Sodium hydride → 3-(3-Methyl-5-nitropyrid-2-yl)-3,3-bis(carbethoxy)propionitrile

HRID 34925

Reaktionsgleichung

Reaktionsgleichung von HRID 34925
[CH2:1]([O:3][C:4](=[O:14])[CH:5]([CH2:11][C:12]#[N:13])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:2].[H-].[Na+].Cl[C:18]1[C:23]([CH3:24])=[CH:22][C:21]([N+:25]([O-:27])=[O:26])=[CH:20][N:19]=1>O1CCCC1>[CH3:24][C:23]1[C:18]([C:5]([C:4]([O:3][CH2:1][CH3:2])=[O:14])([C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH2:11][C:12]#[N:13])=[N:19][CH:20]=[C:21]([N+:25]([O-:27])=[O:26])[CH:22]=1

Komponenten

5

Edukt 3

HCID 24758Sodium hydrideHCID 896482-Chloro-3-methyl-5-nitropyridineHCID 272015Diethyl 2-(cyanomethyl)malonate

Produkt 1

HCID 198517963-(3-Methyl-5-nitropyrid-2-yl)-3,3-bis(carbethoxy)propionitrile

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

2-(Cyanomethyl)malonic acid diethyl ester (G. Casini et al, Ann. Chim. (Rome), 51, 366-74 (1961) (81 g) was reacted with sodium hydride (8.9 g) in tetrahydrofuran at 20° C. 2-Chloro-3-methyl-5-nitropyridine (G. E. Hawkins & A. Roe, J. Org. Chem., 14, 328 (1949)) (58.5 g) was added and the internal temperature was raised to 95°-105° C. (some tetrahydrofuran was distilled off) over 11 hours. The reaction mixture was partitioned between chloroform and water (pH of aqueous phase was lowered to 3), the chloroform extracts were dried and concentrated in vacuo to give an oil (132 g). The oil was distilled under vacuum, the distillate collected at 60°-98° C. (vapour temp.) 0.2 mm Hg was discarded. The residues from the distillation (65 g) were dissolved in chloroform and filtered through a silica column and then concentrated, treated with charcoal and recrystallised from chloroform/petroleum ether (40°-60° C.) to give the title compound (30 g) m.p. 78°-80° C.

Aufarbeitung

  1. distillationwas distilled off) over 11 hours
  2. customThe reaction mixture was partitioned between chloroform and water (pH of aqueous phase was lowered to 3)
  3. dry with materialthe chloroform extracts were dried
  4. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-5721427290914659a2665af3183f24d5
Quelldatensatz
uspto-grants-1988_08
Patentnummer
US04764519

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