Bicarbonate Ion → N-(7-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-ylidene)-2-methylpropane-2-sulfinamide

HRID 1409504Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]2[C:15](=[CH:16][CH:17]=1)[O:14][C:7]1[C:8]([F:13])=[N:9][C:10]([Cl:12])=[CH:11][C:6]=1[C:5]2=O.[CH3:19][C:20]([S:23]([NH2:25])=[O:24])([CH3:22])[CH3:21].C(=O)(O)[O-]>C1COCC1.[Cl-].[Na+].O.C(O[Ti](OCC)(OCC)OCC)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:15](=[CH:16][CH:17]=1)[O:14][C:7]1[C:8]([F:13])=[N:9][C:10]([Cl:12])=[CH:11][C:6]=1[C:5]2=[N:25][S:23]([C:20]([CH3:22])([CH3:21])[CH3:19])=[O:24]

Participants

Conditions

Temperature: 75 °C

Procedure

A mixture of 7-bromo-3-chloro-1-fluoro-5H-chromeno[2,3-c]pyridin-5-one (740 mg, 2.25 mmol, Example 4), 2-methyl-2-propane-sulfinamide (819 mg, 6.76 mmol, Aldrich), and tetraethoxytitanium (6.07 mL, 29.3 mmol, Aldrich) in dry THF (15 mL) was heated at 75° C. for 24 hours under nitrogen atmosphere. The mixture was cooled to RT and brine and aqueous, saturated bicarbonate solution were added while rapidly stirring. After 1 h, the resulting suspension was filtered through celite, and the filter cake was washed with EtOAc. The filtrate was washed with brine and dried over MgSO4. The solvent was removed under reduced pressure and the remaining residue was purified by flash chromatography on silica gel (0-20% EtOAc/hexanes) to afford the title product as an orange solid. MS m/z=423.8 [M+H]+. Calculated for C16H13BrClFN2O2S: 431.71.

Workup

temperatureThe mixture was cooled to RT
filtrationthe resulting suspension was filtered through celite
washthe filter cake was washed with EtOAc
washThe filtrate was washed with brine
dry with materialdried over MgSO4
customThe solvent was removed under reduced pressure
customthe remaining residue was purified by flash chromatography on silica gel (0-20% EtOAc/hexanes)

Sources & evidence

ORD record: ord-fcb6cadf3c334ff8a362511143d243b7
Source dataset: uspto-grants-2014_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08921363B2

Reaction notes

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