Cesium carbonate → 5-Chloro-2-(2,3-dimethoxypropoxy)-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)nicotinonitrile

HRID 1020813

Reaktionsgleichung

Reaktionsgleichung von HRID 1020813
[Cl:1][C:2]1[C:3](Cl)=[N:4][C:5]([O:10][CH2:11][CH:12]([O:16][CH3:17])[CH2:13][O:14][CH3:15])=[C:6]([CH:9]=1)[C:7]#[N:8].[B:19]1([OH:29])[C:23]2[CH:24]=[CH:25][C:26]([OH:28])=[CH:27][C:22]=2[CH2:21][O:20]1.C([O-])([O-])=O.[Cs+].[Cs+]>CS(C)=O>[Cl:1][C:2]1[C:3]([O:28][C:26]2[CH:25]=[CH:24][C:23]3[B:19]([OH:29])[O:20][CH2:21][C:22]=3[CH:27]=2)=[N:4][C:5]([O:10][CH2:11][CH:12]([O:16][CH3:17])[CH2:13][O:14][CH3:15])=[C:6]([CH:9]=1)[C:7]#[N:8]

Komponenten

5

Edukt 3

HCID 10796Cesium carbonateHCID 579686991,3-Dihydro-1-hydroxy-2,1-benzoxaborol-5-olHCID 86661722HCID 86661722, Verbindung

Produkt 1

HCID 533462325-Chloro-2-(2,3-dimethoxypropoxy)-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)nicotinonitrile

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 679Dimethyl SulfoxideLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

Into a 50-mL 3-neck-bottle purged and maintained with an inert atmosphere of nitrogen were placed a solution of 5,6-dichloro-2-(2,3-dimethoxypropoxy)nicotinonitrile (1.40 g, 4.59 mmol, 1.00 equiv, 95%) in DMSO (20 mL), benzo[c][1,2]oxaborole-1,5(3H)-diol (800 mg, 5.07 mmol, 1.10 equiv, 95%) and Cs2CO3 (1.88 g, 5.78 mmol, 1.20 equiv). The resulting solution was stirred for 2 h at 50° C. in an oil bath. The reaction mixture was then cooled and quenched by the addition of 20 mL of water. The resulting solution was extracted with 3×20 mL of ethyl acetate. The organic layers were combined, dried and concentrated under vacuum. The residue was applied onto a silica gel column and eluted with EtOAc/petroleum ether (1:5). This resulted in 1.09 g (57%) of 5-chloro-2-(2,3-dimethoxypropoxy)-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)nicotinonitrile as a white solid. LC-MS (ES, m/z): 405 [M+H]+. 1H-NMR (300 MHz, DMSO-d6) δ (ppm) 9.27 (1H, m); 8.61 (1H, m); 7.82 (1H, d, J=8.1 Hz); 7.34 (1H, m); 7.26 (1H, m); 5.00 (2H, s); 4.12-4.17 (1H, m); 3.97-4.03 (1H, m); 3.25-3.30 (1H, m); 3.17 (6H, s).

Aufarbeitung

  1. customInto a 50-mL 3-neck-bottle purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. temperatureThe reaction mixture was then cooled
  4. customquenched by the addition of 20 mL of water
  5. extractionThe resulting solution was extracted with 3×20 mL of ethyl acetate
  6. customdried
  7. concentrationconcentrated under vacuum
  8. washeluted with EtOAc/petroleum ether (1:5)
  9. customThis resulted in 1.09 g (57%) of 5-chloro-2-(2,3-dimethoxypropoxy)-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)nicotinonitrile as a white solid

Quellen und Nachweise

ORD-Eintrag
ord-b7f1a41a77444f8eb28e05927f5a36c5
Quelldatensatz
uspto-grants-2014_05
Patentnummer
US08716478B2

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