The series of liquid crystalline 4-[(4′-decyloxybiphenyl-4-yl)oxycarbonyl]phthalimide alkane acid methyl esters has been synthesized and studied by DSC, polarized optical microscopy and X-ray diffraction methods. All compounds form a monolayer smectic A phase. It was found that 2-{4-[(4′-decyloxybiphenyl-4-yl)oxycarbonyl]-phthalimido}propanoic acid methyl ester and 4-[(4′-decyloxybiphenyl-4-yl)oxycarbonyl]phthalimidoacetic acid methyl ester also form a ribbon S
phase. It was shown clearly that in the former compound, transition from the S
A1
to S
phase occurs
via an intermediate S
C1
phase. The 6-{4-[(4′-decyloxybiphenyl-4-yl)oxycarbonyl]phthalimido}-hexanoic acid methyl ester exhibits smectic A
1
and C
1
phases only.
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