Dimethyl Sulfide → HCID 68440557, compound

Temperature

0 °C

To a solution of 1-bromo-4-methylthiobenzene (0.21 g) in tetrahydrofuran (10 mL) was added tert-butyllithium (1.6 mol/L pentane solution, 0.67 mL) at −78° C. under an argon atmosphere, and the mixture was stirred for 5 minutes. To the reaction mixture was added a solution of 3-benzyloxy-4-formyl-5-methyl-1-phenyl-1H-pyrazole (0.20 g) in tetrahydrofuran (3 mL), and the mixture was warmed to 0° C. and stirred for 30 minutes. The reaction mixture was poured into a saturated aqueous ammonium chloride solution, and the mixture was extracted with diethyl ether. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. To the residue was added hexane, and the precipitates were collected by filtration to give a white crystals. The obtained crystals were dissolved in methanol (5 mL) and tetrahydrofuran (6 mL). To a solution was added 10% palladium-carbon powder (0.30 g), and the mixture was stirred at room temperature under a hydrogen atmosphere for 16 hours. Insoluble materials were removed by filtration, and the solvent of the filtrate were removed under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=6/1-3/1) to give an oily substance. The obtained oily substance was dissolved in trifluoroacetic acid (1.9 mL) and water (0.1 mL), and to the solution was added dimethyl sulfide (0.2 mL), and the mixture was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=2/1) to give the title compound (0.054 g).

1. stirringstirred for 30 minutes
2. extractionthe mixture was extracted with diethyl ether
3. washThe organic layer was washed with water
4. dry with materialdried over anhydrous magnesium sulfate
5. customthe solvent was removed under reduced pressure
6. additionTo the residue was added hexane
7. filtrationthe precipitates were collected by filtration
8. customto give a white crystals
9. stirringthe mixture was stirred at room temperature under a hydrogen atmosphere for 16 hours
10. customInsoluble materials were removed by filtration
11. customthe solvent of the filtrate were removed under reduced pressure
12. customThe residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=6/1-3/1)
13. customto give an oily substance
14. stirringthe mixture was stirred at room temperature for 3 hours
15. concentrationThe reaction mixture was concentrated under reduced pressure
16. customthe residue was purified by column chromatography on silica gel (eluent: hexane/ethyl acetate=2/1)

ORD record

ord-3fe374af88de490aa1c2f8cd3f2db0c6

Source dataset

uspto-grants-2007_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07294618B2