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

HRID 1526553노트

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HRID 1526553 반응식
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

참가 물질

7

반응물 2

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

생성물 1

HCID 218645635-Chloro-3-methylpyridine-2-carbonitrile수율 76%

시약·촉매·용매 4

HCID 11186Zinc cyanide (Zn(CN)2)촉매HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)촉매HCID 9832798Tris(dibenzylideneacetone) dipalladium촉매HCID 962Water용매

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온도
110 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-9859ff9bf0924feea8a4f8097b05ea35
출처 데이터셋
uspto-grants-2015_07
특허 번호
US09085576B2

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