3-Oxo-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl ester → 3-Methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl ester

HRID 132099

Reaktionsgleichung

Reaktionsgleichung von HRID 132099
[CH2:1]([Li])CCC.[CH3:6][Si:7]([CH3:21])([CH3:20])[CH2:8][CH2:9][O:10][C:11]([CH:13]1[CH2:18][CH2:17][CH2:16][C:15](=O)[CH2:14]1)=[O:12]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[C:11]([O-:12])(=[O:10])[CH3:13].[CH3:6][Si:7]([CH3:21])([CH3:20])[CH2:8][CH2:9][O:10][C:11]([CH:13]1[CH2:18][CH2:17][CH2:16][C:15](=[CH2:1])[CH2:14]1)=[O:12]

Komponenten

6

Edukt 2

HCID 597337803-Oxo-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl esterHCID 178418339Butyllithium

Produkt 2

HCID 175AcetateHCID 597337523-Methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl esterAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 74505Methyltriphenyliphosphonium bromideKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-10 °C

Versuchsvorschrift

A solution of 1.6 M n-butyllithium in hexanes (14.0 mL, 22.4 mmol) was added to a heterogeneous mixture of methyltriphenylphosphonium bromide (8.02 g, 22.4 mmol) in tetrahydrofuran (50 mL) at −10° C. After stirring for 30 min at −10° C., the yellow slurry was cooled to −78° C. and 3-oxo-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl ester (3.41 mg, 14.1 mmol) in tetrahydrofuran (20 mL) was added. After stirring for 10 min at −78° C., the dry ice/acetone bath was removed and the heterogeneous mixture was stirred for 3 h, during which time the solution warmed to ambient temperature. The heterogeneous mixture was concentrated and the residue was flash chromatographed with 99:1, 49:1, 24:1, and 23:2 hexanes:etheyl acetate as the eluant to yield 3.38 g (100% yield) of 3-methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl ester as a clear oil.

Aufarbeitung

  1. temperaturethe yellow slurry was cooled to −78° C.
  2. stirringAfter stirring for 10 min at −78° C.
  3. customthe dry ice/acetone bath was removed
  4. stirringthe heterogeneous mixture was stirred for 3 h, during which time the solution
  5. temperaturewarmed to ambient temperature
  6. concentrationThe heterogeneous mixture was concentrated
  7. customchromatographed with 99:1, 49:1, 24:1, and 23:2 hexanes

Quellen und Nachweise

ORD-Eintrag
ord-2574301570b546bbbd04d4f66b8d5256
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07385085B2

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