Dimethylformamide → 3-Iodoaniline

HRID 971329Notes

Reaction equation

HRID 971329 reaction equation
[I:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4](Br)[CH:3]=1.[C:9]([O-:12])(=[O:11])[CH3:10].[Pd+2:13].[C:14]([O-:17])(=[O:16])[CH3:15].[C:18]([O-:21])([OH:20])=[O:19].[Na+:22].C[N:24](C=O)C>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.CCOC(C)=O>[I:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:6][CH:7]=1)[NH2:24].[CH3:10][C:9]([O-:12])=[O:11].[CH3:15][C:14]([O-:17])=[O:16].[Pd+2:13].[C:18]([O-:21])([OH:20])=[O:19].[Na+:22]

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 11561Benzene, 1-bromo-3-iodo-HCID 167845palladium(II) acetateHCID 516892Sodium Bicarbonate

Product 3

HCID 122713-IodoanilineHCID 167845palladium(II) acetateHCID 516892Sodium Bicarbonate

Reagents, catalysts & solvents 2

HCID 70681Tetrabutylammonium ChlorideCatalyst2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Into 12 mL of dry DMF in an oven dried, nitrogen filled tube was placed M (3.0 g, 15 mmol), 1-iodo-3-bromobenzene (1.6 mL, 13 mmol), palladium(II)acetate (0.42 g, 1.9 mmol), tetrabutylammoniumchloride (3.5 g, 13 mmol), and solid NaHCO3 (2.6 g, 31 mmol). The tube was sealed and heated to 80° C. for 16 hours. The cooled reaction mixture was diluted with EtOAc, passed through a small plug of silica gel to remove the catalyst, and extracted 2× with brine. The solution was then dried over Na2SO4, concentrated, and purified by flash chromatography eluting with 2:1 and 1:1 heptane: EtOAc to afford N (1.8 g, 5 mmol, 40%) (MS;M+H: 356.1, 358.1). Likewise N′ was formed (0.92 g, 3.1 mmol, 77%) (MS;M+H: 293.2) from M (1.0 g, 5 mmol), 3-iodoaniline (0.5 mL, 4.2 mmol), Pd(OAc)2 (0.14 g, 0.62 mmol), Bu4NCl (1.16 g, 4.2 mmol), and NaHCO3 (0.87 g, 10 mmol) in 4 mL of dry DMF.

Workup

  1. dry with materialInto 12 mL of dry DMF in an oven dried
  2. customnitrogen filled tube was placed
  3. customThe tube was sealed
  4. customThe cooled reaction mixture
  5. customto remove the catalyst
  6. extractionextracted 2× with brine
  7. dry with materialThe solution was then dried over Na2SO4
  8. concentrationconcentrated
  9. custompurified by flash chromatography
  10. washeluting with 2:1 and 1:1 heptane
  11. customEtOAc to afford N (1.8 g, 5 mmol, 40%) (MS;M+H: 356.1, 358.1)

Sources & evidence

ORD record
ord-4ff50232ac494a3db684aac59f884101
Source dataset
uspto-grants-2007_12
Patent number
US07312360B2

Reaction notes

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