Ethyl Acetate → Tert-butyl 3-cyanopiperidine-1-carboxylate

HRID 659610ノート

反応式

HRID 659610 の反応式
[C:1]([CH:4]1[CH2:9][CH2:8][CH2:7][N:6]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:5]1)(=O)[NH2:2].O=P(Cl)(Cl)Cl.CC(=O)OCC>N1C=CC=CC=1>[C:1]([CH:4]1[CH2:9][CH2:8][CH2:7][N:6]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:5]1)#[N:2]

参加物

5

反応物 3

HCID 8857Ethyl AcetateHCID 24813Phosphorus oxychlorideHCID 146618953-Carbamoyl-piperidine-1-carboxylic acid tert-butyl ester

生成物 1

HCID 2756785Tert-butyl 3-cyanopiperidine-1-carboxylate収率 57.5%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒

反応条件

温度
0 °C

実験手順

A 250-mL 3-necked round-bottomed flask was charged with a solution of tert-butyl 3-carbamoylpiperidine-1-carboxylate (5 g, 21.49 mmol, 1.00 equiv, 98%) in pyridine (50 mL). To this solution, POCl3 (5 g, 32.24 mmol, 1.50 equiv, 98%) was added drop wise at 0° C. and allowed to stir at 0° C. for 1 hour. The progress was monitored by TLC (EA:PE=1:1). The pyridine was removed by distillation. The mixture was diluted with H2O (40 mL) and pH was adjusted to 8 by addition of aqueous NaHCO3. Then, the resulting mixture was extracted with ethyl acetate (3×30 mL). Combined organic layers were dried over anhydrous sodium sulfate, filtered off and concentrated on a rotary evaporator. The crude was purified by distillation under reduced pressure (30 mm Hg) and the fractions collected at 40° C. to afford tert-butyl 3-cyanopiperidine-1-carboxylate as yellow oil (2.6 g, 53%).

後処理

  1. customThe pyridine was removed by distillation
  2. additionThe mixture was diluted with H2O (40 mL) and pH
  3. additionwas adjusted to 8 by addition of aqueous NaHCO3
  4. extractionThen, the resulting mixture was extracted with ethyl acetate (3×30 mL)
  5. dry with materialCombined organic layers were dried over anhydrous sodium sulfate
  6. filtrationfiltered off
  7. concentrationconcentrated on a rotary evaporator
  8. distillationThe crude was purified by distillation under reduced pressure (30 mm Hg)
  9. customthe fractions collected at 40° C.

出典と根拠

ORDレコード
ord-e29aefe7c1384759844d188b93d1353a
出典データセット
uspto-grants-2011_12
特許番号
US08080566B1

反応ノート

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