperature below 10° C
  7. customto reach room temperature
  8. customThe resulting suspension was transferred to a 4-L separatory funnel
  9. washwashed once with water (1 L)
  10. customThe organic layer was separated
  11. washthe aqueous wash
  12. extractionextracted twice with ether (1 L)
  13. washThe combined organic solutions were washed once with water and once with brine
  14. dry with materialdried over anhydrous magnesium sulfate
  15. filtrationThe suspension was filtered
  16. customthe solvent removed on a rotary evaporator
  17. distillationthe resulting oil distilled twice at 1200 C

Quellen und Nachweise

ORD-Eintrag
ord-643898eb2aef405fb7bb7237608330e7
Quelldatensatz
uspto-grants-2007_11
Patentnummer
US07300739B2

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