Potassium Carbonate → 4-(5-Bromo-pyridin-2-ylmethyl)-thiomorpholine 1,1-dioxide

HRID 1262211Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8]Br)=[N:6][CH:7]=1.[NH:10]1[CH2:15][CH2:14][S:13](=[O:17])(=[O:16])[CH2:12][CH2:11]1.C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8][N:10]2[CH2:15][CH2:14][S:13](=[O:17])(=[O:16])[CH2:12][CH2:11]2)=[N:6][CH:7]=1

Participants

Conditions

Temperature: 40 °C

Procedure

A suspension of 5-bromo-2-bromomethyl-pyridine (1.34 g, 5.34 mmol), thiomorpholine 1,1-dioxide (0.860 g, 6.36 mmol), and potassium carbonate (1.49 g, 10.8 mmol) in acetone (15.0 mL) was stirred at 40° C. overnight. The mixture was cooled to room temperature and the volatiles were evaporated. The residue was partitioned between EtOAc (100 mL) and saturated aqueous ammonium chloride (50 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. Purification by silica gel chromatography using a gradient of 0-100% EtOAc/hex as the eluting solvent to obtain 4-(5-bromo-pyridin-2-ylmethyl)-thiomorpholine 1,1-dioxide as a white solid (1.37 g, 84%). m.p.=129-131° C.; LCMS (m/e) 305 (M+H); 1H-NMR (CDCl3, 400 MHz) δ 8.64 (d, 1H, J=2.3 Hz), 8.82 (dd, 1H, J=2.3 and 8.3 Hz), 7.29 (d, 1H, J=8.3 Hz), 3.78 (s, 2H), 3.13-3.02 (m, 8H).

Workup

temperatureThe mixture was cooled to room temperature
customthe volatiles were evaporated
customThe residue was partitioned between EtOAc (100 mL) and saturated aqueous ammonium chloride (50 mL)
dry with materialThe organic layer was dried over sodium sulfate
filtrationfiltered
concentrationconcentrated under reduced pressure
customPurification by silica gel chromatography

Sources & evidence

ORD record: ord-6fd07cdca4ed4da592769c8012efd9b2
Source dataset: uspto-grants-2013_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08471005B2

Reaction notes

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