Pyridine → Methyl 2,6-dichloro-4-cyanobenzoate

HRID 449898Notes

Reaction equation

HRID 449898 reaction equation
[C:1]([C:4]1[CH:13]=[C:12]([Cl:14])[C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:6]([Cl:15])[CH:5]=1)(=O)[NH2:2].FC(F)(F)C(OC(=O)C(F)(F)F)=O.N1C=CC=CC=1>O>[Cl:14][C:12]1[CH:13]=[C:4]([C:1]#[N:2])[CH:5]=[C:6]([Cl:15])[C:7]=1[C:8]([O:10][CH3:11])=[O:9]

Participants

5

Reactant 3

HCID 1049PyridineHCID 9845Trifluoroacetic anhydrideHCID 67128947Methyl 4-carbamoyl-2,6-dichlorobenzoate

Product 1

HCID 53401291Methyl 2,6-dichloro-4-cyanobenzoateYield 61%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of methyl 4-carbamoyl-2,6-dichlorobenzoate (57 g, 230 mmol), trifluoroacetic anhydride (46 mL) and pyridine (46 mL) in dixoane (400 mL) was stirred at room temperature for 24 hours, 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 (10:1) to give methyl 2,6-dichloro-4-cyanobenzoate (32 g, yield: 61%) as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 3.91 (s, 3H), 7.95 (s, 2H). LCMS (ESI) m/z: 230.1 [M+H+].

Workup

  1. extractionextracted with ethyl acetate (3×300 mL)
  2. washThe combined organic extracts were washed with brine (200 mL)
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by column chromatography on silica gel
  6. washeluting with petroleum-diethyl ether (10:1)

Sources & evidence

ORD record
ord-6651b8a940414f759b78b5a34ef24aea
Source dataset
uspto-grants-2013_07
Patent number
US08486950B2

Reaction notes

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