Ethyl Acetate → 4-bromo-N1-(3-(dimethylamino)propyl)-N1-methylbenzene-1,2-diamine

HRID 1361589Notes

Reaction equation

HRID 1361589 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]([CH3:15])[CH2:9][CH2:10][CH2:11][N:12]([CH3:14])[CH3:13])=[C:4]([N+:16]([O-])=O)[CH:3]=1.Cl[Sn]Cl.CCOC(C)=O.C(=O)(O)[O-].[Na+]>CCO>[Br:1][C:2]1[CH:3]=[C:4]([NH2:16])[C:5]([N:8]([CH2:9][CH2:10][CH2:11][N:12]([CH3:14])[CH3:13])[CH3:15])=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 24479Stannous Chloride2×HCID 516892Sodium BicarbonateHCID 16109013HCID 16109013, compound

Product 1

HCID 594279234-bromo-N1-(3-(dimethylamino)propyl)-N1-methylbenzene-1,2-diamine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
80 °C

Procedure

To N-(4-Bromo-2-nitro-phenyl)-N,N′,N′-trimethyl-propane-1,3-diamine (Example 619, Step 1) (0.54 g, 1.7 mmol) in 20 ml EtOH was added SnCl2 (0.51 g, 2.67 mmol). The mixture was sealed and was heated to 80° C. for 12 h. An additional amount of SnCl2 (0.51 g, 2.67 mmol) was added and heating continued for 12 h. The reaction was cooled to ambient temperature, and was poured into a mixture of EtOAc and saturated aqueous sodium bicarbonate. The mixture was filtered through celite, and the organic layer was removed. The aqueous layer was extracted twice with EtOAc, and the combined organic layers were dried with Na2SO4, filtered, and concentrated to give a cloudy oil. This material was filtered through silica gel with 90/10/1 dichloromethane/MeOH/conc. NH4OH and concentrated in vacuo to give the title compound as a red oil. MS (ES+): 285.9 (M+H)+. Calc'd for C12H20BrN3: 286.21.

Workup

  1. customThe mixture was sealed
  2. temperatureheating
  3. temperatureThe reaction was cooled to ambient temperature
  4. filtrationThe mixture was filtered through celite
  5. customthe organic layer was removed
  6. extractionThe aqueous layer was extracted twice with EtOAc
  7. dry with materialthe combined organic layers were dried with Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give a cloudy oil
  11. filtrationThis material was filtered through silica gel with 90/10/1 dichloromethane/MeOH/conc
  12. concentrationNH4OH and concentrated in vacuo

Sources & evidence

ORD record
ord-482b3534016a481d88d9bcc237957324
Source dataset
uspto-grants-2011_02
Patent number
US07880000B2

Reaction notes

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