Nitrite → 2-Furylglyoxylic acid

HRID 597275Notes

Reaction equation

HRID 597275 reaction equation
C(C1OC=CC=1)(=[O:3])C.N([O-])=O.[Na+].[C:13]([O-:24])(=[O:23])[C:14]1C(=[CH:19][CH:20]=[CH:21][CH:22]=1)C([O-])=O.[Na+].[Na+].N([O-])=O.[OH2:30]>Cl>[O:30]1[CH:19]=[CH:20][CH:21]=[C:22]1[C:14](=[O:3])[C:13]([OH:24])=[O:23]

Participants

7

Reactant 5

HCID 946NitriteHCID 962Water2×HCID 145052-AcetylfuranHCID 85215Disodium 1,2-benzenedicarboxylateHCID 23668193Sodium Nitrite2×

Product 1

HCID 738462-Furylglyoxylic acidYield 64.3%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent2×

Procedure

2-Acetylfuran (22 g) in 6N hydrochloric acid (200 ml) at 65° was treated with a solution of sodium nitrite (35 g) in water (100 ml) over 95 minutes. A 1.3M solution of disodium phthalate (230 ml) was added over 5 minutes whilst a solution of sodium nitrite (28 g) in water (70 ml) was being added over 85 minutes. One hour after the end of the addition of the nitrite the solution was cooled and acidified to pH 1.4 with hydrochloric acid and the precipitated phthalic acid filtered off. The solution was next adjusted to pH 3.5 and extracted with methylene chloride (2 × 100 ml) to remove unreacted 2-acetylfuran (1.8 g; 8%), then adjusted to pH 2.8 and extracted with ethyl acetate (4 × 100 ml) to remove furoic acid and phthalic acid (8.6 g) and finally adjusted to pH 0.2 and extracted with ethyl acetate (5 × 100 ml). Evaporation of the ethyl acetate gave 18 g (64.3%) of fur-2-ylglyoxylic acid m.p. 81°-91° C.

Workup

  1. additionwas being added over 85 minutes
  2. temperaturewas cooled
  3. filtrationthe precipitated phthalic acid filtered off
  4. extractionextracted with methylene chloride (2 × 100 ml)
  5. customto remove unreacted 2-acetylfuran (1.8 g; 8%)
  6. extractionextracted with ethyl acetate (4 × 100 ml)
  7. customto remove furoic acid and phthalic acid (8.6 g)
  8. extractionextracted with ethyl acetate (5 × 100 ml)
  9. customEvaporation of the ethyl acetate

Sources & evidence

ORD record
ord-7c1cfafbe28f40bf9f44b6c422cdaf3d
Source dataset
uspto-grants-1977_03
Patent number
US04013680

Reaction notes

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