Hydrochloric Acid → 2-Amino-4-(aminomethyl)-6-bromophenol

HRID 2218953Notes

Reaction equation

HRID 2218953 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([N+:11]([O-])=O)[C:9]=1[OH:10])[C:5]#[N:6].B.C1COCC1.B.Cl>C1COCC1>[NH2:11][C:8]1[CH:7]=[C:4]([CH2:5][NH2:6])[CH:3]=[C:2]([Br:1])[C:9]=1[OH:10]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6331BoraneHCID 2723981Borane;tetrahydrofuranHCID 3014048Benzonitrile, 3-bromo-4-hydroxy-5-nitro-

Product 1

HCID 597709322-Amino-4-(aminomethyl)-6-bromophenolYield 19.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 3-bromo-4-hydroxy-5-nitrobenzonitrile (1.0 g, 4.11 mmol) in 20.0 mL of dry THF was added dropwise to a solution of BH3/THF 1.0 M in THF (12.3 mL) at 0° C. under N2. The reaction mixture was stirred at room temperature for 24 hours. Excess borane was decomposed by the cautious dropwise addition of 1 N HCl at 0° C. It was extracted with EtOAc, washed with NaHCO3, NaCl saturated solution and dried (Na2SO4 anh.) to give a crude. After purification by column chromatography (CH2Cl2/MeOH 8:2+1% NH4OH), 170 mg (19%) of 2-amino-4-(aminomethyl)-6-bromophenol were obtained. 1H NMR (DMSO-d6) δ 6.67 (s, 1H, H-5); 6.53 (s, 1H, H-3); 3.52 (s, 2H, CH2). 13C NMR (DMSO-d6) δ 139.7, 139.4 (C-1, C-4), 136.0 (C-2), 118.5 (C-5), 113.0 (C-3), 111.5 (C-6), 44.9 (CH2).

Workup

  1. extractionIt was extracted with EtOAc
  2. washwashed with NaHCO3, NaCl saturated solution
  3. dry with materialdried (Na2SO4 anh.)
  4. customto give a crude
  5. customAfter purification by column chromatography (CH2Cl2/MeOH 8:2+1% NH4OH)

Sources & evidence

ORD record
ord-2fd804e21d124504bdb3d49333ca504e
Source dataset
uspto-grants-2008_08
Patent number
US07414036B2

Reaction notes

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