Dicyclohexylamine → 1-(3-Tert-butyl-phenyl)-3-methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl ester

HRID 132100

Reaktionsgleichung

Reaktionsgleichung von HRID 132100
C([Li])CCC.C1(NC2CCCCC2)CCCCC1.[CH3:19][Si:20]([CH3:34])([CH3:33])[CH2:21][CH2:22][O:23][C:24]([CH:26]1[CH2:31][CH2:30][CH2:29][C:28](=[CH2:32])[CH2:27]1)=[O:25].Br[C:36]1[CH:41]=[CH:40][CH:39]=[C:38]([C:42]([CH3:45])([CH3:44])[CH3:43])[CH:37]=1.F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C(Cl)(Cl)Cl.[Pd].[Pd].C(OCC)(=O)C>[CH3:19][Si:20]([CH3:33])([CH3:34])[CH2:21][CH2:22][O:23][C:24]([C:26]1([C:36]2[CH:41]=[CH:40][CH:39]=[C:38]([C:42]([CH3:45])([CH3:44])[CH3:43])[CH:37]=2)[CH2:31][CH2:30][CH2:29][C:28](=[CH2:32])[CH2:27]1)=[O:25]

Komponenten

9

Edukt 5

HCID 7582DicyclohexylamineHCID 3437981-Bromo-3-tert-butylbenzeneHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 597337523-Methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl esterHCID 178418339Butyllithium

Produkt 1

HCID 597337701-(3-Tert-butyl-phenyl)-3-methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl esterAusbeute 81 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11029508Palladium, tris[mu-[(1,2-eta:4,5-eta)-(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one]]di-, compd. with trichloromethane (1:1)KatalysatorHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A 1.6 M solution of n-butyllithium (12.0 mL, 19.2 mmol) was added to a solution of dicyclohexylamine (3.7 mL, 18.6 mmol) in toluene (40 mL). After stirring for 5 min, 3-methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl ester (3.45 g, 14.4 mmol) was added. After stirring for 30 min, 1-bromo-3-tert-butyl-benzene (3.16 g, 14.8 mmol) was added followed by the simultaneous addition of tri-tert-butylphosphonium tetrafluoroborate (220 mg, 758 mmol) and tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (380 mg, 367 mmol). The solution was placed into a preheated oil bath at 60° C. After stirring for 16 h, the solution was directly flash chromatographed with 99:1, 49:1, 24:1, and 23:2 hexanes:ethyl acetate as the eluant to yield 4.31 g (81% yield) of 1-(3-tert-butyl-phenyl)-3-methylene-cyclohexanecarboxylic acid 2-trimethylsilanyl-ethyl ester as a light yellow oil.

Aufarbeitung

  1. stirringAfter stirring for 30 min
  2. customThe solution was placed into a preheated oil bath at 60° C
  3. stirringAfter stirring for 16 h
  4. customchromatographed with 99:1, 49:1, 24:1, and 23:2 hexanes

Quellen und Nachweise

ORD-Eintrag
ord-21fa14fbc5004c0a97e1b04f91375d88
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07385085B2

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