Ammonia → (2-amino-5-bromo-pyridin-3-yl)-(2-ethyl-2H-pyrazol-3-yl)-methanone

HRID 2234666Notes

Reaction equation

HRID 2234666 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:9]([C:11]2[N:12]([CH2:16][CH3:17])[N:13]=[CH:14][CH:15]=2)=[O:10])[C:5](F)=[N:6][CH:7]=1.N.C([N:22](C(C)C)CC)(C)C>>[NH2:22][C:5]1[C:4]([C:9]([C:11]2[N:12]([CH2:16][CH3:17])[N:13]=[CH:14][CH:15]=2)=[O:10])=[CH:3][C:2]([Br:1])=[CH:7][N:6]=1

Participants

4

Reactant 3

HCID 222AmmoniaHCID 81531DiisopropylethylamineHCID 57731543(5-bromo-2-fluoro-pyridin-3-yl)-(2-ethyl-2H-pyrazol-3-yl)-methanone

Product 1

HCID 57731574(2-amino-5-bromo-pyridin-3-yl)-(2-ethyl-2H-pyrazol-3-yl)-methanoneYield 50.2%

Conditions

Temperature
90 °C

Procedure

(5-Bromo-2-fluoro-pyridin-3-yl)-(2-ethyl-2H-pyrazol-3-yl)-methanone (685 mg, 2.29 mmol) was combined with ammonia (0.5M in dioxane, 30 ml, 15.00 mmol) and di-iso-propylethylamine (4 ml, 23.43 mmol). The mixture was stirred for 18 hours at 90° C. The reaction mixture concentrated in vacuo. The crude material was combined with a saturated aqueous solution of sodium bicarbonate, and ethyl acetate and the biphasic mixture was stirred for 1 hour. The organic layer was separated, dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography (0 to 100% [10% methanol in ethyl acetate] in hexanes) to give 339 mg (50%) of (2-amino-5-bromo-pyridin-3-yl)-(2-ethyl-2H-pyrazol-3-yl)-methanone. 1H-NMR (250 MHz, d6-DMSO) δ 8.35 (d, J=2.3 Hz, 1H), 7.99 (d, J=2.5 Hz, 1H), 7.68 (s, 2H), 7.61 (d, J=1.8 Hz, 1H), 6.71 (d, J=1.8 Hz, 1H), 4.35 (quart., J=7.0 Hz, 2H), 1.37 (t, J=7.3 Hz, 3H); MS: m/z 295.1+297.1 (M+H+).

Workup

  1. concentrationThe reaction mixture concentrated in vacuo
  2. stirringthe biphasic mixture was stirred for 1 hour
  3. customThe organic layer was separated
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified by flash chromatography (0 to 100% [10% methanol in ethyl acetate] in hexanes)

Sources & evidence

ORD record
ord-da783848044d4523b8539a14ac53744c
Source dataset
uspto-grants-2010_05
Patent number
US07709645B2

Reaction notes

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