Diethyl Malonate → Ethyl p-tolylacetate

Temperature

160 °C

A dry Schlenk vessel was initially charged with 171 mg [1 mmol] of 4-bromotoluene, 1056 mg [6.6 mmol] of diethyl malonate, 1.12 mg [0.005 mmol] of Pd(OAc)2, 3.19 mg [0.011 mmol] of P(tert-Bu)3×HBF4, 594 mg [2.8 mmol] of dried K3PO4 and 132 mg [0.5 mmol] of 18-crown-6. The reaction vessel was three times evacuated and filled with nitrogen. This was followed by stirring at 160° C. until completion of conversion (8 to 12 hours). After cooling to room temperature, the reaction mixture was diluted with ethyl acetate. The resulting solution was washed successively with 20 ml each of water, saturated aq. NaHCO3 solution and saturated aq. NaCl solution, dried over MgSO4, filtered and concentrated under reduced pressure. Chromatographic purification using silica gel (hexane/ethyl acetate) gave ethyl 4-methylphenylacetate in a yield of 75% of theory.

1. customevacuated
2. additionfilled with nitrogen
3. temperatureAfter cooling to room temperature
4. additionthe reaction mixture was diluted with ethyl acetate
5. washThe resulting solution was washed successively with 20 ml each of water, saturated aq. NaHCO3 solution and saturated aq. NaCl solution
6. dry with materialdried over MgSO4
7. filtrationfiltered
8. concentrationconcentrated under reduced pressure
9. customChromatographic purification

ORD record

ord-d4e2fc71fc5543aea79a2bb58bcaa9e7

Source dataset

uspto-grants-2015_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09096568B2