Ferroelectric Liquid Crystals. Part 9. Laterally substituted phenyl benzoates incorporating a trans-1,4-disubstituted cyclohexane ring

About 65 diverse phenyl benzoates incorporating a trans-1,4-disubstituted cyclohexane ring and at least one lateral substituent have been synthesised. The dependence of the liquid-crystal transition temperatures of these materials on various lateral substituents (F, Cl, CN, and Br) in different positions of the esters has been investigated systematically. The influence of up to four F-atoms in various positions of a standard ester has been thoroughly studied and the optimum combination for a broad smectic C mesomorphic range established. In consequence, three homologous series incorporating the 4-alkoxy-2,3-difluorobenzoic-acid moiety were prepared. An additional C?C bond was introduced into the alkyl chain attached to the cyclohexane ring of some of these esters and the resulting modifications of the transition temperatures determined. Three ester series incorporating a lateral substituent and the optically active (+)-(S)-(1-methylheptyl)oxy substituent have also been synthesised, and similar effects have been observed. These materials can be used as important components of commercial chiral smectic C mixtures for electro-optic display device applications.     

Ferroelectric Liquid Crystals. Part 3. Achiral phenyl benzoates incorporating a trans-4-pentylcyclohexyl moiety

About twenty substituted phenyl benzoates incorporating a trans-4-pentylcyclohexyl moiety have been synthesised. The synthesis, liquid-crystal transition temperatures, and enthalpies of fusion are reported. The effect of variations in chainlength and central linkage on the liquid-crystal transition temperatures is discussed.     

Ferroelectric liquid crystals IV. Chiral alkenyloxyphenyl benzoates

Over forty 4-alkoxyphenyl 4-alkoxybenzoates incorporating an olefinic double bond in one carbon chain and an optically active centre in the second (methyl branched) chain have been prepared. The effect of chain length and the position of the chiral centre on the liquid crystal transition temperatures of the esters has been investigated systematically. Apart from one important exception the double bond was maintained in a terminal position of the carbon chain. Several of the new esters exhibit an enantiotropic chiral smectic C mesophase at and just above room temperature.     

The conformation and vibrational spectra of trans-1,4-dihalocyclohexanes: Part III. trans-1,4-Diiodo-, trans-1,4-bromoiodo- and trans-1,4-dibromocyclohexane

The IR spectra of trans-1,4-diiodo- and trans-1,4-bromoiodocyclohexane as solutes in various solvents, as pellets and as solids under high pressure are recorded in the region 4000–30 cm^?1. Additional spectra of the melts, amorphous and annealed crystalline solids at 90 K and dichroic spectra of oriented crystals are recorded above 200 cm^?1. Raman spectra of the amorphous and annealed solids at 90 K and as solutes in various solvents, are obtained, including polarization measurements. IR and Raman spectra of trans-1,4-di-bromocyclohexane in the temperature range 90–250 K are recorded. Equilibrium mixtures of ee and aa conformers of the title compounds are observed in solution, in the melts and in the amorphous solid at 90 K. The ee conformer only is present in the stable crystal, while the aa conformer predominates in apparently metastable crystals annealed to ca. 205 K. The concentration of the aa conformer increases under high pressure (50 kbar). Fundamental frequencies for both ee and aa conformers are assigned. A normal coordinate analysis is carried out, and the force Fields adjusted to nine halogenated cyclohexanes using the overlay technique.     

The conformation and vibrational spectra of trans-1,4-dihalocyclohexanes: Part II. trans-1,4-Chlorobromocyclohexane and trans-1,4-chloroiodocyclohexane

The IR spectra of trans-1,4-chlorobromo- and trans-1,4-chloroiodocyclohexane were recorded in the region 4000–30 cm^?1 as solutes in various solvents, as KI and polyethylene pellets and as solids under high pressure (1–50 kbar at ambient temperature). Additional spectra of the melts, amorphous and annealed crystalline solids at 90 K and dichroism of oriented polycrystalline films were obtained above 200 cm^?1. Raman spectra of the compounds were recorded in the amorphous and crystalline states at 90 K, and polarization measurements were made in CCl₄ CS₂ and C₆H₆ solution.The title compounds existed as an equilibrium mixture of ee and aa conformers in solution, in the melts and in the amorphous solids at 90 K. When heated to temperatures in the region 165–195 K the amorphous solids apparently crystallized into a metastable form containing the aa conformer, while above 200 K the solids were converted to a stable crystal containing the ee conformer. Under high pressure the concentration of the aa conformer increased and this form was almost exclusively present at ca. 50 kbar nominal pressure.The fundamental frequencies for both conformers were assigned in terms of C_smolecular symmetry. An extensive normal coordinate analysis on six trans-1,4-dihalocyclohexanes was carried out using the overlay technique.     

