Triethylamine → Ethyl [3,5-bis(trifluoromethyl)phenyl]-{4-(isopropoxy)-3-vinylphenyl}phosphinate

HRID 1877310Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1877310
[F:1][C:2]([F:19])([F:18])[C:3]1[CH:4]=[C:5]([PH:13](=[O:17])[O:14][CH2:15][CH3:16])[CH:6]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:8]=1.Br[C:21]1[CH:26]=[CH:25][C:24]([O:27][CH:28]([CH3:30])[CH3:29])=[C:23]([CH:31]=[CH2:32])[CH:22]=1.C(N(CC)CC)C>CN(C=O)C.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.[Pd].[Pd]>[F:10][C:9]([F:12])([F:11])[C:7]1[CH:6]=[C:5]([P:13]([C:21]2[CH:26]=[CH:25][C:24]([O:27][CH:28]([CH3:29])[CH3:30])=[C:23]([CH:31]=[CH2:32])[CH:22]=2)(=[O:17])[O:14][CH2:15][CH3:16])[CH:4]=[C:3]([C:2]([F:1])([F:18])[F:19])[CH:8]=1

Komponenten

6

Edukt 3

HCID 8471TriethylamineHCID 125424254-Bromo-1-isopropoxy-2-vinylbenzeneHCID 178476784HCID 178476784, Verbindung

Produkt 1

HCID 86633213Ethyl [3,5-bis(trifluoromethyl)phenyl]-{4-(isopropoxy)-3-vinylphenyl}phosphinateAusbeute 2,8 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

To a degassed solution of ethyl 3,5-bis(trifluoromethyl)-phenylphosphinate (3.33 g, 15.24 mmol) and 4-bromo-1-isopropoxy-2-vinylbenzene (3.33 mg, 13.8 mmol) in DMF (25 mL) were added the triethylamine (3.85 mL, 27.6 mmol) and tris(dibenzylideneacetone)dipalladium (2.53 g, 2.76 mmol). The mixture was heated in an oil bath at 70° C. overnight. The volatiles were removed in vacuo and the mixture was purified by column chromatography with 20 to 70% ethyl acetate in petroleum ether to afford compound BA3 (185 mg) as an oil in 2.8% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.38 (dd, J=6.1 and 1.4 Hz, 6H) overlapping 1.41 (t, J=7.1 Hz, 3H), 4.11-4.21 (m, 2H), 4.65 (sept., J=6.1 Hz, 1H), 5.33 (dd, J=11.2 Hz and 1.4 Hz, 1H), 5.80 (dd, J=17.9 and 1.2 Hz, 1H), 6.96 (dd, J=8.6 and 3.0 Hz, 1H) overlapping 7.00 (dd, J=18.0 and 11.4 Hz, 1H), 7.63 (ddd, J=11.9, 11.9 and 2.0 Hz, 1H), 7.90 (dd, J=12.7 and 2.1 Hz, 1H), 7.99 (s, 1H), 8.22 (s, 1H), 8.25 (s, 1H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 28.59.

Aufarbeitung

  1. customThe volatiles were removed in vacuo
  2. customthe mixture was purified by column chromatography with 20 to 70% ethyl acetate in petroleum ether
  3. customto afford compound BA3 (185 mg) as an oil in 2.8% yield

Quellen und Nachweise

ORD-Eintrag
ord-469371ced8c24659bc0b51e9d5298904
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08309737B2

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