4-Methoxybenzylamine → N-(4-methoxybenzyl)(5-bromo-2-nitrophenyl)methanamine

HRID 545632Notes

Reaction equation

HRID 545632 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=1)[CH:7]=O.[CH3:13][O:14][C:15]1[CH:22]=[CH:21][C:18]([CH2:19][NH2:20])=[CH:17][CH:16]=1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C(Cl)Cl.CC(O)=O>[CH3:13][O:14][C:15]1[CH:22]=[CH:21][C:18]([CH2:19][NH:20][CH2:7][C:6]2[CH:9]=[C:2]([Br:1])[CH:3]=[CH:4][C:5]=2[N+:10]([O-:12])=[O:11])=[CH:17][CH:16]=1

Participants

6

Reactant 3

HCID 754524-MethoxybenzylamineHCID 972335-Bromo-2-nitrobenzaldehydeHCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 67186987N-(4-methoxybenzyl)(5-bromo-2-nitrophenyl)methanamine

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 6344DichloromethaneSolvent

Procedure

To a stirring mixture of 5-bromo-2-nitrobenzaldehyde (0.46 g, 2.0 mmole (prepared according to a reference: Organic Letters (2003), 5(13), 2251-2253) in DCM (4.0 mL) was added p-methoxybenzyl amine (0.32 mL, 2.4 mmol) and three drops of AcOH. The mixture was stirred at RT for 5 min, after which was added NaB(OAc)3H (0.64 g, 3 mmol) and the entire mixture was stirred for additional 2 hrs. The reaction mixture was quenched with NaHCO3 (aq) and diluted with EtOAc (10 mL). The separated aqueous layer was extracted with EtOAc (2×15 mL) and the combined organic layers were washed with brine, dried over Na2SO4, and concentrated to give a crude residue, which was purified using flash column chromatography (100% hexane to 30% EtOAc/hexanes gradient) to obtain the desired product N-(4-methoxybenzyl)(5-bromo-2-nitrophenyl)methanamine as a pale yellow oil. MS m/e 351 (M+H)+.

Workup

  1. customprepared
  2. stirringthe entire mixture was stirred for additional 2 hrs
  3. customThe reaction mixture was quenched with NaHCO3 (aq)
  4. additiondiluted with EtOAc (10 mL)
  5. extractionThe separated aqueous layer was extracted with EtOAc (2×15 mL)
  6. washthe combined organic layers were washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. customto give a crude residue, which
  10. customwas purified

Sources & evidence

ORD record
ord-292dd94f554c4aba92f8195f227249cf
Source dataset
uspto-grants-2011_05
Patent number
US07935709B2

Reaction notes

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