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

HRID 1986175Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1986175
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

Komponenten

5

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-fa328967377e41c983d2c4c22ddc0373
Quelldatensatz
uspto-grants-2009_06
Patentnummer
US07547691B2

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