Ethyl Acetate → HCID 11463589, compound

HRID 1062421Notes

Reaction equation

HRID 1062421 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9](=[NH:18])[NH:10][C:11]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=1.Br[CH2:20][C:21](=O)[C:22]([O:24][CH2:25][CH3:26])=[O:23].C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>C1(C)C=CC=CC=1.CCCCCC>[Cl:17][C:14]1[CH:15]=[CH:16][C:11]([N:10]2[CH:20]=[C:21]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[N:18]=[C:9]2[C:3]2[CH:4]=[CH:5][C:6]([Cl:8])=[CH:7][C:2]=2[Cl:1])=[CH:12][CH:13]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 66144Ethyl bromopyruvateHCID 178512018HCID 178512018, compound

Product 1

HCID 11463589HCID 11463589, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8058HexaneSolvent

Procedure

To a solution of crude 2,4-dichloro-N-(4-chlorophenyl)benzenecarboximidamide (10.3 g, 34.6 mmol) in toluene (100 mL), ethyl bromopyruvate (4.3 mL, 34.6 mmol) and Na2CO3 (7.3 g, 41.6 mmol) were added. The resulting solution was heated at reflux for 3 h. The reaction mixture was cooled to rt. The solid was filtered off and the solvent was evaporated. The residue was purified by flash chromatography over silica gel (40% ethyl acetate in hexane) to give the product (7.5 g, 52% overall yield from 4-chroloaniline) as a light yellow solid: LC-MS m/z 395 (MH+), retention time 3.91 min (method 1); mp 143-144° C.; Rf=0.63 (50% EtOAc in hexane). 1H NMR (300 MHz, CDCl3) δ 1.39-1.43 (3H, t, J=7.2 Hz), 4.39-4.46 (2H, q, J=6.9 Hz), 7.04-7.08 (2H, m), 7.25-7.50 (5H, m), 7.89 (1H, s).

Workup

  1. temperatureThe resulting solution was heated
  2. temperatureat reflux for 3 h
  3. filtrationThe solid was filtered off
  4. customthe solvent was evaporated
  5. customThe residue was purified by flash chromatography over silica gel (40% ethyl acetate in hexane)
  6. customto give
  7. customthe product (7.5 g, 52% overall yield from 4-chroloaniline) as a light yellow solid

Sources & evidence

ORD record
ord-6d7d131a6d184ab08cecda7b23a2ced8
Source dataset
uspto-grants-2005_11
Patent number
US06960601B2

Reaction notes

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