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

HRID 648795Notes

Reaction equation

HRID 648795 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.C(=O)([O-])[O-].[K+].[K+].CN(C)C=O.Br[CH2:30][CH2:31]Br>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])[CH2:31][CH2:30]2)=[O:16])=[C:4]([CH3:17])[CH:3]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 14150214Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate

Product 1

HCID 14150215Ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylateYield 87%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

Into a 250 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 prepared as in Example A, 5.73 grams (42.0 mmol) of anhydrous potassium carbonate, 20 milliliters of anhydrous dimethylformamide and 1.7 milliliters (20.0 mol) of 1,2-dibromoethane. The resulting mixture was stirred at ambient temperature under a nitrogen atmosphere and irradiated with ultra sound waves using a Bransonic 52 ultrasonic cleaning bath for a period of 4.25 hours. Ice was added to maintain the temperature of the bath between 26° C. and 31° C. After this period, high pressure liquid chromatographic analysis showed the reaction to be complete. The product was isolated by diluting with methylene chloride, filtering off the solids and concentrating under reduced pressure to give a yellow solid. Chromatography on silica gel with a 3:1 volume/volume hexane-ethyl acetate eluent provided 4.58 grams (14.0 mmol) of ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate as a pale yellow solid having a melting point of 87° C.-89° C. The total yield was 87 percent based on a 96.7 weight percent assay of the starting ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate. NMR analysis of the product indicated the following:

Workup

  1. customInto a 250 milliliter three-necked round-bottom reaction flask equipped with a mechanical stirrer
  2. additionthermometer and nitrogen inlet and outlet was added
  3. customirradiated with ultra sound waves
  4. customof 4.25 hours
  5. additionIce was added
  6. temperatureto maintain the temperature of the bath between 26° C. and 31° C
  7. waitAfter this period
  8. customthe reaction
  9. customThe product was isolated
  10. filtrationfiltering off the solids
  11. concentrationconcentrating under reduced pressure
  12. customto give a yellow solid

Sources & evidence

ORD record
ord-75ad6df0c4184526acaee96973ff59aa
Source dataset
uspto-grants-1988_04
Patent number
US04736056

Reaction notes

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