Benzaldehyde → Piperazine

Temperature

50 °C

At room temperature, a three-neck flask equipped with a reflux condenser, internal thermometer, dropping funnel and stirrer under protective nitrogen gas was initially charged with 4.6 g of zinc powder (71 mmol) in 40 ml of ethyl acetate. After 1.13 ml of trimethylchlorosilane had been added, the mixture was heated to 50° C. for 15 min and 10 g of 1-phenylhexan-3-one (57 mmol, prepared by base-catalyzed aldol condensation of benzaldehyde and pentan-2-one and subsequent hydrogenation of the 1-phenylhex-1-en-3-one obtained) were added undiluted. Subsequently, 10.4 g of methyl bromoacetate (68 mmol) were added dropwise within 5 min and the temperature was maintained at 40° C. by external cooling. The mixture was then stirred at 40° C. for 10 min (formation of the zinc alkoxide). After cooling to 10° C., 7.4 g of trimethylchlorosilane (68 mmol) were added and the mixture was heated to 40° C. for 30 min. After the ethyl acetate solvent had been removed (recovery of the anhydrous solvent), 40 ml of pentane were added and 7.4 g of solid piperazine (85 mmol) were subsequently added at 20° C. The mixture was then stirred at 50° C. for 6 h, and the suspension was cooled to −20° C., stirred for 1 h and solid formed (complex of zinc bromide chloride and piperazine) was filtered off. The solid was washed three times with 10 ml of pentane. The mixture was filtered again, pentane was filtered off under reduced pressure (recovery of pentane) and the desired product methyl 3-trimethylsiloxy-3-(2″-phenylethyl)caproate was obtained in a yield of 15.8 g (86% of theory) and a purity of >97% (HPLC). The zinc content of the product was 40 ppm (ICP).

1. customAt room temperature, a three-neck flask equipped with a reflux condenser
2. customobtained)
3. additionwere added undiluted
4. temperaturethe temperature was maintained at 40° C. by external cooling
5. temperatureAfter cooling to 10° C.
6. temperaturethe mixture was heated to 40° C. for 30 min
7. customAfter the ethyl acetate solvent had been removed (recovery of the anhydrous solvent), 40 ml of pentane
8. additionwere added
9. temperaturethe suspension was cooled to −20° C.
10. stirringstirred for 1 h

ORD record

ord-43518c66b6ce4393934ce54ba7fdf8fa

Source dataset

uspto-grants-2005_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06921487B2