Water → HCID 69271080, compound

HRID 2221114Notes

Reaction equation

HRID 2221114 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]2[O:9][CH:8]=[C:7]([CH:10]=O)[C:6]=2[CH:12]=1.[CH2:13]([O:15][C:16](=[O:28])[NH:17][C:18]1[CH:23]=[CH:22][C:21]([NH2:24])=[CH:20][C:19]=1[N+:25]([O-:27])=[O:26])[CH3:14].[BH4-].[Na+].O>CC1C=CC=CC=1C.O1CCOCC1.CO>[CH2:13]([O:15][C:16](=[O:28])[NH:17][C:18]1[CH:23]=[CH:22][C:21]([NH:24][CH2:10][C:7]2[C:6]3[CH:12]=[C:2]([F:1])[CH:3]=[CH:4][C:5]=3[O:9][CH:8]=2)=[CH:20][C:19]=1[N+:25]([O-:27])=[O:26])[CH3:14]

Participants

7

Reactant 4

HCID 962WaterHCID 4311764Sodium borohydrideHCID 20096580HCID 20096580, compoundHCID 251298025-Fluoro-1-benzofuran-3-carbaldehyde

Product 1

HCID 69271080HCID 69271080, compound

Reagents, catalysts & solvents 2

HCID 7237O-XyleneSolventHCID 21966525Dioxane MethanolSolvent

Procedure

In a 3-necked round bottomed flask fitted with a Dean-Stark apparatus 5-Fluoro-benzofuran-3-carbaldehyde (3.59 g, 21.9 mmol) and (4-amino-2-nitro-phenyl)-carbamic acid ethyl ester (4.48 g, 19.9 mmol) were mixed in o-xylene (80 mL) and a catalytic amount of acidic ion exchange resin (Amberlite IRC-84, 100 mg) was added. The mixture was heated to reflux for 5 hours, filtered warm and concentrated in vacuo. This crude product was dissolved in a dioxane:methanol (4:1) mixture (90 mL) and sodiumborohydride (1.50 g, 39.8 mmol) was added portionwise over a period of 30 minutes. The reaction mixture was stirred at ambient temperature over night, then poured into water (200 mL) and extracted with ethyl acetate (3×75 mL). The combined organic fractions were washed with brine, dried (MgSO4) and evaporated to give a crude solid which was purified by chromatography on silica gel (eluent:ethyl acetate:heptane 1:2). This furnished 4.50 g (61%) of the title compound as a red crystalline material. 1H NMR (CDCl3): 1.33 (t, 3H); 4.07 (t, 1H); 4.23 (q, 2H); 4.42 (d, 2H); 6.99 (dd, 1H); 7.05 (dt, 1H); 7.25 (dd, 1H); 7.42 (t, 1H); 7.44 (d, 1H); 7.65 (s, 1H); 8.31 (d, 1H); 9.39 (s, 1H).

Workup

  1. additiona catalytic amount of acidic ion exchange resin (Amberlite IRC-84, 100 mg) was added
  2. temperatureThe mixture was heated
  3. temperatureto reflux for 5 hours
  4. filtrationfiltered
  5. temperaturewarm
  6. concentrationconcentrated in vacuo
  7. additionwas added portionwise over a period of 30 minutes
  8. extractionextracted with ethyl acetate (3×75 mL)
  9. washThe combined organic fractions were washed with brine
  10. dry with materialdried (MgSO4)
  11. customevaporated
  12. customto give a crude solid which
  13. customwas purified by chromatography on silica gel (eluent:ethyl acetate:heptane 1:2)

Sources & evidence

ORD record
ord-9018292ac63647dd8e79d055d7254227
Source dataset
uspto-grants-2008_05
Patent number
US07368472B2

Reaction notes

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