Triphenylphosphine → HCID 136335798, Verbindung

HRID 1801422Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1801422
I[C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:9]2[C:14]([CH3:15])=[CH:13][N:12]=[CH:11][C:10]=2[CH3:16])=[C:4]([CH3:17])[CH:3]=1.[C:18]([C:22]1[CH:27]=[C:26]([CH:28]=[CH2:29])[CH:25]=[C:24]([C:30]([CH3:33])([CH3:32])[CH3:31])[C:23]=1[OH:34])([CH3:21])([CH3:20])[CH3:19].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>CC([O-])=O.CC([O-])=O.[Pd+2]>[C:18]([C:22]1[CH:27]=[C:26]([CH:28]=[CH:29][C:2]2[CH:7]=[C:6]([CH3:8])[C:5]([C:9]3[C:14]([CH3:15])=[CH:13][N:12]=[CH:11][C:10]=3[CH3:16])=[C:4]([CH3:17])[CH:3]=2)[CH:25]=[C:24]([C:30]([CH3:33])([CH3:32])[CH3:31])[C:23]=1[OH:34])([CH3:21])([CH3:20])[CH3:19]

Komponenten

5

Edukt 3

HCID 11776TriphenylphosphineHCID 125766802,6-Di-tert-butyl-4-vinylphenolHCID 58510520HCID 58510520, Verbindung

Produkt 1

HCID 136335798HCID 136335798, VerbindungAusbeute 91,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 167845palladium(II) acetateKatalysator

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A flame-dried sealable Schlenk tube was charged with 11 (1.69 g, 5.0 mmol), 12 (2.32 g, 10.0 mmol), Pd(OAc)2 (112 mg, 0.50 mmol), and PPh3 (131 mg, 0.50 mmol), evacuated, and then backfilled with N2. Next, dry Et3N (10 mL) was added under an N2 flow. The Schlenk tube was next sealed, the mixture was degassed by 3 freeze-thaw cycles, and backfilled with N2. The Schlenk tube was then wrapped with aluminum foil and stirred at 100° C. for 36 h. The reaction mixture was then cooled to room temperature, diluted with methylene chloride (50 mL), filtered through a thin pad of silica gel, and concentrated in vacuo to afford a red solid. The crude product was purified by flash chromatography on silica gel, eluting with 3:1 hexane:ethyl acetate to give the title compound 2.01 g (91.2%) as a colorless solid: mp 234-235° C.; 1H NMR (400 MHz, CDCl3): δ 8.402 (s, 2H), 7.371 (s, 2H), 7.307 (s, 2H), 7.133 (d, 1H, J=16.4 Hz), 6.936 (d, 1H, J=16.0 Hz), 5.331 (s, 1H), 1.951 (s, 6H), 1.911 (s, 6H), 1.499 (s, 18H); 13C NMR (100 MHz, CDCl3): δ 153.971, 148.630, 148.502, 137.347, 136.301, 135.928, 134.817, 131.251, 129.595, 128.876, 125.837, 125.709, 123.598, 34.638, 30.534, 19.997, 16.822; HRMS (EI): m/z 441.3023 [M+]; calcd, 441.3032; Anal. Calcd. for C31H39NO.H2O: C, 81.00; H, 8.99; N, 3.05. Found; C, 81.01; H, 8.64; N, 3.02.

Aufarbeitung

  1. customevacuated
  2. additionNext, dry Et3N (10 mL) was added under an N2 flow
  3. customthe mixture was degassed by 3 freeze-thaw cycles
  4. temperatureThe reaction mixture was then cooled to room temperature
  5. additiondiluted with methylene chloride (50 mL)
  6. filtrationfiltered through a thin pad of silica gel
  7. concentrationconcentrated in vacuo
  8. customto afford a red solid
  9. customThe crude product was purified by flash chromatography on silica gel
  10. washeluting with 3:1 hexane

Quellen und Nachweise

ORD-Eintrag
ord-af20a4ace6b94c4e97aad0c1c9fdd949
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08349222B2

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