Potassium Carbonate → 4-Methoxy-2-fluoro-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzaldehyde

HRID 1057830Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1057830
[F:1][C:2]1[C:9](S(C(F)(F)F)(=O)=O)=[C:8]([O:17][CH3:18])[CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].[CH3:19][C:20]1[C:21](B(O)O)=[CH:22][C:23]2[C:24]([CH3:33])([CH3:32])[CH2:25][CH2:26][C:27]([CH3:31])([CH3:30])[C:28]=2[CH:29]=1.C(=O)([O-])[O-].[K+].[K+]>COCCOC.O.C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:18][O:17][C:8]1[CH:7]=[CH:6][C:3]([CH:4]=[O:5])=[C:2]([F:1])[C:9]=1[C:21]1[C:20]([CH3:19])=[CH:29][C:28]2[C:27]([CH3:31])([CH3:30])[CH2:26][CH2:25][C:24]([CH3:33])([CH3:32])[C:23]=2[CH:22]=1

Komponenten

8

Edukt 3

HCID 11430Potassium CarbonateHCID 10037535(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acidHCID 222683312-Fluoro-4-methoxy-3-trifluoromethanesulfonyl benzaldehyde

Produkt 1

HCID 222682874-Methoxy-2-fluoro-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzaldehydeAusbeute 62 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 80711,2-DimethoxyethaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A mixture of 2-fluoro-4-methoxy-3-trifluoromethanesulfonyl benzaldehyde (1.21 g, 4.01 mmol), (3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acid (1.08 g, 4.41 mmol) and potassium carbonate (2.22 g, 16.04 mmol) in 1,2-dimethoxyethane (30 mL) and water (2 mL) was degassed with argon for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.23 g, 0.2 mmol) was added and the mixture heated at reflux under argon for 16 hours. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (Biotage, eluent: ethyl acetate/hexane, 0.5:8.5) to give 0.87 g of 4-methoxy-2-fluoro-3-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzaldehyde (62%). 1H NMR (500 MHz; CDCl3): δ1.26 (s, 6H), 1.32 (s, 6H), 1.69 (s, 4H), 2.07 (s, 3H), 3.85 (s, 3H), 7.07 (d, J=8.8 Hz, 1H), 7.07 (s, 1H), 7.19 (s, 1H), 7.90 (t, J=8.8 Hz, 1H), 10.25 (s, 1H).

Aufarbeitung

  1. customwas degassed with argon for 30 minutes
  2. temperaturethe mixture heated
  3. temperatureat reflux under argon for 16 hours
  4. washwashed successively with water and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was chromatographed on silica gel (Biotage, eluent: ethyl acetate/hexane, 0.5:8.5)

Quellen und Nachweise

ORD-Eintrag
ord-7a06cf812eca4403af78e9c6c3c79be1
Quelldatensatz
uspto-grants-2003_02
Patentnummer
US06515003B1

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