Hydrochloric Acid → 1-(4-Bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylic acid

HRID 648797Notes

Reaction equation

HRID 648797 reaction equation
BrC1C=CC(NC(=O)CC(OCC)=O)=C(C)C=1.BrCCCl.C(=O)([O-])[O-].[K+].[K+].[OH-].[K+].[Br:30][C:31]1[CH:36]=[CH:35][C:34]([NH:37][C:38]([C:40]2([C:43]([O:45]CC)=[O:44])[CH2:42][CH2:41]2)=[O:39])=[C:33]([CH3:48])[CH:32]=1.Cl>O.CN(C)C=O>[Br:30][C:31]1[CH:36]=[CH:35][C:34]([NH:37][C:38]([C:40]2([C:43]([OH:45])=[O:44])[CH2:41][CH2:42]2)=[O:39])=[C:33]([CH3:48])[CH:32]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 78491-Bromo-2-ChloroethaneHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 14150214Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate2×HCID 14150215Ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate

Product 1

HCID 190969071-(4-Bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylic acidYield 91.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Into a 250 milliliter Erlenmeyer flask equipped with a magnetic stirrer and condenser was added 15.0 grams (0.05 mol) of ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate, 150 milliliters of dimethylformamide and 14.0 grams (0.10 mol) of 1-bromo-2-chloroethane. The resulting mixture was stirred at ambient temperature and potassium carbonate (4.0 grams, 0.03 mol) was added at a rate of 1 gram every 30 minutes. After liquid chromatographic analysis showed the ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate peak disappeared, potassium hydroxide (5.0 grams, 0.09 mol) was added until no ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate remained. The reaction mixture was diluted to 300 milliliters with water and acidified with concentrated HCl to a pH of 1 to afford a solid material. The solid was collected on a Buchner funnel and dried under ambient temperature to give 13.65 grams (0.046 mol) of 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylic acid. The total yield was 91.5 percent based on a 97.6 weight percent liquid chromatographic assay of the starting ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate.

Workup

  1. customInto a 250 milliliter Erlenmeyer flask equipped with a magnetic stirrer and condenser
  2. customto afford a solid material
  3. customThe solid was collected on a Buchner funnel
  4. customdried under ambient temperature

Sources & evidence

ORD record
ord-f55ace27a8304f76b886b357a11b2dbb
Source dataset
uspto-grants-1988_04
Patent number
US04736056

Reaction notes

Loading…