Cesium carbonate → 5-Chloro-6-[(1,3-dihydro-1-hydroxy-2,1-benzoxaborol-5-YL)oxy]-2-[(4-oxopentyl)oxy]-3-pyridinecarbonitrile

HRID 1020812

Reaktionsgleichung

Reaktionsgleichung von HRID 1020812
[Cl:1][C:2]1[C:3](Cl)=[N:4][C:5]([O:10][CH2:11][CH2:12][CH2:13][C:14](=[O:16])[CH3:15])=[C:6]([CH:9]=1)[C:7]#[N:8].[B:18]1([OH:28])[C:22]2[CH:23]=[CH:24][C:25]([OH:27])=[CH:26][C:21]=2[CH2:20][O:19]1.C([O-])([O-])=O.[Cs+].[Cs+]>CS(C)=O>[Cl:1][C:2]1[C:3]([O:27][C:25]2[CH:24]=[CH:23][C:22]3[B:18]([OH:28])[O:19][CH2:20][C:21]=3[CH:26]=2)=[N:4][C:5]([O:10][CH2:11][CH2:12][CH2:13][C:14](=[O:16])[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 86661721HCID 86661721, Verbindung

Produkt 1

HCID 469110665-Chloro-6-[(1,3-dihydro-1-hydroxy-2,1-benzoxaborol-5-YL)oxy]-2-[(4-oxopentyl)oxy]-3-pyridinecarbonitrile

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 679Dimethyl SulfoxideLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

Into a 250-mL 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen were placed a solution of 5,6-dichloro-2-(4-oxopentyloxy)nicotinonitrile (1.12 g, 4.12 mmol, 1.00 equiv) in DMSO (50 mL), benzo[c][1,2]oxaborole-1,5(3H)-diol (650 mg, 4.33 mmol, 1.05 equiv) and Cs2CO3 (1.60 g, 4.92 mmol, 1.20 equiv). The resulting solution was stirred for 2 h at 40° C., then quenched by the addition of 100 mL of ice water. The resulting solution was extracted with 3×50 mL of ethyl acetate. The organic layers were combined, washed with 2×50 mL of water and 1×50 mL of brine, then dried over Na2SO4 and concentrated under vacuum. This resulted in 1.3 g (80%) of 5-chloro-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)-2-(4-oxopentyloxy)nicotinonitrile as a white solid. LC-MS (ES, m/z): 387 [M+H]+. 1H-NMR (300 MHz, DMSO-d6) δ (ppm) 9.28 (1H, s), 8.60 (1H, s), 7.81 (1H, d, J=7.8 Hz), 7.33 (1H, s), 7.25 (1H, d, J=7.8 Hz), 5.02 (2H, s), 4.00 (2H, t), 2.35 (2H, t), 2.05 (3H, s), 1.8-1.6 (2H, m).

Aufarbeitung

  1. customInto a 250-mL 3-necked round-bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. customquenched by the addition of 100 mL of ice water
  4. extractionThe resulting solution was extracted with 3×50 mL of ethyl acetate
  5. washwashed with 2×50 mL of water and 1×50 mL of brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under vacuum
  8. customThis resulted in 1.3 g (80%) of 5-chloro-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)-2-(4-oxopentyloxy)nicotinonitrile as a white solid

Quellen und Nachweise

ORD-Eintrag
ord-8c7ab527a1b04f0d9235ed5946032170
Quelldatensatz
uspto-grants-2014_05
Patentnummer
US08716478B2

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