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

HRID 1153734Notes

Reaction equation

HRID 1153734 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]([CH3:25])=[CH:23][C:22]([N+:26]([O-:28])=[O:27])=[CH:21][N:20]=1>O1CCCC1>[CH3:25][C:24]1[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]=[C:22]([N+:26]([O-:28])=[O:27])[CH:23]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 87005Diethyl (2-cyanoethyl)malonateHCID 896482-Chloro-3-methyl-5-nitropyridine

Product 1

HCID 130942664-(3-Methyl-5-nitropyrid-2-yl)-4,4-bis(carbethoxy)-butyronitrileYield 48.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

2-(2-Cyanoethyl)malonic acid diethyl ester (148.3 g) was reacted with sodium hydride (15.3 g) in tetrahydrofuran at 20° C. 2-Chloro-3-methyl-5-nitropyridine (100 g) was added and the internal temperature was raised to 100° C. (some tetrahydrofuran was distilled off) over 14 hrs. The reaction mixture was partitioned between water and chloroform, the chloroform extract was dried, treated with charcoal and filtered through a silica bed and then evaporated to dryness. Crystallisation of the residue from ethanol gave 4-(3-methyl-5-nitropyrid-2-yl)-4,4-bis(carbethoxy)-butyronitrile (99 g) m.p. 64°-65.5° C.

Workup

  1. distillationwas distilled off) over 14 hrs
  2. customThe reaction mixture was partitioned between water and chloroform
  3. extractionthe chloroform extract
  4. customwas dried
  5. additiontreated with charcoal
  6. filtrationfiltered through a silica bed
  7. customevaporated to dryness
  8. customCrystallisation of the residue from ethanol

Sources & evidence

ORD record
ord-050f45e4431940acaab8eed4cf7ec5bd
Source dataset
uspto-grants-1984_12
Patent number
US04486434

Reaction notes

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