Cesium carbonate → 6-(1-Hydroxy-1,3-dihydro-benzo[c][1,2]oxaborol-5-yloxy)-5-methoxymethoxy-nicotinonitrile

HRID 1255725

Reaktionsgleichung

Cl[C:2]1[C:9]([O:10][CH2:11][O:12][CH3:13])=[CH:8][C:5]([C:6]#[N:7])=[CH:4][N:3]=1.[B:14]1([OH:24])[C:18]2[CH:19]=[CH:20][C:21]([OH:23])=[CH:22][C:17]=2[CH2:16][O:15]1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[OH:24][B:14]1[C:18]2[CH:19]=[CH:20][C:21]([O:23][C:2]3[C:9]([O:10][CH2:11][O:12][CH3:13])=[CH:8][C:5]([C:6]#[N:7])=[CH:4][N:3]=3)=[CH:22][C:17]=2[CH2:16][O:15]1

Komponenten

Reaktionsbedingungen

Temperatur: 80 °C

Versuchsvorschrift

To a mixture of 6-chloro-5-methoxymethoxy-nicotinonitrile (0.68 g, 3.42 mmol) and 3H-benzo[c][1,2]oxaborole-1,5-diol (0.56 g, 3.76 mmol) in DMF (10 mL) was added cesium carbonate (2.45 g, 7.52 mmol). The resulting suspension was heated at 80° C. for overnight. DMF was removed under reduced pressure, the residue was diluted with EtOAc (50 mL), washed with water (10 mL) and brine (10 mL), dried over Na2SO4, filtered, and concentrated to give brown oil. Purification was accomplished by flash chromatography on silica gel using 1-100% MeOH/EtOAc gradient elution to yield the title compound (0.40 g, 40%) as a transparent oil. 1H NMR (400 MHz, DMSO-d6) δ ppm 9.23 (s, 1H), 8.24 (s, 1H), 8.03 (s, 1H), 7.77 (d, J=8.6 Hz, 1H), 7.23 (s, 1H), 7.14 (d, J=7.4 Hz, 1H), 5.40 (s, 2H), 4.98 (s, 2H), 3.45 (s, 3H); MS (ES) m/z: 313 (M+1)+.

Aufarbeitung

customDMF was removed under reduced pressure
additionthe residue was diluted with EtOAc (50 mL)
washwashed with water (10 mL) and brine (10 mL)
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated
customto give brown oil
customPurification
washwas accomplished by flash chromatography on silica gel using 1-100% MeOH/EtOAc gradient elution

Quellen und Nachweise

ORD-Eintrag: ord-28fc57011252498692cbff19012a32e3
Quelldatensatz: uspto-grants-2013_06
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US08461135B2

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