Dimethylformamide → 4-Aminopyridine-2-carbonitrile

HRID 272685

反応式

HRID 272685 の反応式
Cl[C:2]1[CH:7]=[C:6]([NH2:8])[CH:5]=[CH:4][N:3]=1.[CH3:9][N:10](C=O)C>[C-]#N.[C-]#N.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([C:9]#[N:10])[CH:7]=1

参加物

5

反応物 2

HCID 6228DimethylformamideHCID 844322-Chloropyridin-4-amine

生成物 1

HCID 231314544-Aminopyridine-2-carbonitrile収率 20%

試薬・触媒・溶媒 2

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 178418397HCID 178418397、化合物触媒

反応条件

温度
145 °C

実験手順

A mixture of 2-chloro-pyridin-4-ylamine (0.642 g, 5 mmol), Zn(CN)2 (0.323 g, 2.75 mmol) and Pd(PPh3)4 (0.288 g, 0.025 mmol) in 5 mL of DMF was heated at 145° C. for 20 hours. After the reaction mixture cooled to room temperature, it was partitioned between ethyl acetate and H2O. The aqueous layer was extracted with additional ethyl acetate. The combined organic layers were washed with brine, dried (MgSO4), filtered, and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel with 9:1 hexanes/ethyl acetate to provide 0.29 g (20%) of the desired product. MS (DCI) m/e 120 (M+H)+; 1H NMR (300 MHz, DMSO-d6) δ 8.08 (d, J=5.76 Hz, 1H), 6.94 (d, J=2.34 Hz, 1H), 6.68 (dd, J=5.76, 2.37 Hz, 1H), 6.59 (s, 2H).

後処理

  1. temperatureAfter the reaction mixture cooled to room temperature
  2. customit was partitioned between ethyl acetate and H2O
  3. extractionThe aqueous layer was extracted with additional ethyl acetate
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe residue was purified by flash column chromatography on silica gel with 9:1 hexanes/ethyl acetate

出典と根拠

ORDレコード
ord-1ad6cbe210044a6989ad4d2dcdaa3449
出典データセット
uspto-grants-2008_11
特許番号
US07456169B2

関連ノート

読み込み中…