Dimethylformamide → (2-Chloro-6-cyano-naphthalen-1-yl)-acetic acid ethyl ester

HRID 639200Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 639200
[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][C:12](OS(C(F)(F)F)(=O)=O)=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2].[CH3:26][N:27](C=O)C>C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].[C-]#N.[Zn+2].[C-]#N>[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][C:12]([C:26]#[N:27])=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2]

Komponenten

5

Edukt 2

HCID 6228DimethylformamideHCID 86623398(2-Chloro-6-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester

Produkt 1

HCID 68704275(2-Chloro-6-cyano-naphthalen-1-yl)-acetic acid ethyl ester

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysator

Reaktionsbedingungen

Temperatur
125 °C

Versuchsvorschrift

(2-Chloro-6-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester (3.59 g, 9.04 mmol) is dissolved in DMF (30 ml) under an atmosphere of argon. After addition of palladium(0) tetrakis(triphenylphosphane) (418 mg, 0.36 mmol) and zinc(II) cyanide (2.12 g, 18.09 mmol), the reaction mixture is heated to 125° C. After 1 h, TLC analysis indicates complete consumption of starting material. The suspension is cooled to RT and poured onto water. Extraction with EtOAc is followed by washing the organic layer with 1 M aqueous HCl, sat. aqueous NaHCO3 solution and brine. After drying over Na2SO4 and removal of solvent, purification by FCC (hexane/EtOAc 3:1) affords the title compound. 1H NMR (d6-DMSO, 400 MHz): δ 1.06 (t, J=8 Hz, 3H), 3.98 (q, J=8 Hz, 2H), 4.24 (s, 2H), 7.66 (d, J=10 Hz, 1H), 7.79 (d, J=10 Hz, 1H), 7.96 (d, J=10 Hz, 1H), 8.13 (d, J=10 Hz, 1H), 8.54 (s, 1H).

Aufarbeitung

  1. customconsumption of starting material
  2. temperatureThe suspension is cooled to RT
  3. additionpoured onto water
  4. extractionExtraction with EtOAc
  5. washby washing the organic layer with 1 M aqueous HCl, sat. aqueous NaHCO3 solution and brine
  6. dry with materialAfter drying over Na2SO4 and removal of solvent, purification by FCC (hexane/EtOAc 3:1)

Quellen und Nachweise

ORD-Eintrag
ord-d0ee6f39e8a54df08c987918d63e38b7
Quelldatensatz
uspto-grants-2010_04
Patentnummer
US07691861B2

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