Nitromethane → 2-Chloro-5-(4-(2-nitro-ethyl)-benzyl)furan

HRID 77958Notes

Reaction equation

HRID 77958 reaction equation
[Cl:1][C:2]1[O:6][C:5]([CH2:7][C:8]2[CH:15]=[CH:14][C:11]([CH:12]=O)=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.[N+:16]([CH3:19])([O-:18])=[O:17].C([O-])(=O)C.[NH4+].[BH4-].[Na+]>O.C(O)(=O)C>[Cl:1][C:2]1[O:6][C:5]([CH2:7][C:8]2[CH:15]=[CH:14][C:11]([CH2:12][CH2:19][N+:16]([O-:18])=[O:17])=[CH:10][CH:9]=2)=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 6375NitromethaneHCID 517165Ammonium AcetateHCID 4311764Sodium borohydrideHCID 59255186HCID 59255186, compound

Product 1

HCID 592553222-Chloro-5-(4-(2-nitro-ethyl)-benzyl)furanYield 65.9%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

To a mixture of 4-(5-chloro-furan-2-ylmethyl)-benzaldehyde (270 mg, 1.2 mmol) described in Manufacturing Example 62-1-4 and acetic acid (3 mL) were added nitromethane (500 μL, 9.3 mmol) and ammonium acetate (290 mg, 3.7 mmol) at room temperature, which was stirred for 3 hours at 100° C. The reaction mixture was cooled to room temperature, and extracted by addition of water and ethyl acetate. This organic layer was washed with saturated aqueous sodium chloride and dried over anhydrous magnesium sulfate, and was concentrated under a reduced pressure. To a mixture of acetic acid (0.6 mL) and dimethyl sulfoxide (10 mL) was added sodium borohydride (76 mg, 2.0 mmol) at room temperature while cooling appropriately, which was stirred for 10 minutes at room temperature. Water was added to the reaction solution at room temperature, which was then extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride. The organic layer was concentrated under a reduced pressure, and the residue was purified by neutral silica gel column chromatography (ethyl acetate:heptane=1:5) to obtain the title compound (210 mg, 62%).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. extractionextracted by addition of water and ethyl acetate
  3. washThis organic layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationwas concentrated under a reduced pressure
  6. additionTo a mixture of acetic acid (0.6 mL) and dimethyl sulfoxide (10 mL)
  7. temperaturewhile cooling appropriately
  8. stirringwhich was stirred for 10 minutes at room temperature
  9. extractionwhich was then extracted with ethyl acetate
  10. washThe organic layer was washed with saturated aqueous sodium chloride
  11. concentrationThe organic layer was concentrated under a reduced pressure
  12. customthe residue was purified by neutral silica gel column chromatography (ethyl acetate:heptane=1:5)

Sources & evidence

ORD record
ord-f88900a529564f27a292cfae68d2ac8d
Source dataset
uspto-grants-2014_09
Patent number
US08841327B2

Reaction notes

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