Sodium hydride → 4-(5-Methyl-3-nitropyrid-2-yl)-4,4-bis(carbethoxy)butyronitrile

HRID 326080

Reaction equation

HRID 326080 reaction equation
[CH2:1]([O:3][C:4](=[O:15])[CH:5]([CH2:11][CH2:12][C:13]#[N:14])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:2].[H-].[Na+].Cl[C:19]1[C:24]([N+:25]([O-:27])=[O:26])=[CH:23][C:22]([CH3:28])=[CH:21][N:20]=1>O1CCCC1>[CH3:28][C:22]1[CH:23]=[C:24]([N+:25]([O-:27])=[O:26])[C:19]([C:5]([C:4]([O:3][CH2:1][CH3:2])=[O:15])([C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH2:11][CH2:12][C:13]#[N:14])=[N:20][CH:21]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 87005Diethyl (2-cyanoethyl)malonateHCID 8183002-Chloro-5-methyl-3-nitropyridine

Product 1

HCID 202714614-(5-Methyl-3-nitropyrid-2-yl)-4,4-bis(carbethoxy)butyronitrileYield 37.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

2-(2-Cyanoethyl)malonic acid diethylester (40 g) was reacted with sodium hydride (4.4 gm) in tetrahydrofuran at 20° C. 2-Chloro-5-methyl-3-nitro-pyridine (35 g) was added and the internal temperature was raised to 100° C. (some tetrahydrofuran distilled off) over 4.25 hrs. The reaction mixture was partitioned between chloroform and water and treated with charcoal. Vacuum distillation of the chloroform extract and then chromatography (CHCl3, silica column) of the distillation residues gave 4-(5-methyl-3-nitropyrid-2-yl)-4,4-bis (carbethoxy)-butyronitrile (24.5 g) as a yellow solid m.p. 48°-49° C.

Workup

  1. distillationdistilled off) over 4.25 hrs
  2. customThe reaction mixture was partitioned between chloroform and water
  3. additiontreated with charcoal
  4. distillationVacuum distillation of the chloroform
  5. extractionextract

Sources & evidence

ORD record
ord-882e8c6f2e234edd870a34a332a8835a
Source dataset
uspto-grants-1984_04
Patent number
US04444772

Linked notes

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