Laterally 4-nitrobenzyloxycarbonyl substituted phenyl benzoates: The first two-ring mesogens with a lateral branch containing a phenyl ring

The synthesis and properties of laterally 4-nitrobenzyloxycarbonyl substituted phenyl benzoates are described; these compounds represent the first two-ring mesogens having a phenyl ring in the lateral branch. The lengths of the terminal chains of the core carrying the branch have a great influence, as shown by the phase behaviour of two homologous series. Compounds having long alkyloxy groups exhibit enantiotropic smectic A phases. It should be emphasized that the mesophase thermal stability of these strongly branched derivatives can be higher than that of the laterally unsubstituted parent compound. Connecting two of the new mesogens by means of an aliphatic spacer results in a novel type of twin molecule.     

Laterally 4-nitrobenzyloxycarbonyl substituted phenyl benzoates: The first two-ring mesogens with a lateral branch containing a phenyl ring

The synthesis and properties of laterally 4-nitrobenzyloxycarbonyl substituted phenyl benzoates are described; these compounds represent the first two-ring mesogens having a phenyl ring in the lateral branch. The lengths of the terminal chains of the core carrying the branch have a great influence, as shown by the phase behaviour of two homologous series. Compounds having long alkyloxy groups exhibit enantiotropic smectic A phases. It should be emphasized that the mesophase thermal stability of these strongly branched derivatives can be higher than that of the laterally unsubstituted parent compound. Connecting two of the new mesogens by means of an aliphatic spacer results in a novel type of twin molecule.     

Ferroelectric liquid crystals VI. Chiral 5-alkyl-2-phenylpyrimidines

Abstract

Over 50 variously substituted 5-alkyl-2-phenylpyrimidines have been synthesized. The effect of the presence of an additional olefinic double bond in the terminal position of the alkoxy chain or of a trans-1,4-disubstituted cyclohexane ring on the liquid crystal transition temperatures of these systems has been studied in detail. All of the phenyl-pyrimidines studied possess an optically active centre at the point of methyl branching of one of the terminal carbon chains. The dependence of the transition temperatures of these systems on the position of the chiral centre has also been investigated. The effect of chain length has also been studied for various homologous series of mesogens. Almost all of the 5-alkyl-2-phenylpyrimides prepared exhibit enantiotropic chiral smectic C and cholesteric mesophases, some at and just above room temperature.     

Liquid Crystals with Large Negative Dielectric Anisotropy. Part V

Liquid crystals with negative Δϵ can be obtained by incorporating a cyano group in the terminal alkyl substituent or in an ethylene bridge between the cyclic units of the rigid core. The clearing points of such compounds are higher than those of the corresponding derivatives where the cyano group is laterally attached to a phenyl moiety. In compounds where both cyclic units of the rigid core are cyclohexyl, this type of substitution leads to an optimal contribution to ϵ⟂ in contrast to the cyanophenyl derivatives.     

Ferroelectric liquid crystals VI. Chiral 5-alkyl-2-phenylpyrimidines

Over 50 variously substituted 5-alkyl-2-phenylpyrimidines have been synthesized. The effect of the presence of an additional olefinic double bond in the terminal position of the alkoxy chain or of a trans-1,4-disubstituted cyclohexane ring on the liquid crystal transition temperatures of these systems has been studied in detail. All of the phenyl-pyrimidines studied possess an optically active centre at the point of methyl branching of one of the terminal carbon chains. The dependence of the transition temperatures of these systems on the position of the chiral centre has also been investigated. The effect of chain length has also been studied for various homologous series of mesogens. Almost all of the 5-alkyl-2-phenylpyrimides prepared exhibit enantiotropic chiral smectic C and cholesteric mesophases, some at and just above room temperature.     

