Ethyl cyanoacetate → HCID 53675399, compound

HRID 1934406Notes

Reaction equation

HRID 1934406 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].N12CCCN=C1CCCCC2.Br[CH2:21][C:22](=[O:25])[CH2:23][CH3:24]>C1C=CC=CC=1>[CH2:7]([O:6][C:4](=[O:5])[CH:3]([C:1]#[N:2])[CH2:21][C:22](=[O:25])[CH2:23][CH3:24])[CH3:8]

Participants

5

Reactant 3

HCID 7764Ethyl cyanoacetateHCID 131561-Bromo-2-butanoneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene

Product 1

HCID 53675399HCID 53675399, compoundYield 88.9%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

To a 5° C. solution containing 27.8 g (246 mmol) of ethyl cyanoacetate and 38.2 g (251 mmol) of 1,8-diazabicyclo[5.4.0]undec-7ene in 420 mL of benzene was added over 30 minutes a solution of 1-bromo-2-butanone in 70 mL of benzene. The ice bath was removed and the reaction stirred for 1 hour at ambient temperature. At this time, the solids were removed by filtration and washed with 100 mL of methyl tert-butyl ether. The filtrate and the wash were combined and concentrated. The crude product was purified by short path distillation (0.2 torr, 140° C.) to provide 40.0 g (88.9%) of 2-cyano-4-oxohexanoic acid ethyl ester as a colorless oil. nmr (500 MHz, CDCl3) δ1.09 (t, J=7.3 Hz, 3H), 1.31 (t, J=7.1 Hz, 3H), 2.50 (q, J=7.3 Hz, 2H), 2.96 (dd, J=5.5, 18.0 Hz, 1H), 3.16 (dd, J=7.2, 18.0 Hz, 1H), 3.96 (dd, J=5.5, 7.2 Hz, 1H), 4.25 (q, J=7.1 Hz, 2H).

Workup

  1. customThe ice bath was removed
  2. customAt this time, the solids were removed by filtration
  3. washwashed with 100 mL of methyl tert-butyl ether
  4. concentrationconcentrated
  5. distillationThe crude product was purified by short path distillation (0.2 torr, 140° C.)

Sources & evidence

ORD record
ord-676790cff40a41eb9fc74883745c8bec
Source dataset
uspto-grants-2002_05
Patent number
US06384041B1

Reaction notes

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