2-Methylhexan-2-ol → 2-Methylhexan-2-yl methacrylate

HRID 504984Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 504984
C([Li])CCC.[CH3:6][C:7]([OH:13])([CH2:9][CH2:10][CH2:11][CH3:12])[CH3:8].[C:14](Cl)(=[O:18])[C:15]([CH3:17])=[CH2:16]>O1CCCC1>[C:14]([O:13][C:7]([CH3:8])([CH2:9][CH2:10][CH2:11][CH3:12])[CH3:6])(=[O:18])[C:15]([CH3:17])=[CH2:16]

Komponenten

5

Edukt 3

HCID 122402-Methylhexan-2-olHCID 13528Methacryloyl chlorideHCID 178418339Butyllithium

Produkt 1

HCID 544743752-Methylhexan-2-yl methacrylateAusbeute 59 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a flame-dried, nitrogen-purged 500 mL 3-neck roundbottom flask with 250 mL pressure-equalizing addition funnel and magnetic stirbar was charged 81 mL n-butyl lithium (129 mmol, 1 equiv., 1.6 M in hexanes). A degassed solution of 15.0 g 2-methyl-2-hexanol (129 mmol, 1 eq.) in 100 mL anhydrous tetrahydrofuran was charged to the addition funnel and added to the reaction mixture dropwise at 0° C. over 60 minutes. The reaction mixture was warmed for 15 minutes on hot water bath to ensure the reaction was complete. The reaction vessel was cooled to 0° C. and 14.2 g methacryloyl chloride (135 mmol, 1.05 eq.) was added dropwise and allowed to stir for 15 minutes. The addition funnel was replaced with a reflux condenser and the reaction heated to reflux for 20 hours. After the reaction was complete, it was cooled to 0° C. and quenched aqueous sodium bicarbonate. The product was extracted into ethyl ether and the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine and then dried over magnesium sulfate, filtered, concentrated in vacuo, and stored over a small amount of sodium bicarbonate. The crude product mixture was vacuum distilled through a vacuum-jacketed short-path distillation head to afford 14 g (59%) of 2-methylhexan-2-yl methacrylate (XIII) as a colorless liquid.

Aufarbeitung

  1. customTo a flame-dried, nitrogen-purged 500 mL
  2. additionroundbottom flask with 250 mL pressure-equalizing addition funnel
  3. additionadded to the reaction mixture dropwise at 0° C. over 60 minutes
  4. temperatureThe reaction mixture was warmed for 15 minutes on hot water bath
  5. customThe addition funnel was replaced with a reflux condenser
  6. temperaturethe reaction heated
  7. temperatureto reflux for 20 hours
  8. temperatureit was cooled to 0° C.
  9. customquenched aqueous sodium bicarbonate
  10. extractionThe product was extracted into ethyl ether
  11. washthe organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine
  12. dry with materialdried over magnesium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo
  15. distillationdistilled through a vacuum-jacketed short-path distillation head

Quellen und Nachweise

ORD-Eintrag
ord-aeeb7190602243679d21effd30708901
Quelldatensatz
uspto-grants-2010_08
Patentnummer
US07781157B2

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