Stannous chloride dihydrate → 5-Bromo-2-(2,2-dimethylmorpholino)pyridin-3-amine

HRID 1431345Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]([N+:16]([O-])=O)[C:5]([N:8]2[CH2:13][CH2:12][O:11][C:10]([CH3:15])([CH3:14])[CH2:9]2)=[N:6][CH:7]=1.O.O.[Sn](Cl)Cl>CCOC(C)=O>[Br:1][C:2]1[CH:3]=[C:4]([NH2:16])[C:5]([N:8]2[CH2:13][CH2:12][O:11][C:10]([CH3:14])([CH3:15])[CH2:9]2)=[N:6][CH:7]=1

Participants

Conditions

Temperature: 90 °C

Procedure

To a stirred mixture of 4-(5-bromo-3-nitropyridin-2-yl)-2,2-dimethylmorpholine (2.22 g, 7.03 mmol) in EtOAc (30 mL) was added tin(II) chloride dihydrate (8.94 g, 39.6 mmol) in portions. Upon complete addition of the reducing agent, the mixture was carefully heated to 90° C. After 1 h, the reaction was cooled to rt, then washed with 1M NaOH, water, and brine. After drying over anhydrous sodium sulfate and filtration, the organic solvent was removed under reduced pressure. The residue was purified with silica gel chromatography (0-35% EtOAc in hexanes) to provide a colorless film as 5-bromo-2-(2,2-dimethylmorpholino)-pyridin-3-amine. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.59 (1H, d, J=2.2 Hz), 7.13 (1H, d, J=2.3 Hz), 5.10 (2H, s), 3.83 (2H, m), 2.90 (2H, m), 2.77 (2H, s), 1.24 (6H, s).

Workup

additionUpon complete addition of the reducing agent
temperaturethe reaction was cooled to rt
washwashed with 1M NaOH, water, and brine
dry with materialAfter drying over anhydrous sodium sulfate and filtration
customthe organic solvent was removed under reduced pressure
customThe residue was purified with silica gel chromatography (0-35% EtOAc in hexanes)

Sources & evidence

ORD record: ord-aad38e7a896c4bd1ba31d8351ab82db8
Source dataset: uspto-grants-2015_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08940724B2

Reaction notes

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