A new approach to the synthesis of azulene liquid crystals is describe
d based on Hafner's procedure involving reaction of a pyridinium salt
with a cyclopentadienide. The preparation of a variety of liquid cryst
alline materials using this method is described. Variants are reported
with single substituents on the azulene ring in the B-position and do
ubly substituted in the 2,6-positions. The effect of the azulene ring
as a core or dipolar terminal structural element is explored. 6-(5-Alk
yl-1,3-dioxan-2-yl)azulenes are shown to exhibit smectic A phases and
2-cyclohexyl-6-(5-tridecyl-1,3-dioxan-2-yl)azulene show smectic A and
B phases. Phase characterisation of the materials is recorded together
with X-ray measurements on the smectic A phase of one representative
compound. Results of dichroism studies on the azulene mesogens are als
o briefly reviewed.