The kinetics of the reactions of secondary alicyclic amines with bis(4‐nitrophenyl) carbonate ( 1 ), S ‐(4‐nitrophenyl) O ‐(4‐nitrophenyl) thiocarbonate ( 2 ) and S ‐(4‐nitrophenyl) O ‐(4‐nitrophenyl) dithiocarbonate ( 3 ) were studied at 25.0 °C. The reactions of 1 were studied in water and those of 2 and 3 in 44 wt% ethanol–water. These reactions are concerted. The HPLC analyses of the reactions of 2 and 3 with morpholine show that both 4‐nitrophenoxide and 4‐nitrobenzenethiolate ions are the nucleofuges. Copyright © 2013 John Wiley & Sons, Ltd.