Dimethylformamide → Methyl 5-cyano-4-cyclobutyl-2-methylbenzoate

HRID 1487842Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1487842
[CH:1]1([C:5]2[C:14](I)=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[C:7]([CH3:16])[CH:6]=2)[CH2:4][CH2:3][CH2:2]1.[CH3:17][N:18](C=O)C>[C-]#N.[C-]#N.[Zn+2].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>[C:17]([C:14]1[C:5]([CH:1]2[CH2:4][CH2:3][CH2:2]2)=[CH:6][C:7]([CH3:16])=[C:8]([CH:13]=1)[C:9]([O:11][CH3:12])=[O:10])#[N:18]

Komponenten

5

Edukt 2

HCID 6228DimethylformamideHCID 68288363Methyl 4-cyclobutyl-5-iodo-2-methylbenzoate2×

Produkt 1

HCID 68288299Methyl 5-cyano-4-cyclobutyl-2-methylbenzoateAusbeute 88 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysator

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A mixture of methyl 4-cyclobutyl-5-iodo-2-methylbenzoate (compound 6.3, 4.17 g, 12.6 mmol), Zn(CN)2 (2.96 g, 25.2 mmol) and Pd(PPh3)4 (0.73 g, 0.63 mmol) in DMF (30 mL) was degassed and the flask was charged with argon. The mixture was heated at 100° C. under argon overnight. After cooling to ambient temperature, the mixture was quenched with saturated aq. FeSO4 (20 mL) and diluted with EtOAc (200 mL). The greenish solid was removed by filtration through Celite® and the filtrate was partitioned between water and EtOAc. The organics was washed with brine, dried (Na2SO4), filtered, and concentrated under reduced pressure. The residue was purified using silica gel column chromatography (hexanes:EtOAc 30:1 to 20:1) to yield the title compound as a white solid (2.55 g, 88%). 1H NMR (400 MHz, CDCl3) δ 8.16 (s, 1H), 7.28 (s, 1H), 3.90 (s, 3H), 3.86-3.82 (m, 1H), 2.68 (s, 3H), 2.55-2.45 (m, 2H), 2.27-2.04 (m, 3H), 1.89-1.87 (m, 1H).

Aufarbeitung

  1. customwas degassed
  2. additionthe flask was charged with argon
  3. temperatureAfter cooling to ambient temperature
  4. customthe mixture was quenched with saturated aq. FeSO4 (20 mL)
  5. additiondiluted with EtOAc (200 mL)
  6. customThe greenish solid was removed by filtration through Celite®
  7. customthe filtrate was partitioned between water and EtOAc
  8. washThe organics was washed with brine
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe residue was purified

Quellen und Nachweise

ORD-Eintrag
ord-aa5fad12c31842948afd409eeac81e92
Quelldatensatz
uspto-grants-2016_08
Patentnummer
US09428502B2

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