Triethylamine → Methyl 4-carbamoyl-2,6-dichlorobenzoate

HRID 449897Notes

Reaction equation

HRID 449897 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([Cl:15])[C:10]=1[C:11]([O:13][CH3:14])=[O:12])[C:5](O)=[O:6].C([N:18](CC)CC)C.ClC(OCC)=O>C1COCC1.O>[C:5]([C:4]1[CH:3]=[C:2]([Cl:1])[C:10]([C:11]([O:13][CH3:14])=[O:12])=[C:9]([Cl:15])[CH:8]=1)(=[O:6])[NH2:18]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 186730161-Methyl 2,6-dichloro-1,4-benzenedicarboxylate

Product 1

HCID 67128947Methyl 4-carbamoyl-2,6-dichlorobenzoateYield 80%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3,5-dichloro-4-(methoxycarbonyl)benzoic acid (72 g, 289 mmol) and triethylamine (40 mL) in THF (240 mL) at room temperature was added ethyl chloroformate (40 mL). The reaction mixture was stirred for 20 min at room temperature and filtered. To the filtrate was added (NH4)2CO3 (28 g, 292 mmol) and the mixture was stirred at room temperature for 18 hours. The mixture was diluted with water (300 mL) and extracted with ethyl acetate (3×300 mL). The combined organic extracts were washed with brine (200 mL), dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel, eluting with petroleum-diethyl ether (5:1) to give methyl 4-carbamoyl-2,6-dichlorobenzoate (57 g, yield: 80%) as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 3.90 (s, 3H), 7.76 (s, 1H), 7.99 (s, 2H), 8.28 (s, 1H). LCMS (ESI) m/z: 248.0 [M+H+].

Workup

  1. filtrationfiltered
  2. stirringthe mixture was stirred at room temperature for 18 hours
  3. extractionextracted with ethyl acetate (3×300 mL)
  4. washThe combined organic extracts were washed with brine (200 mL)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography on silica gel
  8. washeluting with petroleum-diethyl ether (5:1)

Sources & evidence

ORD record
ord-65a1863cc1e74e6fbac65ae48b08a6a1
Source dataset
uspto-grants-2013_07
Patent number
US08486950B2

Reaction notes

Loading…