Diethyl Malonate → 1,3-Diethyl 2-(3-chloro-4-cyano-2-methylphenyl)propanedioate

HRID 132682Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 132682
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].[Cl:14][C:15]1[C:22]([CH3:23])=[C:21](I)[CH:20]=[CH:19][C:16]=1[C:17]#[N:18]>O1CCOCC1.[Cu]I>[Cl:14][C:15]1[C:22]([CH3:23])=[C:21]([CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])[CH:20]=[CH:19][C:16]=1[C:17]#[N:18]

Komponenten

6

Edukt 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 167319952-Chloro-4-iodo-3-methylbenzonitrile

Produkt 1

HCID 597346011,3-Diethyl 2-(3-chloro-4-cyano-2-methylphenyl)propanedioateAusbeute 82,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a pressure reaction flask containing diethyl malonate (4.1 mL, 27 mmol) in 50 mL of anhydrous dioxane was added NaH (1.1 g, 27.5 mmol, ˜60% in mineral oil) in several portions at RT, and stirred for 30 min. Compound 1E (2.5 g, 9 mmol) and CuI (5.1 g, 26.8 mmol) were added, sealed and heated at 100° C. for 3 days. The reaction was cooled to RT and filtered through a pad of celite. The celite pad was washed with EtOAc. The organics were washed twice with water, dried over Na2SO4, filtered and concentrated. Purification by flash chromatography (silica gel, 110 g ISCO, 10% EtOAc in hexane) gave the title compound (2.3 g).

Aufarbeitung

  1. customTo a pressure reaction flask
  2. customsealed
  3. temperatureThe reaction was cooled to RT
  4. filtrationfiltered through a pad of celite
  5. washThe celite pad was washed with EtOAc
  6. washThe organics were washed twice with water
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by flash chromatography (silica gel, 110 g ISCO, 10% EtOAc in hexane)

Quellen und Nachweise

ORD-Eintrag
ord-730d1a8fd1c14095a000bd19b653c016
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07388027B2

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