Some derivatives of 4-(4-alkoxyphenoxycarbonyl)phenyl 3-alkoxy-2-X-benzoates (X=F, Cl, Br, or CF3) were synthesized by means of an ortho-directed lithiation followed by an electrophilic aromatic substitution reaction, as a key step, and their thermal properties of liquid crystals were examined. These results are discussed in terms of molecular structure and electrostatic effects.