Water → tert-Butyl 3-ethyl-4-oxopiperidine-1-carboxylate

HRID 242576ノート

反応式

HRID 242576 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].N1CC[CH2:17][CH2:16]1.O.ICC>C1C=CC=CC=1.C1(C)C=CC(S(O)(=O)=O)=CC=1>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH2:10][C:11](=[O:14])[CH:12]([CH2:16][CH3:17])[CH2:13]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

参加物

7

反応物 4

HCID 962WaterHCID 6340IodoethaneHCID 31268PyrrolidineHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

生成物 1

HCID 22278903tert-Butyl 3-ethyl-4-oxopiperidine-1-carboxylate

試薬・触媒・溶媒 2

HCID 6101p-Toluenesulfonic acid触媒HCID 241Benzene溶媒

反応条件

温度
100 °C

実験手順

A solution of 4-oxo-piperidine-1-carboxylic acid tert-butyl ester (5 g, 25.1 mmol), pyrollidine (5 mL) and p-toluenesulfonic acid (25 mg) in benzene (100 mL) was heated at reflux for 16 h with azeotropic distillation of water. The resulting enamine solution was cooled to rt and concentrated. The crude enamine was dissolved in acetonitrile (50 mL); iodoethane (4.67 g, 30.1 mmol.) was added and the mixture was heated at 100° C. for 0.5 h, cooled to rt and concentrated. The mixture was dissolved in ethyl acetate (200 mL), washed with 1 N hydrochloric acid, saturated aqueous sodium bicarbonate, and brine. The extract was dried over magnesium sulfate, filtered and concentrated. The crude compound was purified by silica gel chromatography (80% hexanes/20% ethyl acetate) to afford 3-ethyl-4-oxo-piperidine-1-carboxylic acid tert-butyl ester (680 mg).

後処理

  1. concentrationconcentrated
  2. dissolutionThe crude enamine was dissolved in acetonitrile (50 mL)
  3. temperaturecooled to rt
  4. concentrationconcentrated
  5. dissolutionThe mixture was dissolved in ethyl acetate (200 mL)
  6. washwashed with 1 N hydrochloric acid, saturated aqueous sodium bicarbonate, and brine
  7. dry with materialThe extract was dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude compound was purified by silica gel chromatography (80% hexanes/20% ethyl acetate)

出典と根拠

ORDレコード
ord-30ad9d97f9334e24854b2f6a57f097b1
出典データセット
uspto-grants-2014_02
特許番号
US08653096B2

反応ノート

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