Ethyl bromoacetate → HCID 19874452, compound

HRID 728907Notes

Reaction equation

HRID 728907 reaction equation
[H-].[Na+].[OH:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10]1[CH:11]=[C:12]([C:18]#[N:19])[C:13](=[O:17])[NH:14][C:15]=1[CH3:16].Br[CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23].CCOC(C)=O>CN(C=O)C>[C:22]([CH2:21][O:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10]1[CH:11]=[C:12]([C:18]#[N:19])[C:13](=[O:17])[NH:14][C:15]=1[CH3:16])([O:24][CH2:25][CH3:26])=[O:23]

Participants

6

Reactant 4

HCID 7748Ethyl bromoacetateHCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 19874464HCID 19874464, compound

Product 1

HCID 19874452HCID 19874452, compoundYield 35.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

A dispersion of 530 mg of 60% sodium hydride in mineral oil and 10 ml of DMF is treated, dropwise, with a solution of 1.50 g (6.6 mmol) of 5-(2-hydroxyphenyl)-6-methyl-2-oxo-1,2-dihydro-3-pyridinecarbonitrile in 20 ml of DMF. The reaction is stirred 30 min at RT, then cooled in an ice bath and 1.11 g (6.6 mmol) of ethyl bromoacetate in 30 ml of DMF is added dropwise. The reaction is allowed to slowly come to RT and stirred overnight under N2. The mixture is concentrated under vacuum, the residue taken up in 80 ml of water and extracted with EtOAc. The aqueous phase is acidified to pH=5 with 10% HCl and extracted with EtOAc (4×80 ml). The combined EtOAc extracts are dried (MgSO4) and the solvent removed to leave an orange solid. This solid is recrystallizedfrom EtOAc to give 740 mg of 5-(2-carboethoxymethoxyphenyl)-6-methyl-2-oxo-1,2 -dihydro-3-pyridinecarbonitrile as a yellow solid, m.p. 188°-190° C. Yield, 37%. 1H-NMR (d6 -DMSO): δ 1.20 (t,3H): 2.18 (s,3H); 4.15 (q,2H); 4.80 (s,2H); 7.0 (q,2H); 7.20 (d,1H); 7.35 (t,1H); 8.00 (s,1H).

Workup

  1. temperaturecooled in an ice bath
  2. customto slowly come to RT
  3. stirringstirred overnight under N2
  4. concentrationThe mixture is concentrated under vacuum
  5. extractionextracted with EtOAc
  6. extractionextracted with EtOAc (4×80 ml)
  7. dry with materialThe combined EtOAc extracts are dried (MgSO4)
  8. customthe solvent removed
  9. customto leave an orange solid

Sources & evidence

ORD record
ord-359e3067ae5d43da9e049020b366e9db
Source dataset
uspto-grants-1991_09
Patent number
US05051431

Reaction notes

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