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

HRID 485092

Reaction equation

HRID 485092 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-dfb7b561bd274ae5841239121b74ec44
Source dataset
uspto-grants-1985_08
Patent number
US04535163

Linked notes

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