Dimethylformamide → Ethyl (2E)-3-{4-[(3-chloro-4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenoate

HRID 229214Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 229214
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:17]2[CH2:22][C:21]([CH3:24])([CH3:23])[CH2:20][C:19]([CH3:26])([CH3:25])[CH2:18]2)[C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[C:11]([Cl:16])[CH:10]=2)=[CH:4][CH:3]=1.[C:27]([O:31][CH2:32][CH3:33])(=[O:30])[CH:28]=[CH2:29].CCN(CC)CC.CN(C=O)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CCOC(C)=O.O>[Cl:16][C:11]1[CH:10]=[C:9]([C:8](=[C:17]2[CH2:18][C:19]([CH3:26])([CH3:25])[CH2:20][C:21]([CH3:23])([CH3:24])[CH2:22]2)[C:5]2[CH:6]=[CH:7][C:2](/[CH:29]=[CH:28]/[C:27]([O:31][CH2:32][CH3:33])=[O:30])=[CH:3][CH:4]=2)[CH:14]=[CH:13][C:12]=1[OH:15]

Komponenten

8

Edukt 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 686545734-[(4-Bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]-2-chlorophenol

Produkt 1

HCID 68976421Ethyl (2E)-3-{4-[(3-chloro-4-hydroxyphenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}-2-propenoateAusbeute 66 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418476HCID 178418476, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a round-bottomed flask were added 4-[(4-bromophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]-2-chlorophenol (127) (0.38 g, 0.88 mmol), ethyl acrylate (0.96 mL, 8.80 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.062 g, 0.09 mmol), Et3N (0.61 mL, 4.38 mmol) and DMF (10 mL). The stirred reaction mixture was heated overnight at 100° C. under a nitrogen atmosphere. The reaction mixture was allowed to cool to room temperature and transferred to a separatory funnel with the aid of water and EtOAc (100 mL). The layers were separated and the organic phase was washed with water, brine, dried (Na2SO4), filtered, and the filtrate was concentrated to give reddish brown oil. The crude product was purified by chromatography on a silica gel column eluted with a gradient from hexanes to 15% EtOAc:hexanes to give 0.26 g (66%) of compound 128 as a yellow viscous oil. 1H NMR (400 MHz, CDCl3): δ 0.92 (s, 6H), 0.94 (s, 6H), 1.30 (s, 2H), 1.33 (t, J=7.1 Hz, 3H), 1.96 (s, 2H), 1.97 (s, 2H), 4.25 (q, J=7.1 Hz, 2H), 5.43 (s, 1H), 6.39 (d, J=15.9 Hz, 1H), 6.90-7.00 (m, 2H), 7.11 (d, J=1.8 Hz, 1H), 7.16 (d, J=8.1 Hz, 2H), 7.44 (d, J=8.1 Hz, 2H), 7.65 (d, J=15.9 Hz, 1H). LCMS (ESI): m/z, 453 (M+H)+, 451 (M−H)−.

Aufarbeitung

  1. customThe stirred reaction mixture
  2. temperatureto cool to room temperature
  3. customThe layers were separated
  4. washthe organic phase was washed with water, brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated
  8. customto give
  9. customThe crude product was purified by chromatography on a silica gel column
  10. washeluted with a gradient from hexanes to 15% EtOAc

Quellen und Nachweise

ORD-Eintrag
ord-f4b1f7359b1c43539eaf8cdb6bc70542
Quelldatensatz
uspto-grants-2009_07
Patentnummer
US07560589B2

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