Ethyl 4-bromobenzoate → 4-[(Diethoxyphosphorylmethyl)-ethoxyphosphinoyl]-benzoic acid ethyl ester

HRID 50630

Reaktionsgleichung

Reaktionsgleichung von HRID 50630
[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].[CH2:13]([O:15][P:16]([CH2:21][PH:22]([O:24][CH2:25][CH3:26])=[O:23])(=[O:20])[O:17][CH2:18][CH3:19])[CH3:14]>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:22]([CH2:21][P:16]([O:15][CH2:13][CH3:14])([O:17][CH2:18][CH3:19])=[O:20])([O:24][CH2:25][CH3:26])=[O:23])=[CH:7][CH:6]=1)[CH3:2]

Komponenten

6

Edukt 2

HCID 22043Ethyl 4-bromobenzoateHCID 178476825HCID 178476825, Verbindung

Produkt 1

HCID 213024024-[(Diethoxyphosphorylmethyl)-ethoxyphosphinoyl]-benzoic acid ethyl esterAusbeute 58,6 %

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 (3a) (5 g, 0.0218 mol), ethoxyphosphinoylmethyl-phosphonic acid diethyl ester (3b), (5.86 g, 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 rotary evaporator. The desired product (ix) was purified by silica gel flash chromatography to give a pale yellow oil (5.01 g). 1H NMR (300 MHz, CDCl3) δ (ppm)): 0.96 (t, J=7.07 Hz, 3H), 1.13 (m, 9H), 2.41 (t, J=18.2 Hz, 2H), 3.84 (m, 6H), 4.17 (q, J=7.11 Hz, 2H), 7.71 (m, 2H), 7.92 (m, 2H)., 31P NMR (121 MHz, CDCl3) δ32.8 and 19.7.

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 rotary evaporator
  8. customThe desired product (ix) was purified by silica gel flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-a6bbe25a24454bd8bb8aad854e0bcfda
Quelldatensatz
uspto-grants-2004_03
Patentnummer
US06713462B2

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