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Potassium Cyanide → 2-(2,6-Dichloropyridin-3-yl)acetonitrile

HRID 241770
ノート
印刷プレビュー

反応式

HRID 241770 の反応式
[C-]#N.[K+].Br[CH2:5][C:6]1[C:7]([Cl:13])=[N:8][C:9]([Cl:12])=[CH:10][CH:11]=1.BrCC1(CBr)C=CC(Cl)=[N:18][CH:17]1Cl>O.C(O)C>[Cl:13][C:7]1[C:6]([CH2:5][C:17]#[N:18])=[CH:11][CH:10]=[C:9]([Cl:12])[N:8]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 3

HCID 9032Potassium Cyanide2 回HCID 122653943-(Bromomethyl)-2,6-dichloropyridine2 回HCID 668505573,3-Dibromomethyl-2,6-dichloro-pyridine

生成物 1

HCID 122653992-(2,6-Dichloropyridin-3-yl)acetonitrile

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 962Water
溶媒

反応条件

温度
40 °C

実験手順

Potassium cyanide (1.0 g) was dissolved in water by heating to 40° C. A mixture of 3-bromomethyl-2,6-dichloro-pyridine, 3,3-dibromomethyl-2,6-dichloro-pyridine, and 2,6-dichloro-3-methyl-pyridine (Example 4.1) (3.2 g) suspended in ethanol (20 ml) was added dropwise at 40° C. over a period of 30 minutes. The reaction mixture was heated to reflux for 3 hours. The reaction mixture was cooled to 40° C. and another equivalent of potassium cyanide was added. The reaction mixture was heated to reflux for a further 3 hours and then stored at ambient temperature for 16 hours. The reaction mixture was filtered to remove the solids and the solids were washed with ethyl acetate. The combined filtrates were concentrated. The residue was diluted with ethyl acetate. The organic solution washed with aqueous sodium hydrogen carbonate (saturated) and brine, dried over magnesium sulfate, and concentrated. This residue was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane from 3:100 to 1:1) to give slightly impure (2,6-dichloro-pyrid-3-yl)-acetonitrile (1.5 g) which solidified on standing. This material was used without further purification. 1H-NMR (400 MHz, CDCl3): 3.83 (s, 2H), 7.37 (d, 1H), 7.85 (d, 1H) ppm.

後処理

  1. additionwas added dropwise at 40° C. over a period of 30 minutes
  2. temperatureThe reaction mixture was heated
  3. temperatureto reflux for 3 hours
  4. temperatureThe reaction mixture was cooled to 40° C.
  5. temperatureThe reaction mixture was heated
  6. temperatureto reflux for a further 3 hours
  7. filtrationThe reaction mixture was filtered
  8. customto remove the solids
  9. washthe solids were washed with ethyl acetate
  10. concentrationThe combined filtrates were concentrated
  11. additionThe residue was diluted with ethyl acetate
  12. washThe organic solution washed with aqueous sodium hydrogen carbonate (saturated) and brine
  13. dry with materialdried over magnesium sulfate
  14. concentrationconcentrated
  15. customThis residue was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane from 3:100 to 1:1)

出典と根拠

ORDレコード
ord-3cddb2add19e433aa9014bc9285adc64
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08653078B2

反応ノート

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