2,2,6,6-Tetramethyl-4-piperidone → (2,2,6,6-Tetramethylpiperidin-4-ylidene)acetonitrile

HRID 1986175ノート

反応式

HRID 1986175 の反応式
CC(C)([O-])C.[K+].C(OP([CH2:15][C:16]#[N:17])(=O)OCC)C.[CH3:18][C:19]1([CH3:28])[CH2:24][C:23](=O)[CH2:22][C:21]([CH3:27])([CH3:26])[NH:20]1>C1COCC1>[CH3:18][C:19]1([CH3:28])[CH2:24][C:23](=[CH:15][C:16]#[N:17])[CH2:22][C:21]([CH3:27])([CH3:26])[NH:20]1

参加物

5

反応物 3

HCID 132202,2,6,6-Tetramethyl-4-piperidoneHCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxide

生成物 1

HCID 21559280(2,2,6,6-Tetramethylpiperidin-4-ylidene)acetonitrile収率 33%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

Potassium tert-butoxide (9.40 g, 83.7 mmol) is suspended in THF (175 mL), then cooled to 0° C. Cyanomethyl-phosphonic acid diethyl ester (16.0 g, 90.2 mmol) is added over five minutes. After stirring for 20 minutes, 2,2,6,6-tetramethylpiperidin-4-one (10.0 g, 64.4 mmol) dissolved in THF (50 mL) is added to the reaction mixture at −78° C. After the addition is complete the cold bath is removed. The reaction is stirred overnight, then enough water is added to dissolve any suspended salts. The organic layer is separated and the aqueous layer is extracted with EtOAc. The organic layers are combined, concentrated, then the residue is chromatographed on silica gel, eluting with 0-3% 2M NH3/MeOH in dichloromethane to give 3.77 g of (2,2,6,6-tetramethylpiperidin-4-ylidene)-acetonitrile (33% yield).

後処理

  1. additionis added to the reaction mixture at −78° C
  2. additionAfter the addition
  3. customis removed
  4. stirringThe reaction is stirred overnight
  5. additionenough water is added
  6. dissolutionto dissolve any suspended salts
  7. customThe organic layer is separated
  8. extractionthe aqueous layer is extracted with EtOAc
  9. concentrationconcentrated
  10. customthe residue is chromatographed on silica gel
  11. washeluting with 0-3% 2M NH3/MeOH in dichloromethane

出典と根拠

ORDレコード
ord-fa328967377e41c983d2c4c22ddc0373
出典データセット
uspto-grants-2009_06
特許番号
US07547691B2

反応ノート

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