Methyl iodide → Methyl 5-bromo-2-methylbenzoate

HRID 230235

Reaction equation

HRID 230235 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:11])=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8].Br[C:13]1C(C)=C(C=CC=1)C(O)=O.CI.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[CH3:13][O:8][C:7](=[O:9])[C:6]1[CH:10]=[C:2]([Br:1])[CH:3]=[CH:4][C:5]=1[CH3:11]

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 3460045-Bromo-2-methylbenzoic acidHCID 27355903-Bromo-2-methylbenzoic Acid

Product 1

HCID 316201Methyl 5-bromo-2-methylbenzoate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A 60:40 mixture of 5-bromo-2-methyl benzoic acid and 3-bromo-2-methyl benzoic acid (8.0 g, 0.037 mol) was dissolved in N,N′-dimethylformamide (130 mL). Methyl iodide (2.28 mL, 2.3 mol) and potassium carbonate (5.11 g, 0.037 mol) were added in sequence at room temperature. The mixture was stirred at room temperature for 2 hours at which point the reaction was determined to be complete by HPLC. The solvent was removed under high vacuum and the resulting residue was passed through a silica gel column using 5% ethyl acetate in hexanes as the eluent. The mixture of isomers was obtained as an oil and then separated by preparative normal phase HPLC using 0.5% isopropyl alcohol in hexanes as the eluent. The title compound was obtained as a white solid (1.38 g, 29%). 1H NMR (300.132 MHz, CDCl3) δ 8.04 (d, J=2.2 Hz, 1H), 7.50 (dd, J=8.2, 2.2 Hz, 1H), 7.12 (d, J=8.2 Hz, 1H), 3.89 (s, 3H), 2.54 (s, 3H).

Workup

  1. customThe solvent was removed under high vacuum
  2. additionThe mixture of isomers
  3. customwas obtained as an oil
  4. customseparated by preparative normal phase

Sources & evidence

ORD record
ord-7b151fd409a947519efff1a986c3af90
Source dataset
uspto-grants-2009_07
Patent number
US07566727B2

Linked notes

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