3-Bromo-4-methoxybenzonitrile → (3-Bromo-4-methoxyphenyl)methanamine

HRID 1420693Notes

Reaction equation

HRID 1420693 reaction equation
B.O1CCCC1.[Br:7][C:8]1[CH:13]=[C:12]([C:14]#[N:15])[CH:11]=[CH:10][C:9]=1[O:16][CH3:17]>O1CCCC1>[NH3:15].[Br:7][C:8]1[CH:13]=[C:12]([CH2:14][NH2:15])[CH:11]=[CH:10][C:9]=1[O:16][CH3:17]

Participants

5

Reactant 2

HCID 7360493-Bromo-4-methoxybenzonitrileHCID 2723981Borane;tetrahydrofuran

Product 2

HCID 222AmmoniaHCID 22026276(3-Bromo-4-methoxyphenyl)methanamineYield 142%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-10 °C

Procedure

Borane-tetrahydrofuran complex (1.0 M solution in tetrahydrofuran. 250 ml) was added to a solution of 2-bromo-4-cyanoanisole (17 g) in tetrahydrofuran (150 ml). The mixture was heated at reflux for 2 hours then cooled to -10° C. and carefully quenched with 6N HCl (130 ml). The mixture was basified with 4N NaOH then extracted with ethyl acetate. The organic layer was separated, dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by flash chromatography, eluting with 120:8:1 dichloromethane:methanol:ammonia, to give the title compound (12.3 g, 71%); δH (250MHz, CDCl3) 3.80 (2H, s, CH2NH2), 3.92 (3H, s, ArOCH3), 6.85 (1H, d, J 8.4Hz, 6-H), 7.20 (1H, dd, J 8.4, 2.1Hz, 5-H), 7.51 (1H, d, J 2.1Hz, 3-H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 2 hours
  3. customcarefully quenched with 6N HCl (130 ml)
  4. extractionthen extracted with ethyl acetate
  5. customThe organic layer was separated
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography
  10. washeluting with 120:8:1 dichloromethane

Sources & evidence

ORD record
ord-cec10be46df84572a5f7c79f32a16e7c
Source dataset
uspto-grants-2000_06
Patent number
US06071928

Reaction notes

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