5-Nitrofurfural → HCID 86623885, compound

HRID 1696666Notes

Reaction equation

HRID 1696666 reaction equation
[H-].[Na+].[F:3][C:4]1([F:17])[O:16][C:7]2=[CH:8][C:9]3[NH:13][C:12](=[S:14])[NH:11][C:10]=3[CH:15]=[C:6]2[O:5]1.[N+]([C:21]1[O:25][C:24]([CH:26]=[O:27])=[CH:23][CH:22]=1)([O-])=O>O1CCCC1>[F:17][C:4]1([F:3])[O:5][C:6]2=[CH:15][C:10]3[NH:11][C:12]([S:14][C:21]4[O:25][C:24]([CH:26]=[O:27])=[CH:23][CH:22]=4)=[N:13][C:9]=3[CH:8]=[C:7]2[O:16]1

Participants

5

Reactant 3

HCID 127745-NitrofurfuralHCID 24758Sodium hydrideHCID 11401952HCID 11401952, compound

Product 1

HCID 86623885HCID 86623885, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Aldehyde intermediate preparation: Sodium hydride (60% dispersion in mineral oil, 0.212 g, 5.3 mmol) in tetrahydrofuran (3 ml) is added dropwise over a 15 minute period to a solution of 2,2-difluoro-5,7-dihydro-[1,3]dioxolo[4′,5′:4,5]benzo[1,2-d]imidazole-6-thione (0.763 g, 3.31 mmol) in tetrahydrofuran (5 ml). The mixture is stirred at room temperature for 2 hours. 5-nitro-2-furaldehyde (0.468 g, 3.31 mmol) in 7 ml of tetrahydrofuran is then added dropwise over a 15 minute period and the mixture is stirred for 2 hours at room temperature. The reaction mixture is then concentrated under reduced pressure and the residue is dissolved in 100 ml of ethyl acetate and washed with water (2×30 ml). The organic phase is dried over MgSO4 and concentrated under reduced pressure. The residue is purified on a silica gel column (120 g) eluted with a mixture of dichloromethane and methanol (92/5, v/v). The fractions containing the expected product are concentrated under reduced pressure and the residue is triturated in diisopropylether and pentane and dried under vacuum to yield 5-(2,2-difluoro-5H-[1,3]dioxolo[4′,5′:4,5]benzo[1,2-d]imidazol-6-ylsulfanyl)-furan-2-carbaldehyde as a brown powder. Yield=56%. Analytical LC/MS (method B): retention time=3.66 min., m/z=324.97 (positive ion mode).

Workup

  1. stirringthe mixture is stirred for 2 hours at room temperature
  2. concentrationThe reaction mixture is then concentrated under reduced pressure
  3. dissolutionthe residue is dissolved in 100 ml of ethyl acetate
  4. washwashed with water (2×30 ml)
  5. dry with materialThe organic phase is dried over MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe residue is purified on a silica gel column (120 g)
  8. washeluted with a mixture of dichloromethane and methanol (92/5
  9. additionThe fractions containing the expected product
  10. concentrationare concentrated under reduced pressure
  11. customthe residue is triturated in diisopropylether
  12. dry with materialpentane and dried under vacuum

Sources & evidence

ORD record
ord-bba81e2d14234fd2af07191e82038a8a
Source dataset
uspto-grants-2012_04
Patent number
US08163768B2

Reaction notes

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