Methylamine → [5-Bromo-2-(3,4-dichloro-phenoxy)-benzyl]-methyl-amine

HRID 499002Notes

Reaction equation

HRID 499002 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:10][C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[C:13]([Cl:18])[CH:12]=2)=[C:6]([CH:9]=1)[CH:7]=O.[CH3:19][NH2:20].[BH4-].[Na+]>CO>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:10][C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[C:13]([Cl:18])[CH:12]=2)=[C:6]([CH:9]=1)[CH2:7][NH:20][CH3:19]

Participants

5

Reactant 3

HCID 6329MethylamineHCID 4311764Sodium borohydrideHCID 120170305-Bromo-2-(3,4-dichlorophenoxy)benzaldehyde

Product 1

HCID 9947009[5-Bromo-2-(3,4-dichloro-phenoxy)-benzyl]-methyl-amineYield 97%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a mixture of 5-bromo-2-(3,4-dichloro-phenoxy)-benzaldehyde (4.74 g, 13.8 mmol) in MeOH (250 mL) was added MeNH2 (40% aq.; 20 mL, 260 mmol), and the resulting mixture was stirred at rt until homogeneous. The mixture was cooled to 0° C. and treated with NaBH4 (1.05 g, 27.8 mmol) portionwise. After 24 h, the mixture was concentrated and the residue was diluted with 1 N NaOH and extracted with DCM. The combined organic layers were dried (Na2SO4) and concentrated. The crude product was purified by FCC to provide the desired product (4.80 g, 97%). MS (ESI): mass calcd. for C14H12BrCl2NO, 358.95; m/z found, 360.1 [M+H]+. 1H NMR (CDCl3): 7.61 (d, J=2.5, 1H), 7.40-7.37 (m, 2H), 7.03 (d, J=2.8, 1H), 6.82-6.79 (m, 2H), 3.72 (s, 2H), 2.44 (s, 3H), 1.30-1.21 (m, 1H).

Workup

  1. temperatureThe mixture was cooled to 0° C.
  2. concentrationthe mixture was concentrated
  3. additionthe residue was diluted with 1 N NaOH
  4. extractionextracted with DCM
  5. dry with materialThe combined organic layers were dried (Na2SO4)
  6. concentrationconcentrated
  7. customThe crude product was purified by FCC

Sources & evidence

ORD record
ord-3ae549d54a8b415bbc522d5b18171081
Source dataset
uspto-grants-2010_08
Patent number
US07767666B2

Reaction notes

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