Pyridine → 2-[(2,4-Dichlorophenyl)methyl]-4,4-dimethylisoxazolidine-3,5-dione

HRID 1155464ノート

反応式

HRID 1155464 の反応式
N1C=CC=CC=1.[CH3:7][C:8]([CH3:15])([C:12](Cl)=[O:13])[C:9](Cl)=[O:10].[Cl:16][C:17]1[CH:22]=[C:21]([Cl:23])[CH:20]=[CH:19][C:18]=1[CH2:24][NH:25][OH:26]>C(Cl)Cl>[Cl:16][C:17]1[CH:22]=[C:21]([Cl:23])[CH:20]=[CH:19][C:18]=1[CH2:24][N:25]1[C:9](=[O:10])[C:8]([CH3:15])([CH3:7])[C:12](=[O:13])[O:26]1

参加物

5

反応物 3

HCID 1049PyridineHCID 4523180Dimethylmalonyl DichlorideHCID 12811042N-[(2,4-dichlorophenyl)methyl]hydroxylamine2 回

生成物 1

HCID 128110492-[(2,4-Dichlorophenyl)methyl]-4,4-dimethylisoxazolidine-3,5-dione収率 45%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
0 °C

実験手順

Seventy-five ml of methylene chloride and 9.6 ml (0.12 mole) of pyridine were placed in a flask under argon and cooled to 0° C. To this solution 8.4 grams (0.05 mole) dimethylmalonylchloride in 20 ml methylene chloride was added dropwise with stirring. This mixture was cooled to -70° C. and 9.6 g (0.05 mole) of N-(2,4-dichlorophenylmethyl)hydroxylamine (Intermediate E) was added in a single portion, and the temperature rose to 35° C. Stirring was continued for two hours at -10° C., and at ambient temperature for about 18 hours. The reaction mixture was washed with 2 N hydrochloric acid and saturated aqueous sodium chloride solution, and the methylene chloride layer was dried over sodium sulfate, which was removed by filtration. The filtrate was evaporated under reduced pressure and the resulting viscous liquid was subjected to column chromatography on silica gel. Elution was accomplished with 25% ethyl acetate in hexane. Cuts 3-11 were combined and solvent was removed under reduced pressure, yielding a light orange viscous liquid. This solidified as 6.5 grams of product (45% yield); mp 68°-69.5° C. The nmr and ir spectra were consistent with the assigned structure.

後処理

  1. temperatureThis mixture was cooled to -70° C.
  2. customrose to 35° C
  3. stirringStirring
  4. waitat ambient temperature for about 18 hours
  5. washThe reaction mixture was washed with 2 N hydrochloric acid and saturated aqueous sodium chloride solution
  6. dry with materialthe methylene chloride layer was dried over sodium sulfate, which
  7. customwas removed by filtration
  8. customThe filtrate was evaporated under reduced pressure
  9. washElution
  10. customsolvent was removed under reduced pressure
  11. customyielding a light orange viscous liquid

出典と根拠

ORDレコード
ord-1edd481d6272483894b741add030eabf
出典データセット
uspto-grants-1981_11
特許番号
US04302238

反応ノート

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