Sodium hydride → Methyl 2-(1-methylpiperidin-4-yl)acetate

HRID 742324Notizen

Reaktionsgleichung

C(OP([CH2:9][C:10]([O:12][CH3:13])=[O:11])(OCC)=O)C.[H-].[Na+].[CH3:16][N:17]1[CH2:22][CH2:21][C:20](=O)[CH2:19][CH2:18]1>C1COCC1>[CH3:16][N:17]1[CH2:22][CH2:21][CH:20]([CH2:9][C:10]([O:12][CH3:13])=[O:11])[CH2:19][CH2:18]1

Komponenten

Reaktionsbedingungen

Temperatur: 60 °C

Versuchsvorschrift

Methyl diethylphosphonoacetate (88.69 g, 0.422 mol) was added dropwise to a stirred suspension of sodium hydride (18.56 g, 60% dispersion in oil, 0.464 mol) in THF (300 ml) under nitrogen, at such a rate as to maintain the temperature below 30° C. The mixture was stirred for 1 h and a solution of N-methyl-4-piperidinone (47.71 g, 0.422 mol) in THF (150 ml) was added dropwise. The mixture was heated at 60° C. for 4.5 h before removing the solvent under vacuum and redissolving the residue in dichloromethane (300 ml) and water (200 ml). The dichloromethane phase was separated, washed successively with water (200 ml) and saturated sodium bisulphite solution (2×70 ml) and dried (MgSO4). The crude product was chromategraphed on silica gel, eluting with methanol/ether (5:95) to give the title-product (19.75 g, 28%). 1H NMR (250 MHz, CDCl3) δ (3H, s, N-CH3), 2.35 (2H, t, J=6 Hz, CH2), 2.40-2.50 (4H, m, 2 of CH2), 3.00 (2H, t, J=6 Hz, CH2), 3.70 (3H, s, CO2CH3), 5.65 (1H, s, vinyl CH).

Aufarbeitung

temperatureat such a rate as to maintain the temperature below 30° C
custombefore removing the solvent under vacuum
dissolutionredissolving the residue in dichloromethane (300 ml)
customThe dichloromethane phase was separated
washwashed successively with water (200 ml) and saturated sodium bisulphite solution (2×70 ml)
dry with materialdried (MgSO4)
washeluting with methanol/ether (5:95)

Quellen und Nachweise

ORD-Eintrag: ord-960e12df9aed4e6baf8949d4b864ad17
Quelldatensatz: uspto-grants-1996_09
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US05554629

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