Hydrochloric Acid → HCID 19021827, compound

Temperature

-10 °C

A 1.0M solution of lithium bis(trimethyl)silylamide in THF (28.7 mL, 28.77 mmol) was added to 30 mL of dry THF stirring under N2, and the solution was cooled to -10° C. A solution of 1.54 g (13.7 mmol) 1,2-cyclohexanedione in 7 mL of THF was added in a slow stream via syringe. The reaction mixture turned darkreddish brown. The reaction mixture was stirred for 15 min at -10° C. and then cooled to -50° C. A solution of 4-methylphenyl 4-methyl-benzenethiosulfonate (3.5 g, 14.2 mmol) in 10 mL of THF at -50° C. was added in one portion via syringe. The reaction mixture was stirred for 2 h at -50° C. and allowed to warm at ambient temperature until approximately 0° C., and then 100 mL of 0.1 N HCl was added. The mixture was extracted with 300 mL and then 100 mL of diethyl ether, and the combined organic extracts were dried over anhydrous sodium sulfate. Concentration in vacuo provided a yellow solid which was purified by flash chromatography over silica gel using CH2Cl2, 10% EtOAc/Hexane, and then 3% MeOH/CH2Cl2 as eluent. The desired product, 2-hydroxy-3-[(4-methylphenyl)thio]-2-cyclohexenone [Compound Iy], was isolated as a white solid (1.939 g, 60%).

1. temperaturecooled to -50° C
2. stirringThe reaction mixture was stirred for 2 h at -50° C.
3. temperatureto warm at ambient temperature until approximately 0° C.
4. extractionThe mixture was extracted with 300 mL
5. dry with material100 mL of diethyl ether, and the combined organic extracts were dried over anhydrous sodium sulfate
6. concentrationConcentration in vacuo
7. customprovided a yellow solid which
8. customwas purified by flash chromatography over silica gel

ORD record

ord-bda4e10e2b774376ac4ae53faa9cb493

Source dataset

uspto-grants-1994_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05318989