Carbon tetrabromide → 4-(2-Bromo-ethoxy)-2-hydroxy-benzoic acid methyl ester

HRID 29645Notes

Reaction equation

HRID 29645 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH2:12]O)=[CH:6][C:5]=1[OH:14].C(Br)(Br)(Br)[Br:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH2:12][Br:17])=[CH:6][C:5]=1[OH:14]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromide2×HCID 11776Triphenylphosphine2×HCID 586358Methyl 4-(2-hydroxyethoxy)salicylate

Product 1

HCID 574195214-(2-Bromo-ethoxy)-2-hydroxy-benzoic acid methyl esterYield 78.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-hydroxy-4-(2-hydroxy-ethoxy)-benzoic acid methyl ester (3.025 g, 14.25 mmol) in methylene chloride (80 mL) was added carbon tetrabromide (6.216 g, 18.74 mmol) and triphenylphosphine (5.012 g, 19.10 mmol). The reaction was stirred 3 hours at room temperature then additional carbon tetrabromide (1.967 g, 5.931 mmol) and triphenylphosphine (1.568 g, 5.97 mmol) was added and stirring continued overnight. The reaction mixture was concentrated in vacuo and the residue was purified by flash chromatography using ethyl acetate/hexanes (10/90 to 20/80) to afford 4-(2-bromo-ethoxy)-2-hydroxy-benzoic acid methyl ester (3.070 g, 78%) as a white solid. 1H NMR (300 MHz, CDCl3); δ 11.00 (s, 1H), 7.76 (d, 2H), 6.46 (m, 2H), 4.32 (t, 2H), 3.93 (s, 3H), 3.65 (t, 2H).

Workup

  1. stirringstirring continued overnight
  2. concentrationThe reaction mixture was concentrated in vacuo
  3. customthe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-0bc883cc188645dcb39f9fa1d85c14ca
Source dataset
uspto-grants-2008_09
Patent number
US07420083B2

Reaction notes

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