Methyl cyanoacetate → Methyl 1-cyanocyclopentane-1-carboxylate

HRID 617619Notes

Reaction equation

HRID 617619 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH3:7])=[O:5])#[N:2].C([O-])([O-])=O.[K+].[K+].Br[CH2:15][CH2:16][CH2:17][CH2:18]Br>CN(C=O)C>[C:1]([C:3]1([C:4]([O:6][CH3:7])=[O:5])[CH2:18][CH2:17][CH2:16][CH2:15]1)#[N:2]

Participants

5

Reactant 3

HCID 7747Methyl cyanoacetateHCID 80561,4-DibromobutaneHCID 11430Potassium Carbonate

Product 1

HCID 22736532Methyl 1-cyanocyclopentane-1-carboxylateYield 77,094.203%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
75 °C

Procedure

To a 22 L flask equipped with a mechanical stirrer, thermometer and condenser containing a nitrogen inlet was added dry DMF (8 L) and methyl cyanoacetate (800 g, 8.07 mol). Stirring was started and K2CO3 (2.67 kg, 19.3 mol) and then 1,4-dibromobutane (1.74 kg, 8.07 mmol) were added. The exothermic reaction mixture (temperature increased to 75° C.) was stirred at room temperature for 16 h followed by heating at 60-75° C. for 3 h. Approximately 2.5 L of solvent were removed under reduced pressure and the residue was diluted with water (8 L). The resultant mixture was extracted with Et2O (2×2 L) and the combined organic phases were washed with 1 N aqueous HCl and brine. Drying (MgSO4), filtering and concentrating afforded an orange liquid. This material was distilled (fraction boiling at 80° C., 0.7 mm Hg collected) to provide methyl 1-cyanocyclopentanecarboxylate as a clear colorless liquid (953 g, 77% yield). 1H-NMR (400 MHz, CDCl3) δ 3.80 (s, 3 H), 2.29-2.22 (m, 4 H), 1.90-1.84 (m, 4 H); 13C NMR (100.6 MHz, CDCl3) δ 169.2, 119.9, 52.6, 46.6, 36.9, 24.3; EI-MS exact mass calcd for C8H11NO2 : 153.0790; found: 153.0785.

Workup

  1. customTo a 22 L flask equipped with a mechanical stirrer
  2. additionthermometer and condenser containing a nitrogen inlet
  3. stirringwas stirred at room temperature for 16 h
  4. temperatureby heating at 60-75° C. for 3 h
  5. customApproximately 2.5 L of solvent were removed under reduced pressure
  6. additionthe residue was diluted with water (8 L)
  7. extractionThe resultant mixture was extracted with Et2O (2×2 L)
  8. washthe combined organic phases were washed with 1 N aqueous HCl and brine
  9. dry with materialDrying (MgSO4)
  10. filtrationfiltering
  11. concentrationconcentrating
  12. customafforded an orange liquid
  13. distillationThis material was distilled
  14. custom(fraction boiling at 80° C., 0.7 mm Hg collected)

Sources & evidence

ORD record
ord-2ca0aae1883a43e1a357678589ec99fa
Source dataset
uspto-grants-1999_09
Patent number
US05948935

Reaction notes

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