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

HRID 2284497ノート

反応式

HRID 2284497 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-1959efbaddfc467b8baf5e3b0aec2314
出典データセット
uspto-grants-2015_09
特許番号
US09145429B2

反応ノート

読み込み中…