Triethylamine → Ethyl phenyl-{4-(isopropoxy)-3-vinylphenyl}phosphinate

HRID 1618073Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1618073
[C:1]1([PH:7](=[O:11])[O:8][CH2:9][CH3:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:13]1[CH:18]=[CH:17][C:16]([O:19][CH:20]([CH3:22])[CH3:21])=[C:15]([CH:23]=[CH2:24])[CH:14]=1.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:1]1([P:7]([C:13]2[CH:18]=[CH:17][C:16]([O:19][CH:20]([CH3:21])[CH3:22])=[C:15]([CH:23]=[CH2:24])[CH:14]=2)(=[O:11])[O:8][CH2:9][CH3:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Komponenten

7

Edukt 3

HCID 8471TriethylamineHCID 125424254-Bromo-1-isopropoxy-2-vinylbenzeneHCID 178476779HCID 178476779, Verbindung

Produkt 1

HCID 66650560Ethyl phenyl-{4-(isopropoxy)-3-vinylphenyl}phosphinateAusbeute 87 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)KatalysatorHCID 6342AcetonitrileLösungsmittel

Reaktionsbedingungen

Temperatur
68 °C

Versuchsvorschrift

To a degassed mixture of ethyl phenylphosphinate (1.87 g, 11.0 mmol) and 4-bromo-1-isopropoxy-2-vinylbenzene (2.43 g, 10.0 mmol), which was commercially available, in acetonitrile (66 mL) were added triethylamine (3.1 mL, 22.0 mmol), palladium acetate (112 mg, 0.5 mmol), and 1,1′-bis(diphenylphosphino)ferrocene (277 mg, 0.5 mmol). The mixture was further degassed and heated at 68° C. for 24 hrs. The volatiles were removed in vacuo, and the crude was purified by column chromatography using 50 to 80% ethyl acetate in petroleum ether to afford compound BA4 (3.74 g) in 87% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.36 (d, J=5.7 Hz, 6H), 1.37 (t, J=6.9 Hz, 3H), 4.15-4.05 (m, 2H), 4.62 (sept., J=6.0 Hz, 1H), 5.28 (dd, J=11.2 and 1.4 Hz, 1H), 5.78 (dd, J=17.7 and 1.4 Hz, 1H), 6.91 (dd, J=8.45 and 3.0 Hz, 1H), 6.99 (dd, J=17.9 and 11.4 Hz, 1H), 7.41-7.47 (m, 2H), 7.47-7.55 (m, 1H), 7.63 (ddd, J=11.7, 8.5 and 2.0 Hz, 1H), 7.79 (dd, J=12.3 and 1.4 Hz, 1H), 7.81 (dt, J=12.3 and 1.4 Hz, 1H), 7.90 (dd, J=12.4 and 2.0 Hz, 1H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 32.61.

Aufarbeitung

  1. customThe mixture was further degassed
  2. customThe volatiles were removed in vacuo
  3. customthe crude was purified by column chromatography
  4. customto afford compound BA4 (3.74 g) in 87% yield

Quellen und Nachweise

ORD-Eintrag
ord-18f6e7546c3543bcac2b597a9d97822d
Quelldatensatz
uspto-grants-2014_07
Patentnummer
US08765966B2

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