Water → Methyl 5-bromo-2-isopropoxycarbonylaminobenzoate

HRID 507018Notes

Reaction equation

HRID 507018 reaction equation
Cl[C:2]([O:4][CH:5]([CH3:7])[CH3:6])=[O:3].[NH2:8][C:9]1[CH:18]=[CH:17][C:16]([Br:19])=[CH:15][C:10]=1[C:11]([O:13][CH3:14])=[O:12].N1C=CC=CC=1.O>ClCCl>[Br:19][C:16]1[CH:17]=[CH:18][C:9]([NH:8][C:2]([O:4][CH:5]([CH3:7])[CH3:6])=[O:3])=[C:10]([CH:15]=1)[C:11]([O:13][CH3:14])=[O:12]

Participants

6

Reactant 4

HCID 962WaterHCID 1049PyridineHCID 7917Isopropyl chloroformateHCID 736224Methyl 2-amino-5-bromobenzoate

Product 1

HCID 59432449Methyl 5-bromo-2-isopropoxycarbonylaminobenzoateYield 86%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Add isopropyl chloroformate (36.9 mL, 36.9 mmol, 1.0 M in toluene) dropwise to a solution of methyl 2-amino-5-bromobenzoate (5.0 g, 24.6 mmol) and pyridine (80.0 mL, 36.9 mmol) in dichloromethane (80 mL) at room temperature under an atmosphere of nitrogen and stir for 1.5 h. Pour the reaction into water (100 mL) and separate the layers. Extract the aqueous layer with dichloromethane (2×40 mL) and combine the organic extracts and wash with 2 N hydrochloric acid, saturated sodium hydrogen carbonate, and brine (80 mL each). Dry the organic layer over anhydrous sodium sulfate, filter, and remove the solvent under reduced pressure to afford the title compound as a pale yellow solid (6.68 g, 86%). 1H NMR (CDCl3) δ 1.31 (d, J=6.3 Hz, 6H), 3.92 (s, 3H), 5.03 (septet, J=6.3 Hz, 1H), 7.61 (dd, J=1.9, 8.5 Hz, 1H), 8.11 (d, J=1.9 Hz, 1H), 8.40 (d, J=8.5 Hz, 1H), 10.31 (br s, 1H). ESI MS m/z 316 [C12H14BrNO4+H]+.

Workup

  1. additionPour
  2. customseparate the layers
  3. extractionExtract the aqueous layer with dichloromethane (2×40 mL)
  4. washwash with 2 N hydrochloric acid, saturated sodium hydrogen carbonate, and brine (80 mL each)
  5. dry with materialDry the organic layer over anhydrous sodium sulfate
  6. filtrationfilter
  7. customremove the solvent under reduced pressure

Sources & evidence

ORD record
ord-ae6f0e51730d42e8855f6af38a257533
Source dataset
uspto-grants-2010_08
Patent number
US07786108B2

Reaction notes

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