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

HRID 1986175노트

반응식

HRID 1986175 반응식
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

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
0 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-fa328967377e41c983d2c4c22ddc0373
출처 데이터셋
uspto-grants-2009_06
특허 번호
US07547691B2

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