Citric Acid → 4-Allyloxy-2,3-dihydroxybenzaldehyde

HRID 218266Notes

Reaction equation

HRID 218266 reaction equation
[Sn](Cl)(Cl)(Cl)Cl.[CH2:6]([O:9][C:10]1[CH:16]=[CH:15][CH:14]=[C:12]([OH:13])[C:11]=1[OH:17])[CH:7]=[CH2:8].[C:18]([O-])(O)=[O:19].[Na+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C(Cl)Cl>[CH2:6]([O:9][C:10]1[CH:16]=[CH:15][C:14]([CH:18]=[O:19])=[C:12]([OH:13])[C:11]=1[OH:17])[CH:7]=[CH2:8]

Participants

6

Reactant 4

HCID 311Citric AcidHCID 24287Tin tetrachlorideHCID 516892Sodium BicarbonateHCID 122088813-Allyloxycatechol

Product 1

HCID 601306764-Allyloxy-2,3-dihydroxybenzaldehyde

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Tin tetrachloride (0.31 g, 0.14 mL, 1.32 mmol) was added to a solution of 39 (0.20 g, 1.20 mmol) and αα′-dichloromethyl methyl ether (0.15 g, 0.12 mL, 1.32 mmol) in CH2Cl2 at −78° C. The pale brown reaction mixture was stirred at this temperature for 1.5 h, then poured into an excess of saturated NaHCO3 aq. cooled at 0° C. The mixture was stirred for 15 min, acidified to pH 5 by the addition of 5% w/v citric acid then extracted with CH2Cl2 (3×). The organic phase was dried (Na2SO4) and evaporated to dryness to give 40 compound (0.18 g, 76%) which was used as such in the next step.

Workup

  1. stirringThe mixture was stirred for 15 min
  2. additionacidified to pH 5 by the addition of 5%
  3. extractionthen extracted with CH2Cl2 (3×)
  4. dry with materialThe organic phase was dried (Na2SO4)
  5. customevaporated to dryness

Sources & evidence

ORD record
ord-cf4b3ba945be4e85a33c545cd72d5f8c
Source dataset
uspto-grants-2012_06
Patent number
US08198302B2

Reaction notes

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