Water → HCID 69417575, compound

HRID 1594515Notes

Reaction equation

HRID 1594515 reaction equation
[Cl:1][C:2]1[C:8]([Cl:9])=[CH:7][C:5]([NH2:6])=[C:4]([N+:10]([O-])=O)[CH:3]=1.Br[CH2:14][C:15]1[CH:23]=[CH:22][C:18]([C:19]([O-:21])=[O:20])=[CH:17][CH:16]=1.[C:24]([O-])([O-])=O.[K+].[K+].Cl[Sn]Cl.O.C([O-])(O)=O.[Na+]>CN(C=O)C.CCOC(C)=O>[NH2:6][C:5]1[CH:7]=[C:8]([Cl:9])[C:2]([Cl:1])=[CH:3][C:4]=1[NH:10][CH2:14][C:15]1[CH:23]=[CH:22][C:18]([C:19]([O:21][CH3:24])=[O:20])=[CH:17][CH:16]=1

Participants

9

Reactant 6

HCID 962WaterHCID 11430Potassium CarbonateHCID 24479Stannous ChlorideHCID 811494,5-Dichloro-2-nitroanilineHCID 516892Sodium BicarbonateHCID 6919881HCID 6919881, compound

Product 1

HCID 69417575HCID 69417575, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

4,5-Dichloro-2-nitroaniline (10 mmol, 2.07 g), 4-bromomethylbenzoate (10 mmol, 2.29 g) and K2CO3 (12 mmol, 1.66 g) were stirred in DMF (10 mL) at ambient temperature for 16 h. The reaction mixture was partitioned between CH2Cl2 and brine, and the organic phase was dried with Na2SO4 and concentrated in vacuo. The monobenzylated product was obtained by flash chromatography on silica eluting with 15% EtOAc in hexanes as a bright orange solid. A portion of the nitro compound (7.4 mmol, 2.6 g) and SnCl2.2 H2O (22 mmol, 5.0 g) were heated in 40 mL of DMF at 40° C. for 16 h. The reaction mixture was poured into EtOAc and saturated NaHCO3 and stirred to afford a precipitate, which was removed by filtration through celite. The organic phase was dried with Na2SO4 and concentrated in vacuo to a brown oil. Flash chromatography on silica eluting with a step gradient of 20%, 30% and 35% EtOAc in hexanes provided the product as a pale yellow solid. LC-MS (ESI, Method C) 3.54 min, m/z 325.2 (M+1).

Workup

  1. customThe reaction mixture was partitioned between CH2Cl2 and brine
  2. dry with materialthe organic phase was dried with Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe monobenzylated product was obtained by flash chromatography on silica eluting with 15% EtOAc in hexanes as a bright orange solid
  5. customto afford a precipitate, which
  6. customwas removed by filtration through celite
  7. dry with materialThe organic phase was dried with Na2SO4
  8. concentrationconcentrated in vacuo to a brown oil

Sources & evidence

ORD record
ord-45bce04108ec4a02a8027b88bcc1ff60
Source dataset
uspto-grants-2007_11
Patent number
US07301036B2

Reaction notes

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