Hydrochloric Acid → HCID 16079271, compound

Temperature

0 °C

Tetramethylethylenediamine (TMEDA) (10.44 mL, 8.035 g, 69.15 mmol) was added via syringe to n-BuLi (43.22 mL of 1.6 M in hexanes, 69.15 mmol) and the solution was chilled to 0° C. A solution of 4-chlorothiophenol (5.00 g, 34.57 mmol) in cyclohexane (25 mL) was added with stirring over 1 hour. The resulting tan slurry was stirred overnight at room temperature, chilled to 0° C., and DMF (2.94 mL, 2.78 g, 38.03 mmol) was added via syringe over 2 minutes. The resulting gummy slurry was stirred at room temperature for 30 hours and became a powdery suspension. A mixture of 2 N HCl and ice was added to the reaction mixture until the pH became acidic (pH=1). During this addition, the mixture warmed and became first red and then pale yellow. This mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4, (filtered and concentrated in vacuo yielding a clear red-brown oil. This oil was triturated with hexanes yielding a red-brown semisolid. This semisolid was purified by plug flash chromatography over silica gel, eluting with 1:1, hexanes:dichloromethane to afford 5-chloro-thiosalicylaldehyde (0.858 g, 14%) as an intensely yellow solid suitable for use without further purification.

1. stirringThe resulting tan slurry was stirred overnight at room temperature
2. temperaturechilled to 0° C.
3. stirringThe resulting gummy slurry was stirred at room temperature for 30 hours
4. additionwas added to the reaction mixture until the pH
5. additionDuring this addition
6. temperaturethe mixture warmed
7. extractionThis mixture was extracted with ethyl acetate
8. washThe combined organic layers were washed with brine
9. dry with materialdried over MgSO4
10. filtration(filtered
11. concentrationconcentrated in vacuo
12. customyielding a clear red-brown oil
13. customThis oil was triturated with hexanes yielding a red-brown semisolid
14. customThis semisolid was purified by plug flash chromatography over silica gel
15. washeluting with 1:1, hexanes

ORD record

ord-ab9c715fb5e74d47bea0f62ba88c4468

Source dataset

uspto-grants-2004_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06806288B1