Methanol → Methyl 2-methyl-5-nitrobenzoate

HRID 2379368Notes

Reaction equation

HRID 2379368 reaction equation
S(Cl)(Cl)=O.[CH3:5][C:6]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:7]=1[C:8]([OH:10])=[O:9].[CH3:18]O>>[CH3:5][C:6]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:7]=1[C:8]([O:10][CH3:18])=[O:9]

Participants

4

Reactant 3

HCID 887Methanol2×HCID 24386Thionyl ChlorideHCID 5196832-Methyl-5-nitrobenzoic acid

Product 1

HCID 4377758Methyl 2-methyl-5-nitrobenzoateYield 98%

Conditions

Temperature
0 °C

Procedure

To methanol (150 ml) at 0° C. under nitrogen was added dropwise thionyl chloride (4.0 ml, 54.8 mmol) over 2 min. The mixture was stirred at 0° C. for 15 min, before adding a solution of 2-methyl-5-nitrobenzoic acid (4.99 g, 27.5 mmol) in methanol (50 ml) by cannula over 5 min. The mixture was then allowed to warm to room temperature before heating at 50° C. for 18 h under nitrogen. The solvents were evaporated in vacuo and the residue stirred with water (100 ml) and dichloromethane (100 ml). The aqueous layer was basified with potassium carbonate, separated and reextracted with more dichloromethane (100 ml). The two organic extracts were combined, dried (MgSO4), and evaporated in vacuo to leave the title compound (5.24 g, 98%) as a white solid. 1H NMR (360 MHz, CDCl3) δ 2.72 (3H, s), 3.96 (3H, s), 7.44 (1H, d, J=8.3 Hz), 8.24 (1H, dd, J=8.4 and 2.6 Hz), 8.78 (1H, d, J=2.6 Hz).

Workup

  1. temperatureto warm to room temperature
  2. temperaturebefore heating at 50° C. for 18 h under nitrogen
  3. customThe solvents were evaporated in vacuo
  4. stirringthe residue stirred with water (100 ml) and dichloromethane (100 ml)
  5. customseparated
  6. dry with materialdried (MgSO4)
  7. customevaporated in vacuo

Sources & evidence

ORD record
ord-043ca57a6c874679a9bb104ecece368b
Source dataset
uspto-grants-1994_11
Patent number
US05360802

Reaction notes

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