Dimethylformamide → 1-(2-aminopyrimidin-4-yl)-1H-1,3-benzodiazole-6-carbonitrile

HRID 1398506Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1398506
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:9]=[CH:8][N:7]([C:10]3[CH:15]=[CH:14][N:13]=[C:12]([NH2:16])[N:11]=3)[C:6]=2[CH:17]=1.[Cl-].[NH4+].[CH3:20][N:21](C=O)C>[C-]#N.[Zn+2].[C-]#N.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>[NH2:16][C:12]1[N:11]=[C:10]([N:7]2[C:6]3[CH:17]=[C:2]([C:20]#[N:21])[CH:3]=[CH:4][C:5]=3[N:9]=[CH:8]2)[CH:15]=[CH:14][N:13]=1

Komponenten

6

Edukt 3

HCID 6228DimethylformamideHCID 25517Ammonium ChlorideHCID 681819584-(6-bromo-1H-benzo[d]imidazol-1-yl)pyrimidin-2-amine

Produkt 1

HCID 681835231-(2-aminopyrimidin-4-yl)-1H-1,3-benzodiazole-6-carbonitrile

Reagenzien, Katalysatoren, Lösungsmittel 2

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

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a round bottom flask equipped with a condenser and nitrogen bubbler attached to a bleach scrubber bath was added 4-(6-bromo-1H-1,3-benzodiazol-1-yl)pyrimidin-2-amine (90% purity, 83 mg, 0.26 mmol) and zinc cyanide (30.23 mg, 0.26 mmol) in de-gassed DMF (2 mL). Tetrakis(triphenylphosphine)palladium (29.75 mg, 0.03 mmol) was then added and the reaction heated stirred at 100° C. under nitrogen for 30 min. The reaction mixture was allowed to cool to RT and poured into saturated aqueous ammonium chloride (6 mL) and extracted into DCM (×2). The combined organics were dried over Na2SO4, filtered and concentrated in vacuo. The residue was combined with the precipitate formed during the aqueous work up process and was purified by flash chromatography (Isolute column, 10% MeOH in DCM) to afford the title compound as a pale beige solid; 1H NMR (500 MHz, DMSO) δ 6.90-7.42 (3H, m), 7.76 (1H, dd, J=8.35, 1.58 Hz), 7.94 (1H, d, J=8.04 Hz), 8.40 (1H, d, J=5.52 Hz), 9.20 (1H, d, J=0.95 Hz), 9.33 (1H, s); LC-MS: m/z=+236.95 (M+H)+.

Aufarbeitung

  1. customTo a round bottom flask equipped with a condenser
  2. customnitrogen bubbler attached to a bleach scrubber bath
  3. temperaturethe reaction heated
  4. temperatureto cool to RT
  5. extractionextracted into DCM (×2)
  6. dry with materialThe combined organics were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customformed during the aqueous work up process
  10. customwas purified by flash chromatography (Isolute column, 10% MeOH in DCM)

Quellen und Nachweise

ORD-Eintrag
ord-905c9dfde48843d6ae73a8325939de33
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08901313B2

Notizen zur Reaktion

Wird geladen…