N-(Alkyl) imino derivatives of trifluoroacetyl phenol of the general formula 1,2-C 6 H 4 [C(=NR)CF 3 ][OH] (R=H, 3a; Me, 3b; n Pr, 3c; i Pr, 3d; CH 2 CH 2 NH 2 , 3e; CH 2 CH 2 CH 2 NH 2 , 3f; CH 2 CH 2 CH 2 CH 2 NH 2 , 3g; CH 2 CH 2 OH, 3h; CH 2 CH 2 NMe 2 , 3i) were synthesized from 2-trifluoroacetyl phenol and the corresponding primary amines RNH 2 . The molecular structures of 3b [monoclinic, P2 1 /n,a = 6.641 (3),b = 18.044(8), c = 7.716(3) , β = 99.95 (4) °], 3d [orthorhombic, P2 1 2 1 2 1 ,a = 7.784(2), b = 9.291(2), c = 15.942(4) ] and 3i [monoclinic,P 2 1 /n, a = 8.660(2), b = 18.135(2), c = 13.300(2) , β = 99.83 (2) °] were determined. In the solid state, 3b, 3d and 3i exist exclusively as E isomers with intermolecular hydrogen bridges, whereas according to the 1H and 19F NMR spectra in chloroform solution, compounds3b , 3c and 3d isomerize to give a mixture of 66% Z and 34% E isomers.