Dimethylformamide → 5-Methyl-2-sulfanylbenzaldehyde

Temperature

0 °C

Tetramethylethylenediamine (TMEDA) (12.6 mL, 83.5 mmol) was added via syringe to n-BuLi (33 mL of 1.6 M in hexanes, 82.5 mmol) and the solution was chilled to 0° C. A solution of p-thiocresol (4.53 g, 36.5 mmol) in cyclohexane (40 mL) was added with stirring over 5 minutes. The resulting tan slurry was stirred overnight at room temperature, chilled to 0° C., and DMF (4.0 mL, 3.77 g, 51.6 mmol) was added via syringe over 2 minutes. The resulting gummy slurry was stirred at room temperature for 1.3 hours. The reaction mixture was added to 3 N HCR (150 mL). 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 brown oil. This oil was purified by flash chromatography over silica gel, eluting with 10% ethyl acetate-hexanes to afford 5-methyl-2-mercaptobenzaldehyde (4.47 g, 69%) 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 1.3 hours
4. additionThe reaction mixture was added to 3 N HCR (150 mL)
5. extractionThis mixture was extracted with ethyl acetate
6. washThe combined organic layers were washed with brine
7. dry with materialdried over MgSO4
8. filtrationfiltered
9. concentrationconcentrated in vacuo
10. customyielding a brown oil
11. customThis oil was purified by flash chromatography over silica gel
12. washeluting with 10% ethyl acetate-hexanes

ORD record

ord-7de6d122c0184c5395ea7cf1df935205

Source dataset

uspto-grants-2006_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07138411B2