Dimethylformamide → Ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate

HRID 648802Notes

Reaction equation

HRID 648802 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:16])[CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:4]([CH3:17])[CH:3]=1.Cl[CH2:19][CH2:20]OS(C1C=CC(C)=CC=1)(=O)=O.C(=O)([O-])[O-].[K+].[K+].CN(C)C=O>C(Cl)Cl.CCCCCC.C(OCC)(=O)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]([C:10]2([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:20][CH2:19]2)=[O:16])=[C:4]([CH3:17])[CH:3]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 6639Ethanol, 2-chloro-, 1-(4-methylbenzenesulfonate)HCID 11430Potassium CarbonateHCID 14150214Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate

Product 1

HCID 14150215Ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylateYield 35%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

Into a 50 milliliter three-necked round-bottom reaction flask equipped with a mechanical stirrer, thermometer and nitrogen inlet and outlet was added 5.0 grams (17.0 mmol) of ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate, 3.91 grams (16.7 mmol) of 2-chloroethyl-paratoluenesulfonate, 5.74 grams (41.6 mmol) of anhydrous potassium carbonate and 17 milliliters of anhydrous dimethylformamide. The resulting mixture was stirred at ambient temperature under a nitrogen atmosphere for a period of 4 days. The product was then isolated by diluting with methylene chloride, filtering off the solids and concentrating under reduced pressure to give a solid material. Chromatography on silica gel with a 3:1 volume/volume hexane-ethyl acetate eluent provided 1.89 grams (5.8 mmol) of ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate as a white solid having a melting point of 87.5° C.-89.0° C. The total yield was 35 percent based on a 96.7 weight percent assay of the staring ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate. NMR analysis of the product indicated the following:

Workup

  1. customInto a 50 milliliter three-necked round-bottom reaction flask equipped with a mechanical stirrer
  2. customThe product was then isolated
  3. filtrationfiltering off the solids
  4. concentrationconcentrating under reduced pressure
  5. customto give a solid material

Sources & evidence

ORD record
ord-99b48d6e410549bd97c092fda57d0bf9
Source dataset
uspto-grants-1988_04
Patent number
US04736056

Reaction notes

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