Dimethylacetamide → 5-Chloro-3-methylpyridine-2-carbonitrile

HRID 1526553ノート

反応式

HRID 1526553 の反応式
Br[C:2]1[C:7]([CH3:8])=[CH:6][C:5]([Cl:9])=[CH:4][N:3]=1.C[C:11]([N:13](C)C)=O>O.[C-]#N.[Zn+2].[C-]#N.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[Cl:9][C:5]1[CH:6]=[C:7]([CH3:8])[C:2]([C:11]#[N:13])=[N:3][CH:4]=1

参加物

7

反応物 2

HCID 31374DimethylacetamideHCID 126309852-Bromo-5-chloro-3-methylpyridine

生成物 1

HCID 218645635-Chloro-3-methylpyridine-2-carbonitrile収率 76%

試薬・触媒・溶媒 4

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 9832798Tris(dibenzylideneacetone) dipalladium触媒HCID 962Water溶媒

反応条件

温度
110 °C

実験手順

A mixture of 2-bromo-5-chloro-3-methylpyridine (45 g, 218 mmol), zinc cyanide (8.30 mL, 131 mmol), tris(dibenzylideneacetone) dipalladium (0) (4.99 g, 5.45 mmol), and 1,1′-bis(diphenylphosphino)ferrocene (6.04 g, 10.90 mmol) in dimethylacetamide (40 mL) was heated to 110° C. for 4 hours. The reaction mixture was cooled to RT, diluted with water and extracted with ethyl acetate. The organic phase obtained was concentrated under reduced pressure and residue purified by chromatography on silica gel using ISCO eluting with 0-60% EtOAc/hex to afford the title compound 5-chloro-3-methylpicolinonitrile (25.4 g, 166 mmol, 76% yield). LC/MS (ESI+) m/z=153.1 (M+H).

後処理

  1. temperatureThe reaction mixture was cooled to RT
  2. extractionextracted with ethyl acetate
  3. customThe organic phase obtained
  4. concentrationwas concentrated under reduced pressure and residue
  5. custompurified by chromatography on silica gel using ISCO
  6. washeluting with 0-60% EtOAc/hex

出典と根拠

ORDレコード
ord-9859ff9bf0924feea8a4f8097b05ea35
出典データセット
uspto-grants-2015_07
特許番号
US09085576B2

反応ノート

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