Protocatechuic Acid → HCID 11524671, compound

HRID 733332Notes

Reaction equation

HRID 733332 reaction equation
[CH2:1](Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH:9][C:10]1[CH:11]=[C:12]([CH:16]=[CH:17][C:18]=1[OH:19])[C:13]([OH:15])=[O:14].C(=O)([O-])[O-].[K+].[K+].Cl>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O.O>[CH2:1]([O:9][C:10]1[CH:11]=[C:12]([CH:16]=[CH:17][C:18]=1[O:19][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:13]([O:15][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 72Protocatechuic AcidHCID 313Hydrochloric AcidHCID 7498Benzyl BromideHCID 11430Potassium Carbonate

Product 1

HCID 11524671HCID 11524671, compoundYield 9.4%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Benzyl bromide (1.50 cm3, 2.16 g, 12.6 mmol) was added to a stirred suspension of 3,4-dihydroxybenzoic acid (1.00 g, 6.49 mmol), potassium carbonate (1.97 g, 14.3 mmol) and a catalytic amount of tetrabutylammonium iodide in N,N-dimethylformamide (50 cm3). The suspension was stirred under nitrogen overnight then water (500 cm3) and 5% hydrochloric acid (50 cm3) were added, and the mixture was extracted with diethyl ether (3×100 cm3). The combined extracts were washed with water (3×100 cm3) and brine (100 cm3), then dried (Na2SO4) and evaporated to an orange oil. Flash column chromatography (eluent: 10-20% ethyl acetate in light petroleum) gave first benzyl 3,4-dibenzyloxybenzoate (168 mg, 6%), identical to that prepared above. Further elution then gave benzyl 4-benzyloxy-3-hydroxybenzoate (1.312 g, 60%) as a pale yellow oil. The position of the benzyloxy group was deduced from an n.O.e. observed between the proton at position 5 and the methylene protons of the benzyloxy group at position 4.

Workup

  1. extractionthe mixture was extracted with diethyl ether (3×100 cm3)
  2. washThe combined extracts were washed with water (3×100 cm3) and brine (100 cm3)
  3. dry with materialdried (Na2SO4)
  4. customevaporated to an orange oil

Sources & evidence

ORD record
ord-abcff43a058a4081bc16bba593a36ed4
Source dataset
uspto-grants-2009_09
Patent number
US07589170B1

Reaction notes

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