1,2-Dimethoxyethane → 4-Ethenyl-2-hydroxybenzoic acid

HRID 1399520Notes

Reaction equation

HRID 1399520 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7](I)=[CH:6][C:5]=1[OH:11].C(=O)([O-])[O-].[Na+].[Na+].CO[CH2:21][CH2:22]OC>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[OH:11][C:5]1[CH:6]=[C:7]([CH:21]=[CH2:22])[CH:8]=[CH:9][C:4]=1[C:3]([OH:2])=[O:12].[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH:21]=[CH2:22])=[CH:6][C:5]=1[OH:11]

Participants

6

Reactant 3

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 11380407Methyl 4-iodosalicylate

Product 2

HCID 199369764-Ethenyl-2-hydroxybenzoic acidHCID 200893762-Hydroxy-4-vinyl-benzoic acid methyl ester

Reagents, catalysts & solvents 1

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Procedure

A round-bottom flask is charged with 2-Hydroxy-4-iodo-benzoic acid methyl ester, 26-01 (12.0 g, 43.2 mmol), 2,4,6-Trivinyl-cyclotriboroxane-pyridine complex (11.4 g, 47.5 mmol), tetrakis(triphenylphosphine) palladium (2.49 g, 2.16 mmol), 2.0 M aqueous solution of sodium carbonate (25.9 mL, 51.7 mmol), and 1,2-dimethoxyethane (50 mL), deoxygenated by alternating between vacuum and argon (3×), and refluxed under argon pressure for 3 h, and then stirred 18 h at ambient temperature. Volatiles are stripped in vacuo, the residue is suspended in 1N HCl (800 mL) and extracted with EtOAc (600 mL, 300 mL, and then 300 mL). The combined organic extracts are washed brine, dried over NaSO4, and purified by chromatography (silica gel, 5-30% EtOAc in heptane) to afford 2-Hydroxy-4-vinyl-benzoic acid, 26-02 (3.70 g) and 2-Hydroxy-4-vinyl-benzoic acid methyl ester (0.300 g).

Workup

  1. customdeoxygenated
  2. temperaturerefluxed under argon pressure for 3 h
  3. extractionextracted with EtOAc (600 mL, 300 mL
  4. washThe combined organic extracts are washed brine
  5. dry with materialdried over NaSO4
  6. custompurified by chromatography (silica gel, 5-30% EtOAc in heptane)

Sources & evidence

ORD record
ord-3ae8bbb512454f04926b9ff095bd7a34
Source dataset
uspto-grants-2014_12
Patent number
US08906904B2

Reaction notes

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