Lawesson's reagent → (R)-5-(5-bromo-2-fluoro-phenyl)-5-methyl-1,1-dioxo-1lambda6-thio morpholin-3-thione

HRID 920164Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:18])=[C:6]([C@@:8]2([CH3:17])[NH:13][C:12](=O)[CH2:11][S:10](=[O:16])(=[O:15])[CH2:9]2)[CH:7]=1.COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:28])=CC=1>O1CCOCC1.C([O-])(O)=O.[Na+]>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:18])=[C:6]([C@@:8]2([CH3:17])[NH:13][C:12](=[S:28])[CH2:11][S:10](=[O:16])(=[O:15])[CH2:9]2)[CH:7]=1

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of (R)-5-(5-bromo-2-fluoro-phenyl)-5-methyl-1,1-dioxo-1λ6-thio morpholin-3-one (3.11 g, 9.25 mmol, Eq: 1.00) in dioxane (72.3 ml) was added Lawesson's reagent (2.99 g, 7.4 mmol, Eq: 0.8) at 23° C. The mixture was stirred for 2 hours at 80° C. Diluted with sat. NaHCO3-sol., extracted with ethyl acetate, washed with brine, dried over Na2SO4 and filtered off. Removal of solvent in vacuum left a yellow oil (5.8 g), which was purified by flash chromatography on 50 g silica gel with 0-50% ethyl acetate in heptane to give the (R)-5-(5-bromo-2-fluoro-phenyl)-5-methyl-1,1-dioxo-1λ6-thio morpholin-3-thione (2.7 g, 7.67 mmol, 82.9% yield) as a light yellow foam. MS (ISN): m/z=350.1 [M−H]− and 352.2 [M+2−H]−.

Workup

extraction, extracted with ethyl acetate
washwashed with brine
dry with materialdried over Na2SO4
filtrationfiltered off
customRemoval of solvent in vacuum
waitleft a yellow oil (5.8 g), which
customwas purified by flash chromatography on 50 g silica gel with 0-50% ethyl acetate in heptane

Sources & evidence

ORD record: ord-2cd23f63788346ff9d25eee93b589bba
Source dataset: uspto-grants-2016_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09273042B2

Reaction notes

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