Catechol → Benzo[1,3]dioxole-2,2-dicarboxylic acid diethyl ester

HRID 10616

Reaction equation

HRID 10616 reaction equation
[C:1]1([C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[OH:4])[OH:2].Br[C:10](Br)([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:11]([O:13][CH2:14][CH3:15])=[O:12].C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[CH2:19]([O:18][C:16]([C:10]1([C:11]([O:13][CH2:14][CH3:15])=[O:12])[O:4][C:3]2[CH:5]=[CH:6][CH:7]=[CH:8][C:1]=2[O:2]1)=[O:17])[CH3:20]

Participants

5

Reactant 3

HCID 289CatecholHCID 11430Potassium CarbonateHCID 69427Propanedioic acid, 2,2-dibromo-, 1,3-diethyl ester

Product 1

HCID 12969876Benzo[1,3]dioxole-2,2-dicarboxylic acid diethyl esterYield 73.2%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

Ex-1A: Catechol (2.2 g, 20 mmol) was dissolved in acetone. Diethyl dibromomalonate (7.0 g, 22 mmol) and potassium carbonate (2.76 g) were added, and the mixture was stirred at room temperature overnight. The solvent was removed under reduced pressure, and water was added to the residue. The residue was extracted with dichloromethane, and the organic phase was washed with brine, dried over magnesium sulfate and evaporated. Chromatography (hexanes/ethyl acetate, 4:1) gave 3.9 g of benzo[1,3]dioxole-2,2-dicarboxylic acid diethyl ester. 1H-NMR (CDCl3) δ 6.90–6.97 (m, 4H), 4.37 (q, J=7 Hz, 4H), 1.32 (t, J=7 Hz, 6H).

Workup

  1. customThe solvent was removed under reduced pressure, and water
  2. additionwas added to the residue
  3. extractionThe residue was extracted with dichloromethane
  4. washthe organic phase was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. customevaporated

Sources & evidence

ORD record
ord-0fb2734542694c16affef6dddddfd246
Source dataset
uspto-grants-2006_08
Patent number
US07094801B2

Linked notes

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