Ethyl 4-bromobenzoate → Ethyl 4-(diethoxyphosphoryl)benzoate

HRID 50628

Reaktionsgleichung

Reaktionsgleichung von HRID 50628
[CH2:1]([O:3][C:4](=[O:12])[C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][CH:6]=1)[CH3:2].[P:13]([O-:20])([O:17][CH2:18][CH3:19])[O:14][CH2:15][CH3:16]>C(#N)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.CN1CCOCC1>[CH2:1]([O:3][C:4](=[O:12])[C:5]1[CH:10]=[CH:9][C:8]([P:13]([O:17][CH2:18][CH3:19])([O:14][CH2:15][CH3:16])=[O:20])=[CH:7][CH:6]=1)[CH3:2]

Komponenten

6

Edukt 2

HCID 22043Ethyl 4-bromobenzoateHCID 3780918Diethylphosphite

Produkt 1

HCID 2773693Ethyl 4-(diethoxyphosphoryl)benzoateAusbeute 67,9 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 79724-MethylmorpholineKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

A sealed pressure flask, flushed with N2, containing a mixture of 4-bromo-benzoic acid ethyl ester (2a) (5 g, 0.0218 mol), diethyl phosphite (3.093 mL, 0.024 mol), NMM (2.88 mL, 0.0262 mmol) and Pd(PPh3)4 (2.017 g, 0.00175 mol) in acetonitrile (20 mL) was stirred at ambient temperature for 5-10 min, then heated at 90° C. for 18 hours. The reaction mixture was filtered through celite, and the celite was washed with EtOAc (3×30 mL) until the filtrate showed little or no evidence of product by HPLC. The combined organics were dried over Na2SO4 and concentrated on a rotary evaporator. The desired product was purified by silica gel flash chromatography to give a pale yellow oil (4.24 g). 1H NMR (300 MHz, CDCl3) δ (ppm)) 1.36 (m, 6H), 1.42 (t, J=7 Hz, 3H), 4.16 (m, 4H), 4.42 (q, J=7 Hz, 2H), 7.93 (m, 2H), 8.15 (m, 2H). 31P NMR (121 MHz, CDCl3) δ17.63.

Aufarbeitung

  1. customA sealed pressure flask, flushed with N2
  2. additioncontaining
  3. temperatureheated at 90° C. for 18 hours
  4. filtrationThe reaction mixture was filtered through celite
  5. washthe celite was washed with EtOAc (3×30 mL) until the filtrate
  6. dry with materialThe combined organics were dried over Na2SO4
  7. concentrationconcentrated on a rotary evaporator
  8. customThe desired product was purified by silica gel flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-f4b44a2492fb47cf93b9bdf88797f5df
Quelldatensatz
uspto-grants-2004_03
Patentnummer
US06713462B2

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