Chiral 1,4-morpholin-2,5-dione derivatives as α-glucosidase inhibitors: Part 2

A series of chiral 1,4-morpholin-2,5-dione derivatives were synthesized starting from chiral synthons 1 and 2, diastereomeric monolactim ethers derived from l-valine. The compounds investigated, were inactive toward β-glucosidase, α-mannosidase and α-galactosidase but behave as noncompetitive inhibitors against the α-glucosidase (from Saccharomices cervisiae) with some showing a good inhibition ability (0.05 < K_i < 0.18 mM).     

Chiral 1,4-bensodiazepines. V. - synthesis and properties of 1,4-benzodiazepin-2-ones containing α-amino acids as a part of the 1,4-diazepine ring

Chiral 1,4-benzodiazepin-2-ones XIII-XXIIII (Scheme 1) were prepared starting from N-protected α-amino acids and 2-amino-5chlorobenzeophenone; the intermediates I-XII were isolated and identified. Spectroscopie propertiec of these componds are discussed (ir, nmr); their optical stability, as well as the cyclization rate for XII-XIII in buffer solution have been determined.     

Stable Liquid Crystals with Large Negative Dielectric Anisotropy. Part IV

Stable liquid crystals with negative dielectric anisotropy containing the bicyclo [2.2.2]octyl group were synthesized. The incorporation of this moiety in the molecules increased the thermodynamic stability of the mesophase and lowered the smectic tendency. These new compounds can be useful in liquid crystal mixtures for homeotropic nematic displays.     

Liquid crystalline benzothiophenes. Part 3: 2,4- and 2,7-disubstituted benzothiophenes

Five series of compounds based on 2,4- and 2,7-disubstituted benzothiophenes have been prepared and studied with respect to their mesomorphic properties. The molecular structure was modified by prolonging the molecular arms (varying the alkyl chain length) and orientation of the ester linkages. It was established that the transition temperatures and the type of the formed phases strictly depend on the ester orientation and only limited number of prepared compounds exhibited mesomorphic behaviour. Based on X-ray patterns, columnar phases were identified and found that they have centred crystallographic unit cell differing in the lattice parameters for homologous compounds. Although the bend angle of the studied materials is around 90° only, they exhibited formation of phases typical of the bent-shaped liquid crystals.     

Electrolytic reduction of 2-butyne-1,4-diol as a route to trans-2-butene-1,4-diol

The effect of the cathode material on the electrochemical transformations of 2-butyne-1,4-diol at atmospheric pressure was studied by chromatographic analysis. The optimal parameters of the selective synthesis of trans-2-butene-1,4-diol were determined.     

Photocontrolled Phase Transitions and Reflection Behaviors of Smectic Liquid Crystals by a Chiral Azobenzene

The photocontrolled phase transitions and reflection behaviors of a smectic liquid crystal, 4‐octyl‐4′‐cyanobiphenyl (8CB), tuned by a chiral azobenzene, are systematically investigated. For the smectic 8CB doped with the chiral azobenzene (1R)‐(?)‐4‐n‐hexyl‐4′‐menthylazobenzene (ABE), the initial smectic phase can be switched to cholesteric and then to isotropic upon UV irradiation due to the trans‐to‐cis photoisomerization of ABE; however, no reflection band is observed. For the smectic 8CB doped with ABE and the chiral agent (S)‐(?)‐1,1′‐binaphthyl‐2,2′‐diol (BN), a reflection band located in the short‐wavelength infrared region is observed, which disappears after further UV irradiation. For the smectic 8CB doped with ABE and a chiral agent with higher helical twisting power, (S)‐2,2′‐methylendioxy‐1,1′‐binaphthalene (DBN), a phototunable system with cholesteric pitch short enough to reflect visible light is demonstrated. With a given concentration of the chiral dopant DBN, a reversible reflection color transition is realized tuned by the isomerization of azobenzene. The reverse phase transition from isotropic to cholesteric and then to smectic can be recovered upon visible irradiation. The photocontrolled phase transitions in smectic liquid crystals and the corresponding changes in reflection band switched by photoisomerization of azobenzene may provide impetus for their practical application in optical memories, displays, and switches.