Potassium Carbonate → Benzoic acid, 5-amino-2-chloro-4-methyl-, methyl ester

HRID 2065736Notes

Reaction equation

HRID 2065736 reaction equation
[CH3:1][O:2][C:3](=[O:13])[C:4]1[C:9](Br)=[C:8]([NH2:11])[CH:7]=[CH:6][C:5]=1[Cl:12].[C:14](=O)([O-])[O-].[K+].[K+].CB1OB(C)OB(C)O1>O1CCOCC1.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[C:8]([NH2:11])[C:7]([CH3:14])=[CH:6][C:5]=1[Cl:12]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 574072TrimethylboroxineHCID 68606931HCID 68606931, compound

Product 1

HCID 57423009Benzoic acid, 5-amino-2-chloro-4-methyl-, methyl esterYield 71.6%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

To a solution of 5-amino-6-bromo-2-chloro-benzoic acid methyl ester (0.5 g, 1.89 mmol) in dioxane (10 ml) and water (1 ml) was added potassium carbonate (0.784 g, 5.67 mmol), PdCl2(dppf) (0.54 g, 0.189 mmol) and trimethyl boroxine (0.276 ml, 1.985 mmol). The mixture was stirred at 110° C. for 18 hours, then cooled to room temperature and filtered. The filtrate was concentrated to dryness under reduced pressure. Purification of the residue by flash chromatography (hexanes:EtOAc 8:2) gave 0.270 g (71%) of 5-amino-2-chloro-4-methyl-benzoic acid methyl ester as a tan solid.

Workup

  1. temperaturecooled to room temperature
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated to dryness under reduced pressure
  4. customPurification of the residue by flash chromatography (hexanes:EtOAc 8:2)

Sources & evidence

ORD record
ord-d6d07fa856a2452187d218b821a7811b
Source dataset
uspto-grants-2012_10
Patent number
US08288552B2

Reaction notes

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