The highly regioselective C-N bond formation between phenytoin and acrylic/fumaric esters was accomplished. Solvent-free media Michael addition of phenytoin to acrylic esters led to the selective synthesis of N3-substituted phenytoins (as mono-Michael adducts) in the presence of tetrabutylammonium bromide (TBAB) and potassium carbonate under ultrasonic irradiation conditions at room temperature. These reactions produced N1,N3-disubstituted phenytoins (as bis-Michael adducts) at 70 ºC. Surprisingly, the addition of phenytoin to fumaric esters, instead of acrylic esters, selectively provided only N3-substituted phenytoins at both room temperature and 70 ºC under the same conditions.