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

HRID 1020811

Reaktionsgleichung

Reaktionsgleichung von HRID 1020811
[Cl:1][C:2]1[C:3](Cl)=[N:4][C:5]([O:10][CH2:11][CH2:12][O:13][CH:14]([CH3:16])[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][O:13][CH:14]([CH3:16])[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 866617205,6-Dichloro-2-(2-isopropoxyethoxy)nicotinonitrile

Produkt 1

HCID 533445865-Chloro-6-(1-hydroxy-1,3-dihydrobenzo(c)(1,2)oxaborol-5-yloxy)-2-(2-isopropoxyethoxy)nicotinonitrile

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-(2-isopropoxyethoxy)nicotinonitrile (1.13 g, 4.12 mmol, 1.00 equiv) in DMSO (80 mL), benzo[c][1,2]oxaborole-1,5(3H)-diol (650 mg, 4.33 mmol, 1.00 equiv) and Cs2CO3 (1.6 g, 4.91 mmol, 1.20 equiv). The resulting mixture was stirred for 2 h at 40° C., then quenched by the addition of 50 mL of water. The resulting solution was extracted with 3×30 mL of ethyl acetate. The organic layers were combined, washed with 2×50 mL of water, then dried over anhydrous sodium sulfate and concentrated under vacuum. This resulted in 5-chloro-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)-2-(2-isopropoxyethoxy)nicotinonitrile (1.3 g, 80%) as a white solid. LC-MS (ES, m/z): 389 [M+H]+. 1H-NMR (300 MHz, DMSO-d6) δ (ppm) 9.260 (1H, s), 8.596 (1H, s), 7.817-7.791 (1H, d, J=7.8 Hz), 7.337 (1H, s), 7.268-7.235 (1H, m), 5.007 (2H, s), 4.105-4.072 (2H, t), 3.495-3.435 (2H, m), 3.415-3.395 (1H, t), 1.016-0.995 (6H, d, J=6.3 Hz).

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 50 mL of water
  4. extractionThe resulting solution was extracted with 3×30 mL of ethyl acetate
  5. washwashed with 2×50 mL of water
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under vacuum
  8. customThis resulted in 5-chloro-6-(1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaborol-5-yloxy)-2-(2-isopropoxyethoxy)nicotinonitrile (1.3 g, 80%) as a white solid

Quellen und Nachweise

ORD-Eintrag
ord-11c7d85d8e1c499eb644b01746017b2d
Quelldatensatz
uspto-grants-2014_05
Patentnummer
US08716478B2

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