Diethyl Malonate → Diethyl 2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)malonate

HRID 2416011Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2416011
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Cl[C:15]1[C:20]([Cl:21])=[CH:19][C:18]([C:22]([F:25])([F:24])[F:23])=[CH:17][N:16]=1.[H][H]>CN(C)C=O.C(OCC)C.C(O)(=O)C>[Cl:21][C:20]1[C:15]([CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:3]([O:11][CH2:12][CH3:13])=[O:10])=[N:16][CH:17]=[C:18]([C:22]([F:24])([F:23])[F:25])[CH:19]=1

Komponenten

8

Edukt 4

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 1122342,3-Dichloro-5-(trifluoromethyl)pyridineHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 2774041Diethyl 2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)malonate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 3283Diethyl EtherLösungsmittel2×HCID 6228DimethylformamideLösungsmittel3×

Versuchsvorschrift

To a suspension of 60% sodium hydride in mineral oil (5.28 g) in dry dimethylformamide (50 ml) at 0° C. was added a solution of diethyl malonate (10 ml) in dry dimethylformamide (25 ml) and the mixture was stirred for 30 minutes. A solution of 2,3-dichloro-5-(trifluoromethyl)pyridine (9.8 ml) in dry dimethylformamide (10 ml) was added dropwise and the mixture warmed with stirring to 22° C. over 18 hours. Acetic acid (7.5 ml) in diethyl ether (20 ml) was added dropwise and the mixture was stirred until hydrogen evolution had ceased. The mixture was diluted with diethyl ether (600 ml) and then water washed (3×200 ml). The organic extract was dried (MgSO4) and evaporated onto flash silica. Chromatography over silica eluting with 0-20% diethyl ether in light petroleum (b.p. 40-60° C.) gave the title compound. 1H N.M.R. (CDCl3) δ(ppm) 1.28 (6H, t, 2×CH3CH2), 4.30 (4H, q, 2×CH2CH3), 5.24 (1H, s, CH(CO2Et)2), 7.96 (1H, s, py-H), 8.74 (1H, s, py-H).

Aufarbeitung

  1. temperaturethe mixture warmed
  2. stirringwith stirring to 22° C. over 18 hours
  3. washwater washed (3×200 ml)
  4. extractionThe organic extract
  5. dry with materialwas dried (MgSO4)
  6. customevaporated onto flash silica

Quellen und Nachweise

ORD-Eintrag
ord-bba6530dd2944fc8b08ebec9357b4535
Quelldatensatz
uspto-grants-2004_11
Patentnummer
US06821992B1

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