Ammonium Chloride → HCID 118046519, compound

HRID 595839Notes

Reaction equation

HRID 595839 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([N:11]2[CH2:16][CH2:15][O:14][CH2:13][CH2:12]2)[CH:5]=[N:6][C:7]=1[N+:8]([O-])=O.[NH4+].[Cl-]>CO.[Zn]>[Br:1][C:2]1[C:7]([NH2:8])=[N:6][CH:5]=[C:4]([N:11]2[CH2:12][CH2:13][O:14][CH2:15][CH2:16]2)[CH:3]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 66664889HCID 66664889, compound

Product 1

HCID 118046519HCID 118046519, compoundYield 52.6%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 4-(5-Bromo-6-nitropyridin-3-yl)morpholine (2 g, 6.9 mmol) in MeOH (150 mL) in a round bottom flask was added Zn dust (4.54 g, 69.4 mmol). The reaction mixture was cooled to 0° C. Solid NH4Cl (3.71 g, 69.4 mmol) was added in portions, over 5 min. The heterogeneous reaction mixture was stirred at room temperature for 2 h, filtered through a plug of Celite washing the filter cake with methanol and ethanol. The filtrate was concentrated to a brownish solid which was purified by flash column chromatography on silica gel (ISCO, 80 g column, 0-70% EtOAc/heptane in 15 min and 70% EtOAc to 25 min), obtaining 3-bromo-5-morpholinopyridin-2-amine (936 mg, 52.2%) as a slightly off white solid. LCMS (m/z): 258.2 (MH+), 0.35 min; 1H NMR (400 MHz, CDCl3) δ ppm 7.75 (d, J=2.3 Hz, 1H) 7.40-7.30 (m, 1H) 4.66 (br. s., 2H) 3.91-3.74 (m, 4H) 3.07-2.90 (m, 4H).

Workup

  1. filtrationfiltered through a plug of Celite
  2. washwashing the filter cake with methanol and ethanol
  3. concentrationThe filtrate was concentrated to a brownish solid which
  4. customwas purified by flash column chromatography on silica gel (ISCO, 80 g column, 0-70% EtOAc/heptane in 15 min and 70% EtOAc to 25 min)

Sources & evidence

ORD record
ord-201015cb6af249b5a61f12e09877f0a7
Source dataset
uspto-grants-2016_01
Patent number
US09242996B2

Reaction notes

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