Summary: | New liquid crystals have been synthesized and their transition phases have been studied. It was found that a family of (-)-2-methyl 2R,3S-epithio-4'-alkoxybiphenyl pentanoates are liquid crystals but a similar system of ( + )-2-methyl 2S,3R-epoxy-4'-alkoxybiphenyl pentanoates are not. Of the liquid crystals, MEAOBP-S-7 exhibits smectic A and B phases; MEAOBP-S-8 and MEAOBP-S-9 show only the smectic B phases; MEAOBP-S-10 shows a monotropic chiral smectic C phase. This distinction is in agreement with the argument that the internal dipolar interaction of the molecule plays an important role in determining liquid crystalline behaviour of this ester system.
The reaction rate of the racemization of optically active binaphthyl can be moderately increased in the presence of finely divided titanium dioxide (anatase) powder. This first order catalyzed reaction has a proportional relationship with the concentrations of both the catalyst and the binaphthyl.
The catalyzed reaction can be poisoned permanently by the addition of polynuclear aromatic compounds and the poisoning efficiency is dependent of the number of the aromatic rings the poison posesses. By comparison with the catalyzed racemizations of binaphthyl by platinum, nickel and carbon and from the kinetic and mechanistic studies on the titanium dioxide catalyzed racemization, we conclude that (1) this catalytic phenomenon is common among heterogeneous inorganic solids and can be extended to other simple reactions, and that (2) the mechanism of the catalysis probably involves a radical anion intermediate. === Science, Faculty of === Chemistry, Department of === Graduate
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