Acetonitrile → 3-Iodobenzoylacetonitrile

HRID 1278884

Reaktionsgleichung

Reaktionsgleichung von HRID 1278884
C([Li])CCC.C(N[CH:10]([CH3:12])[CH3:11])(C)C.[Li+].CC([N-]C(C)C)C.[C:21](#[N:23])[CH3:22].[I:24]C1C=CC(C(OCC)=O)=CC=1.[Cl-].[NH4+].[O:38]1[CH2:42][CH2:41][CH2:40][CH2:39]1>>[I:24][C:42]1[CH:41]=[C:40]([CH:12]=[CH:10][CH:11]=1)[C:39]([CH2:22][C:21]#[N:23])=[O:38]

Komponenten

8

Reaktionsbedingungen

Temperatur
-50 °C

Versuchsvorschrift

n-Butyllithium (30.5 ml, 76 mmol, 2.5 M solution in hexane) was added dropwise to a cooled (0° C.) solution of diisopropylamine (10.6 ml, 76 mmol) in 10 ml dry tetrahydrofuran. Once addition was complete, the solution was kept at 0° C. for 10 minutes and was then cooled to −50° C. This cold LDA solution was then added to a −50° C. solution of acetonitrile (2.37,ml, 45.3 mmol) and ethyl 4-iodobenzoate (10.0 g, 36.2 mmol) in dry tetrahydrofuran (18 ml). Once addition was complete, the reaction was stirred at −50° C. for 3 hours and was subsequently warmed to 0° C. Saturated ammonium chloride was added (20 ml) and the reaction mixture was allowed to warm to room temperature. The product was extracted into ether and washed with 1N hydrochloric acid (50 ml). The organics were washed with brine (50 ml), dried over MgSO4 and then concentrated in vacuo to a red oil. The oil was purified through a small plug of silica gel using 3:1-2:1 hexanes/ethyl acetate as eluent. Concentration of the column fractions in vacuo gave 2-(3-iodobenzoyl)-acetonitrile (8.3 g) as a yellow oil.

Aufarbeitung

  1. additionOnce addition
  2. additionOnce addition
  3. temperaturewas subsequently warmed to 0° C
  4. temperatureto warm to room temperature
  5. extractionThe product was extracted into ether
  6. washwashed with 1N hydrochloric acid (50 ml)
  7. washThe organics were washed with brine (50 ml)
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated in vacuo to a red oil
  10. customThe oil was purified through a small plug of silica gel using 3:1-2:1 hexanes/ethyl acetate as eluent

Quellen und Nachweise

ORD-Eintrag
ord-2abb775eaa1a4d25a2139ac05ade2cf1
Quelldatensatz
uspto-grants-2002_09
Patentnummer
US06444696B1

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