Diethyl Malonate → Diethyl 2-(3-(cyclopropylmethoxy)-4-nitrophenyl)malonate

HRID 385397

Reaktionsgleichung

Reaktionsgleichung von HRID 385397
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].[CH:14]1([CH2:17][O:18][C:19]2[CH:24]=[C:23](F)[CH:22]=[CH:21][C:20]=2[N+:26]([O-:28])=[O:27])[CH2:16][CH2:15]1>CN(C=O)C>[CH:14]1([CH2:17][O:18][C:19]2[CH:24]=[C:23]([CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])[CH:22]=[CH:21][C:20]=2[N+:26]([O-:28])=[O:27])[CH2:15][CH2:16]1

Komponenten

5

Edukt 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 589984092-Cyclopropylmethoxy-4-fluoro-1-nitrobenzene

Produkt 1

HCID 57995590Diethyl 2-(3-(cyclopropylmethoxy)-4-nitrophenyl)malonateAusbeute 42,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel2×

Versuchsvorschrift

Diethyl malonate (9.8 g, 1.1 eq) was added to a stirred suspension of sodium hydride (60% in mineral oil, 2.09 g) in DMF (88 mL) over 15 min. at 0° C. under nitrogen. The reaction mixture was allowed to warm to room temperature and stirred for 1 h. A solution of 2-cyclopropylmethoxy-4-fluoro-1-nitrobenzene (10 g, 1 eq) in DMF (88 mL) was added drop wise at 0° C., and the reaction mixture was heated to 100° C. for 3 h. The reaction mixture was allowed to cool to room temperature, poured into ice water and extracted with EtOAc (3×100 mL). The combined organic phases were washed with water (3×100 mL) and brine (100 mL), dried (MgSO4) and filtered. Evaporation of the volatiles under reduced pressure gave 10.0 g of crude product which was purified by chromatography over silica gel (hexane/EtOAc) gave of diethyl 2-(3-(cyclopropylmethoxy)-4-nitrophenyl)malonate (7.0 g). 1H-NMR (CDCl3, 200 MHz): 0.4 (m, 2H), 0.71 (m, 2H), 1.3 (m, 1H), 1.3 (t, 6H), 3.96 (d, 2H), 4.25 (q, 4H), 4.5 (s, 1H), 7.02 (d, 1H), 7.18 (s, 1H), 7.81 (d, 2H).

Aufarbeitung

  1. temperaturethe reaction mixture was heated to 100° C. for 3 h
  2. temperatureto cool to room temperature
  3. extractionextracted with EtOAc (3×100 mL)
  4. washThe combined organic phases were washed with water (3×100 mL) and brine (100 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customEvaporation of the volatiles under reduced pressure
  8. customgave 10.0 g of crude product which
  9. customwas purified by chromatography over silica gel (hexane/EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-688799fdd0bc45a4862ee3e923436532
Quelldatensatz
uspto-grants-2013_02
Patentnummer
US08367863B2

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