Dimethylcarbamoyl Chloride → 6-Acetylpicolinonitrile

HRID 1735974노트

반응식

HRID 1735974 반응식
[C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][N+:5]=1[O-])(=[O:3])[CH3:2].[CH3:11][N:12](C)C(Cl)=O.C([Si](C)(C)C)#N.C([O-])([O-])=O.[K+].[K+]>C(Cl)Cl>[C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:11]#[N:12])[N:5]=1)(=[O:3])[CH3:2]

참가 물질

6

반응물 4

HCID 6598Dimethylcarbamoyl Chloride2회HCID 11430Potassium CarbonateHCID 82115Trimethylsilyl cyanide2회HCID 3379981-(1-Oxidopyridin-6-yl)ethanone

생성물 1

HCID 152188056-Acetylpicolinonitrile

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

To a solution of 2-acetylpyridine-N-oxide (0.098 mol) in 200 ml of methylene chloride was added dimethylcarbamyl chloride (0.1 mol) and the reaction mixture was allowed to react at room temperature under nitrogen for 24 hours. Additional dimethylcarbamyl chloride (0.1 mol) was added followed by cyanotrimethylsilane (0.22 mol), and the resulting mixture was allowed to react at 20° C. for 2 days. An additional 4 ml (0.03 mol) of cyanotrimethylsilane was then added, and the mixture was stirred at room temperature for another 24 hours. A solution of 200 ml of 10% K2CO3 was added to the reaction mixture and the resulting mixture was stirred for 45 minutes. The aqueous layer was extracted with 100 ml methylene chloride twice, the organic layers were combined and dried (K2CO3). After stripping the solvent, 16.9 g of crude product was isolated. The crude product obtained was chromatographed over Florisil® to isolate the desired products and the by-products with elution by the series of solvents: 2-acetyl-6-cyanopyridine (3a) (2g, 50% CH2Cl2 /hexane), 2-cyano-6-(1-cyano-1-trimethysilyloxy)ethylpyridine (3b) (0.81 g, CH2Cl2), 2-cyano-6-(1-cyano-1-dimethylcarbamoyloxy)ethylpyridine (3c) (1.67 g, 25:72 EtOAc/CH2Cl2), 2-(1-cyano-1-hydroxy)ethylpyridine (3d) (0.42 g, 50:50 EtOAc/CH2Cl2), and 2-(1-cyano-1-dimethylcarbamoyloxy)ethylpyridine-1-N-oxide (3e) (1.8 g, EtOAc). The products exhibited the following properties.

후처리

  1. customto react at room temperature under nitrogen for 24 hours
  2. customto react at 20° C. for 2 days
  3. stirringthe resulting mixture was stirred for 45 minutes
  4. extractionThe aqueous layer was extracted with 100 ml methylene chloride twice
  5. dry with materialdried (K2CO3)
  6. custom16.9 g of crude product was isolated
  7. customThe crude product obtained
  8. customwas chromatographed over Florisil®

출처 및 근거

ORD 기록
ord-3b52f7d520f64a7a93666b9731fdf243
출처 데이터셋
uspto-grants-1996_07
특허 번호
US05539117

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