Trimethyl orthoformate → Methyl 3-chloro-2-methylbenzoate

HRID 915354Notes

Reaction equation

HRID 915354 reaction equation
[Cl:1][C:2]1[C:3]([CH3:11])=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[CH:12](OC)(OC)OC>CO>[CH3:12][O:6][C:5](=[O:7])[C:4]1[CH:8]=[CH:9][CH:10]=[C:2]([Cl:1])[C:3]=1[CH3:11]

Participants

4

Reactant 2

HCID 9005Trimethyl orthoformateHCID 820103-Chloro-2-methylbenzoic acid

Product 1

HCID 5077673Methyl 3-chloro-2-methylbenzoateYield 96.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

Alternatively, to a suspension of 3-chloro-2-methylbenzoic acid (6.8 g, 40 mmol) in methanol (40 mL) was added trimethyl orthoformate (4.4 mL, 40 mmol). HCl gas was then bubbled through the suspension for 20 minutes. The resulting solution was then heated in a 60° C. oil bath. After stirring at 60° C. for 16 hours, the solution was allowed to cool to ambient temperature and concentrated under reduced pressure to afford a thick yellow paste. The semi-solid was melted under reduced pressure using a heat gun, and then cooled to afford 3-chloro-2-methylbenzoic acid methyl ester (7.1 g, 95% yield) as a yellow crystalline solid: 1H-NMR (400 MHz, CDCl3): δ 7.70 (1H, d, J=7.8 Hz), 7.51 (1H, d, J=7.8 Hz), 7.17 (1H, t, J=7.8 Hz), 3.91 (s, 3H), 2.60 (s, 3H) ppm.

Workup

  1. customHCl gas was then bubbled through the suspension for 20 minutes
  2. temperatureto cool to ambient temperature
  3. concentrationconcentrated under reduced pressure
  4. customto afford a thick yellow paste
  5. temperaturecooled

Sources & evidence

ORD record
ord-a29b57fe62964f598d0686b5e8f8f0f3
Source dataset
uspto-grants-2007_09
Patent number
US07265131B2

Reaction notes

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