Ethyl 2-methylacetoacetate → 2-(3-Amino-2-cyano-4-nitrophenyl)-2-methyl-3-oxobutyric acid ethyl ester

HRID 1634226Notes

Reaction equation

HRID 1634226 reaction equation
[NH2:1][C:2]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6](Cl)[C:3]=1[C:4]#[N:5].[CH3:14][CH:15]([C:21]([CH3:23])=[O:22])[C:16]([O:18][CH2:19][CH3:20])=[O:17].C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.CCOC(C)=O>[CH2:19]([O:18][C:16](=[O:17])[C:15]([C:6]1[CH:7]=[CH:8][C:9]([N+:10]([O-:12])=[O:11])=[C:2]([NH2:1])[C:3]=1[C:4]#[N:5])([CH3:14])[C:21](=[O:22])[CH3:23])[CH3:20]

Participants

6

Reactant 3

HCID 701Ethyl 2-methylacetoacetateHCID 11430Potassium CarbonateHCID 112756272-Amino-6-chloro-3-nitro-benzonitrile

Product 1

HCID 112667142-(3-Amino-2-cyano-4-nitrophenyl)-2-methyl-3-oxobutyric acid ethyl esterYield 46%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-amino-6-chloro-3-nitrobenzonitrile (1.97 g, 10 mmol) and ethyl 2-methylacetoacetate (3.6 g, 25 mmol) in DMF (10 mL) was added finely powdered K2CO3, and the mixture stirred vigorously for 24 h. The deep red mixture was diluted with EtOAc and washed in turn with 2M HCl, water and brine. The residue after evaporation was purified by flash chromatography in hexane/EtOAc 3:1 to yield 2-(3-amino-2-cyano-4-nitrophenyl)-2-methyl-3-oxobutyric acid ethyl ester as an oil (1.39 g, 46%), MS (NH3 CI) 323 (M+NH4+), 293 (M+NH4—NO+).

Workup

  1. washwashed in turn with 2M HCl, water and brine
  2. customThe residue after evaporation
  3. customwas purified by flash chromatography in hexane/EtOAc 3:1

Sources & evidence

ORD record
ord-7c40e6e70fae4faeab55fe122ac0ba9f
Source dataset
uspto-grants-2003_01
Patent number
US06506769B2

Reaction notes

Loading…