Pyridine → 2-(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-(4-fluoro-benzyl)-N-methoxy-acetamide

HRID 1836463

Reaktionsgleichung

Reaktionsgleichung von HRID 1836463
[CH3:1][C:2]1([CH3:12])[O:6][C:5](=[CH:7][C:8](Cl)=[O:9])[C:4](=[O:11])[O:3]1.[F:13][C:14]1[CH:23]=[CH:22][C:17]([CH2:18][NH:19][O:20][CH3:21])=[CH:16][CH:15]=1.N1C=CC=CC=1>ClCCl>[CH3:1][C:2]1([CH3:12])[O:6][C:5](=[CH:7][C:8]([N:19]([CH2:18][C:17]2[CH:22]=[CH:23][C:14]([F:13])=[CH:15][CH:16]=2)[O:20][CH3:21])=[O:9])[C:4](=[O:11])[O:3]1

Komponenten

5

Edukt 3

HCID 1049PyridineHCID 12147060Benzenemethanamine, 4-fluoro-N-methoxy-HCID 85435482(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-acetyl chloride

Produkt 1

HCID 730332332-(2,2-Dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-(4-fluoro-benzyl)-N-methoxy-acetamideAusbeute 93,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
22 °C

Versuchsvorschrift

A solution of (2,2-dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-acetyl chloride (2.45 g, 12.9 mmol) in dichloromethane (15 ml) was added dropwise over 10 minutes to a cold (0-5° C.) mixture of N-4-fluorobenzyl-O-methyl-hydroxylamine (2.0 g, 12.9 mmol) and pyridine (2.1 ml, 25.7 mmol) in dichloromethane (50 ml). The cooling bath was then removed and the solution was stirred at 22° C. for 30 minutes. The reaction mixture was then quenched by the addition of water and ethyl acetate. The organic phase was washed successively with 0.1 N hydrochloric acid, saturated sodium bicarbonate, brine and dried (magnesium sulfate). Evaporation of the solvent and chromatography of the residue on silica gel (toluene-ethyl acetate, 8:2) gave 3.72 g (93% yield) of the title amide as white crystals after recrystallization from ethyl acetate/hexanes. Differential scanning calorimetry shows a sharp endotherm at 107° C. 1HNMR 400 MHz (CDCl3) δ (ppm): 1.75 (6H, s), 3.68 (3H, s), 4.79 (2H, s), 6.38 (1H, s), 7.0 (2H, m), 7.34 (2H, m). 13CNMR 100 MHz (CDCl3) δ (ppm): 26.81, 48.43, 63.03, 94.48, 114.22, 115.31, 115.56, 130.47, 132.03, 146.95, 161.21, 162.46, 163.65, 164.43. 19FNMR 377 MHz(CDCl3) δ (ppm): 114.97. Anal. calcd for C15H16FNO5: C, 58.25; H, 5.21; N, 4.52; Found: C, 58.33; H, 5.38; N, 4.51.

Aufarbeitung

  1. customThe cooling bath was then removed
  2. customThe reaction mixture was then quenched by the addition of water and ethyl acetate
  3. washThe organic phase was washed successively with 0.1 N hydrochloric acid, saturated sodium bicarbonate, brine
  4. dry with materialdried (magnesium sulfate)
  5. customEvaporation of the solvent and chromatography of the residue on silica gel (toluene-ethyl acetate, 8:2)

Quellen und Nachweise

ORD-Eintrag
ord-24d39672dd2b413c828b24c1270d7ec4
Quelldatensatz
uspto-grants-2004_08
Patentnummer
US06777440B2

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