Oxalyl chloride → 4-Chloro-3-ethoxy-5-nitro-benzoic acid methyl ester

HRID 1990861Notes

Reaction equation

HRID 1990861 reaction equation
[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7](O)=[C:6]([O:14][CH2:15][CH3:16])[CH:5]=1.C(Cl)(=O)C([Cl:21])=O>CN(C=O)C>[CH3:1][O:2][C:3](=[O:17])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([Cl:21])=[C:6]([O:14][CH2:15][CH3:16])[CH:5]=1

Participants

4

Reactant 2

HCID 65578Oxalyl chlorideHCID 686988033-Ethoxy-4-hydroxy-5-nitro-benzoic acid methyl ester

Product 1

HCID 686994194-Chloro-3-ethoxy-5-nitro-benzoic acid methyl esterYield 91.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 3-ethoxy-4-hydroxy-5-nitro-benzoic acid methyl ester (2.0 g, 8.29 mmol, 1.0 equiv) in anhydrous DMF (100 mL) at −25° C. under Ar was added slowly oxalyl chloride (1.40 mL, 2.11 g, 16.58 mmol, 2.0 equiv) over a period of 30 min. After the addition was completed the reaction mixture was heated to 80° C. for 3 h. The reaction mixture was poured on ice, the yellow precipitate washed with cold dichloromethane (3×20 mL), filtered and dried providing 1.97 g (86%) of the title compound. 1H NMR (300 MHz, CDCl3): δ 1.53 (t, J=7.0 Hz, 3H), 3.96 (s, 3H), 4.24 (q, J=7.0 Hz, 2H), 7.74 (d, J=1.8 Hz, 1H), 8.00 (d, J=1.8 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ 14.47, 52.91, 66.17, 115.93, 117.25, 120.95, 129.82, 149.61, 156.03, 164.56. MS (ISP): 276.9 [M+NH4]+.

Workup

  1. additionAfter the addition
  2. additionThe reaction mixture was poured on ice
  3. washthe yellow precipitate washed with cold dichloromethane (3×20 mL)
  4. filtrationfiltered
  5. customdried

Sources & evidence

ORD record
ord-f9f0c9ef723f452b9e6ea9e11096dbdd
Source dataset
uspto-grants-2010_01
Patent number
US07645753B2

Reaction notes

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