Dimethylcarbamoyl Chloride → 6-Acetylpicolinonitrile

HRID 2226825ノート

反応式

HRID 2226825 の反応式
[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]

参加物

6

反応物 4

HCID 6598Dimethylcarbamoyl Chloride2 回HCID 11430Potassium CarbonateHCID 82115Trimethylsilyl cyanide2 回HCID 3379981-(1-Oxidopyridin-6-yl)ethanone

生成物 1

HCID 152188056-Acetylpicolinonitrile

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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) (2 g, 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.

後処理

  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®

出典と根拠

ORDレコード
ord-84e4f7ba5f934f9a81e3912742a59a9f
出典データセット
uspto-grants-1994_09
特許番号
US05350696

反応ノート

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