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

HRID 648798Notes

Reaction equation

HRID 648798 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]CC)=[O:12])=[C:4]([CH3:17])[CH:3]=1.C(=O)([O-])[O-].[K+].[K+].Br[CH2:25][CH2:26]Br.[OH-].[K+].Cl>O.CN(C)C=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]([C:10]2([C:11]([OH:13])=[O:12])[CH2:26][CH2:25]2)=[O:16])=[C:4]([CH3:17])[CH:3]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 14150214Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate

Product 1

HCID 190969071-(4-Bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylic acidYield 80%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Into a 250 milliliter Erlenmeyer flask equipped with a magnetic stirrer was added 15.0 grams (0.05 mol) of ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate prepared as in Example A, 16.56 grams (0.12 mol) of potassium carbonate, 150 milliliters of dimethylformamide and 5.16 milliliters (0.06 mol) of 1,2-dibromethane. The resulting mixture was stirred at ambient temperature for a period of 23 hours (liquid chromatographic analysis indicated 87 percent and 95 percent conversions after 2 and 6 hours respectively). Potassium hydroxide (4.0 grams, 0.07 mol) was then added in one gram increments until no ethyl 1-[(4-bromo-2-methylphenylaminocarbonyl)cyclopropanecarboxylate remained. The reaction mixture was diluted to 900 milliliters with water and acidified with concentrated HCl to a pH of 1-2 to afford a yellow percipitate. The yellow precipitate was dried for a period of about 18 hours in an unheated vacuum oven to give 11.88 gram (0.04 mol) of 1-(4-bromo-2-methylpheylaminocarbonyl)cyclopropanecarboxylic acid. The total yield was 80 percent based on a 96.7 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
  2. additionwas added
  3. customafter 2 and 6 hours
  4. customto afford a yellow percipitate
  5. customThe yellow precipitate was dried for a period of about 18 hours in an unheated vacuum oven

Sources & evidence

ORD record
ord-7c4181c65bad4d2088d0d2c2f0771123
Source dataset
uspto-grants-1988_04
Patent number
US04736056

Reaction notes

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