Methyl chloroformate → Methyl 5-chloro-2-nitrobenzoate

HRID 1032972Notes

Reaction equation

HRID 1032972 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N+:11]([O-:13])=[O:12])=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8].[CH3:14]CN(CC)CC.ClC(OC)=O>C(Cl)Cl.CCOC(C)=O.CCCCCC>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N+:11]([O-:13])=[O:12])=[C:6]([CH:10]=1)[C:7]([O:9][CH3:14])=[O:8]

Participants

6

Reactant 3

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 172865-Chloro-2-nitrobenzoic acid

Product 1

HCID 171018Methyl 5-chloro-2-nitrobenzoate

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To a solution of 10 g (49.6 mmol) of 5-chloro-2-nitrobenzoic acid and 9 mL (64.5 mmol) Et3N in 300 ml CH2Cl2 at 0° C. was added 4.6 mL (59.5 mmol) methyl chloroformate. The cold bath was removed and after 10 minutes, 0.200 mL methanol was added. Bubbles of CO2 could be seen rising from the solution. After 2 hours, the mixture was diluted with Et2O, was washed with 5% HCl, was washed with saturated NaHCO3 solution, was washed with brine, was dried over MgSO4 and decolorized with charcoal, then was stripped of solvent in vacuo to give the product. Rf 0.35 in 15% EtOAc/hexane, visualized by UV; 1H-NMR (400 MHz, CDCl3): δ7.92 (d, J=8.6 Hz, 1H), 7.69 (d, J=2.3 Hz, 1H), 7.59 (dd, J1 =2.2 Hz, J2 =8.8 Hz, 1H), 3.94 (s, 3H).

Workup

  1. customThe cold bath was removed and after 10 minutes
  2. addition0.200 mL methanol was added
  3. additionthe mixture was diluted with Et2O
  4. washwas washed with 5% HCl
  5. washwas washed with saturated NaHCO3 solution
  6. washwas washed with brine
  7. dry with materialwas dried over MgSO4
  8. customto give the product

Sources & evidence

ORD record
ord-a2af978b5ac344bc8e3b56f6dceaeb44
Source dataset
uspto-grants-1994_05
Patent number
US05308846

Reaction notes

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