Ethyl Acetate → (NE,R)-N-[1-(3-chloro-2-fluorophenyl)ethylidene]-2-methylpropane-2-sulfinamide

HRID 930413

Reaction equation

[Cl:1][C:2]1[C:3]([F:11])=[C:4]([C:8](=O)[CH3:9])[CH:5]=[CH:6][CH:7]=1.[CH3:12][C:13]([S@:16]([NH2:18])=[O:17])([CH3:15])[CH3:14].CCOC(C)=O.C([O-])(O)=O.[Na+]>C1COCC1.[Cl-].[Na+].O.C(O[Ti](OCC)(OCC)OCC)C>[Cl:1][C:2]1[C:3]([F:11])=[C:4](/[C:8](=[N:18]/[S@@:16]([C:13]([CH3:15])([CH3:14])[CH3:12])=[O:17])/[CH3:9])[CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 70 °C

Procedure

To a solution of 1-(3-chloro-2-fluorophenyl)ethanone (5.60 g, 31.5 mmol) and (R)-2-methylpropane-2-sulfinamide (5.72 g, 47.2 mmol) in THF (50.0 mL) was added tetraethoxytitanium (16.50 mL, 79 mmol) and the overall bright yellow solution was heated at 70° C. for overnight. The reaction was slightly cooled with ice-water bath, then was added EtOAc (50 mL), NaHCO3 (10 mL), and brine (10 mL). The slurry was filtered through a short path of Celite and the wet cake was washed with EtOAc. The resulted bright yellow solution was phase separated, and the organic layer was concentrated to afford the title compound (8.3 g, 30.1 mmol, 96% yield) as a light yellow oil. This material was used in the next step without purification. MS m/z=276.0 [M+H]+. Calculated for C12H15ClFNOS: 275.77.

Workup

temperatureThe reaction was slightly cooled with ice-water bath
filtrationThe slurry was filtered through a short path of Celite
washthe wet cake was washed with EtOAc
customseparated
concentrationthe organic layer was concentrated

Sources & evidence

ORD record: ord-d619eefffc7e41c49d079b63da1b4f74
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09296734B2

Linked notes

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