3'-Bromoacetophenone → 1-(3-Sulfanylphenyl)ethan-1-one

温度

50 °C

A solution of 3′-bromoacetophenone (10 g, 50 mmol), N,N-diisopropylethylamine (18 mL, 0.10 mol), 3-mercaptopropionic acid 2-ethylhexyl ester (11 mL, 48 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.29 g, 0.50 mmol) and tris(dibenzylideneacetone)palladium(0) (0.46 g, 0.50 mmol) in 1,4-dioxane (250 mL) was stirred at 100° C. for 2 days. After the reaction solution was filtered with celite, the filtrate was concentrated in vacuo until the volume became one third approximately. Water (200 mL) was added thereto, extracted with ethyl acetate (200 mL). The organic layer was washed with brine (200 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give a mixture including 3-(3-acetylphenyl)thiopropionic acid 2-ethylhexyl ester (19 g). This mixture (17 g) was dissolved in tetrahydrofuran (200 mL), sodium ethoxide (7.0 g, 0.10 mol) in ethanol (40 mL) was added thereto, and then the whole was stirred at 50° C. for 2 hours. Water (200 mL) was added to the reaction solution and washed with ethyl acetate (200 mL). 1N Hydrochloric acid (100 mL) was added to the aqueous layer and extracted with ethyl acetate (300 mL), then the organic layer was washed with brine (100 mL) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to give the title reference compound (6.2 g) as a brown oil (Yield 81%).

1. filtrationAfter the reaction solution was filtered with celite
2. concentrationthe filtrate was concentrated in vacuo until the volume
3. additionWater (200 mL) was added
4. extractionextracted with ethyl acetate (200 mL)
5. washThe organic layer was washed with brine (200 mL)
6. dry with materialdried over anhydrous magnesium sulfate
7. customThe solvent was removed under reduced pressure
8. customto give a mixture
9. washwashed with ethyl acetate (200 mL)
10. addition1N Hydrochloric acid (100 mL) was added to the aqueous layer
11. extractionextracted with ethyl acetate (300 mL)
12. washthe organic layer was washed with brine (100 mL)
13. dry with materialdried over anhydrous magnesium sulfate
14. customThe solvent was removed under reduced pressure

ORDレコード

ord-44e9585a74824e2d97e3ec3bab9c276e

出典データセット

uspto-grants-2011_07

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07977371B2