Hydrochloric Acid → Bis(3-methylphenyl)methanone

Temperatur

-15 °C

An oven-dried, three-necked 1-L flask equipped with magnetic stirring bar, gas inlet, dropping funnel, and condenser was flushed with nitrogen and loaded with m-tolunitrile (49.1 g, 419 mmol) and THF (30 mL). A solution of m-tolyl magnesium chloride in THF (1 M, 440 mL) was added dropwise at such a rate that the internal temperature was kept below 50° C. The mixture was heated to reflux for 18 h, then cooled to −15° C., and hydrolyzed with ice-water (210 mL) and aqueous HCl (36.5%, 300 mL). The mixture was stirred at room temperature for 30 min and heated to 80° C. for 18 h. Most of the THF (400 mL) was removed by distillation. The solution was extracted with MTBE (250 mL, 3×200 mL). The combined organic layers were washed with saturated NaHCO3 solution (200 mL) and saturated NaCl solution (200 mL), dried over MgSO4, and concentrated under vacuum to give di-m-tolyl-methanone (99.5 g, quantitative) as a red oil, which was used without further purification for the next step. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 7.62 (s, 2H), 7.54 (d, 2H, J=7.0 Hz), 7.36-7.31 (m, 4H), 2.37 (s, 6H). 13C NMR (75 MHz, CDCl3=77.23 ppm): δ (ppm): 197.1, 138.1, 133.2, 130.5, 128.3, 127.4, 21.4 [lit. ref.: Coops, J.; Nauta, W. Th.; Ernsting, M. J. E.; Faber, M. A. C. Recueil 1940, 57, 1109].

1. customAn oven-dried, three-necked 1-L flask equipped with magnetic stirring bar, gas inlet
2. customwas flushed with nitrogen
3. customwas kept below 50° C
4. temperatureThe mixture was heated
5. temperatureto reflux for 18 h
6. temperatureheated to 80° C. for 18 h
7. customMost of the THF (400 mL) was removed by distillation
8. extractionThe solution was extracted with MTBE (250 mL, 3×200 mL)
9. washThe combined organic layers were washed with saturated NaHCO3 solution (200 mL) and saturated NaCl solution (200 mL)
10. dry with materialdried over MgSO4
11. concentrationconcentrated under vacuum

ORD-Eintrag

ord-d8ced86643c248bfb5770cad39cc75a7

Quelldatensatz

uspto-grants-2013_07

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08497301B2