Oxygen → Thianthren-1-ol

To a cooled (−78° C.) solution of thianthrene (10 g, 46.23 mmol) in anhydrous THF (200 ml) was added t-BuLi (1.7M in pentane, 40.81 ml, 69.34 mmol), under a nitrogen atmosphere, over a period of 10 minutes and the resulting yellow solution was then allowed to warm to room temperature and stirred vigorously for a further 16 hours. EtMgBr (3M in THF, 23 ml, 69.34 mmol) was then added in a dropwise fashion to the cooled (0° C.) reaction mixture which was then stirred for a further 45 minutes before oxygen was bubbled through the solution. After two hours the reaction was quenched by dropwise addition of 1M NaOH (100 ml) and washed with EtOAc (1×300 ml) before being acidified to pH4 with aqueous 1M HCl. The mixture was then extracted with EtOAc (3×100 mL),dried (MgSO4), filtered and concentrated in vacuo to give a mild amber slurry that was purified by flash chromatography (SiO2) (10:1, Ethyl acetate/Hexanes), to give the title compound (3.82 g, 36%) as a yellow solid. m/z (LC-MS, ESP):, RT=4.62 min, (M++1)=231

1. temperaturecooled
2. custom(0° C.) reaction mixture which
3. customwas bubbled through the solution
4. customAfter two hours the reaction was quenched by dropwise addition of 1M NaOH (100 ml)
5. washwashed with EtOAc (1×300 ml)
6. extractionThe mixture was then extracted with EtOAc (3×100 mL),dried (MgSO4),
7. filtrationfiltered
8. concentrationconcentrated in vacuo
9. customto give a mild amber slurry that
10. customwas purified by flash chromatography (SiO2) (10:1, Ethyl acetate/Hexanes)

ORD record

ord-76a248e004c4433f8e5b089409fa7051

Source dataset

uspto-grants-2008_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07429660B2