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

HRID 1020813

反応式

HRID 1020813 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
50 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-b7f1a41a77444f8eb28e05927f5a36c5
出典データセット
uspto-grants-2014_05
特許番号
US08716478B2

関連ノート

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