Dimethyl Sulfate → N-Boc-2-Methyl-Piperidine

HRID 840680

Reaktionsgleichung

[C:1]([N:8]1[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[CH3:14]N(CCN(C)C)C.[Li]C(CC)C.S(OC)(OC)(=O)=O>CCOCC.O>[C:1]([N:8]1[CH2:9][CH2:10][CH2:11][CH2:12][CH:13]1[CH3:14])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2]

Komponenten

Reaktionsbedingungen

Temperatur: -78 °C

Versuchsvorschrift

A solution of N-Boc-Piperidine (15.0 g, 80.95 mmol) in ether (160 mL) was cooled to −78° C. and treated with TMEDA (15.9 mL, 105.2 mmol) followed by sec-BuLi (85 mL, 105.2 mmol) dropwise. The mixture was stirred for 3 h at −78° C. and then treated with a solution of dimethyl sulfate (15.3 mL, 161.9 mmol) in 65 mL of ether. The mixture was warmed to room temperature and then was diluted with water and extracted with ether. The combined extracts were dried over K2CO3 and then concentrated to give a crude product as a colorless oil. The product was purified by column chromatography on silca gel with 5% EtOAc/hexane to afford 16.0 g (81%) of product as a clear oil which was homogeneous by TLC analysis. 1H NMR (300 MHz) 67 4.33 (m, 1 H), 3.92-3.81 (pair of br. d, 1 H), 2.81-2.72 (dt, 1H), 1.60-1.36 (m, 15 H), 1.09-1.07 (d, 3 H); 13C NMR (75 MHz) 154.9 (s), 78.6 (s), 45.9 (s), 38.6 (s), 29.9 (s), 28.4 (s), 25.6 (s), 18.6 (s), 15.6 (s), ppm.

Aufarbeitung

temperatureThe mixture was warmed to room temperature
extractionextracted with ether
dry with materialThe combined extracts were dried over K2CO3
concentrationconcentrated
customto give a crude product as a colorless oil
customThe product was purified by column chromatography on silca gel with 5% EtOAc/hexane

Quellen und Nachweise

ORD-Eintrag: ord-04bcec3d8e0849d38352a346ae5610cd
Quelldatensatz: uspto-grants-2002_04
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US06369078B1

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