Synthesis and properties of optically active 1,3-diols and their derivatives as chiral dopants for ferroelectric liquid crystals

Abstract

New chiral dopants β-hydroxy ketones 1, 1,3-diols 2, 1,3-dioxanes 3 and 1,3-dioxan-2-ones 4 were designed and synthesized. Reaction of (R)-1,2-epoxyoctane with carbanions derived from 2-(4-substituted phenyl)-1,3-dithianes followed by hydrolysis of the resulting hydroxy dithianes afforded 1. Reduction of 1 gave the diols 2, which yielded 3 upon acetalization and 4 upon carbonation. The syn isomers of 2, 3, and 4 exhibited larger spontaneous polarizations, when applied as chiral dopants, than the anti isomers or hydroxy ketones 1.     

Thermal and evolved gas analyses of the oxidation of a cellulose/copper(II) oxide mixture

Cellulosic biomass is a promising alternative energy resource from the viewpoint of sustainability. The use of waste materials as cellulosic biomass could additionally contribute to a recycling society. It is thus essential to develop safer processes in order to expand utilization of cellulosic biomass as a useful resource in the future. For example, in some cases, construction wastes contain wood preservatives, including metal oxides that can act as catalysts for the oxidation of organic materials. Copper(II) oxide (CuO) is a major component in wood preservatives and is known to catalyze the oxidation of cellulose. There is, therefore, possibility for spontaneous ignition within large piles of wood chips from construction wastes. In this study, we focused on the thermal behavior of a cellulose/CuO mixture, measured using a Calvet-type heat flux calorimeter. In addition, Fourier transform infrared spectroscopy and gas chromatography were applied to analyze the oxidative decomposition gases of the cellulose/CuO mixture, and a reaction mechanism was proposed. It was revealed that CuO promotes the oxidative decomposition of cellulose and increases the quantity of the gases that evolved from cellulose with a catalytic cycle. The influence of CuO on oxidation of cellulose is greater at lower temperatures and spontaneous ignition, fires, and explosions are likely to increase when wood chips containing CuO are stored for long periods of time.     

Dimesitylborylethynylated Arenes: Unique Electronic and Photophysical Properties Caused by Ethynediyl (C≡C) Spacers

Herein, we report the synthesis and electrochemical and photophysical properties of aromatic hydrocarbons having one or two dimesitylborylethynyl peripherals. The mono- ( 1 ) and diboryl compounds ( 2 ), readily prepared by nucleophilic substitution reaction, are fairly stable to air and moisture in the solid state. The inserted ethynediyl (C≡C) spacer cancels the steric hindrance between the bulky dimesitylboryl groups and aromatic rings, leading to effective π conjugation over the B−C≡C−Ar linkages, as revealed by cyclic voltammetry. Despite the small structural differences, the photophysical properties of the benzene, naphthalene, and anthracene derivatives are different. Virtually no emission was observed from the benzene derivatives, whereas the anthracene derivatives emitted with high quantum yields both in solution and in the solid state. Notably, the naphthalene derivatives showed aggregation-induced emission behavior. Unlike the common sterically congested triarylborane derivatives reported so far, the anthracene derivatives showed π–π*-type absorption and emission bands, which derive from efficient intramolecular orbital interactions between the boron centers and anthracene moieties, as supported by DFT calculations. As a result, the dimesitylborylethynyl substituents effectively lower the LUMO levels of the aromatic hydrocarbon parts, whereas the HOMO levels are almost unaffected, thereby leading to materials with controllable HOMO–LUMO gaps.     

α- and γ-Regiocontrol and Enantiospecificity in the Copper-Catalyzed Substitution Reaction of Propargylic Phosphates with Grignard Reagents

The regioselectivity (r.s.) and enantiospecificity (e.s.) of the substitution reactions of secondary propargylic alcohol derivatives using reagents derived from ArMgBr and Cu salts were studied. First, the picolinate, 3-methylpicolinate, and diethylphosphonate derivatives of Ph(CH₂)₂CH(OH)C≡CTMS were reacted with PhMgBr/CuCN in ratios of 2.5:2.7–2.5:0.25. The use of 2.5:0.25 ratio in THF/DME (6:1) at 0 °C for 1 h afforded the α-substitution product from the phosphate with ≥98 % r.s. and 99 % e.s. CuBr⋅Me₂S gave similar selectivity. The reaction system was then applied to phosphates derived from R¹CH(OH)C≡CR² and ArMgBr to obtain synthetically sufficient r.s. and e.s. values with R²=TMS, Ph, whereas iPr was borderline in terms of size as an R¹ substituent. The presence of a substituent at the o-position of Ar marginally affected the selectivity. We also found that the use of PhMgBr/Cu(acac)₂ in a 2:1 ratio in THF produced the γ-substitution products (allenes) with high r.s. and e.s.     

Macroscopic energy diffusion for a chain of anharmonic oscillators

We study the energy diffusion in a chain of anharmonic oscillators where the Hamiltonian dynamics is perturbed by a local energy conserving noise. We prove that under diffusive rescaling of space–time, energy fluctuations diffuse and evolve following an infinite dimensional linear stochastic differential equation driven by the linearized heat equation. We also give variational expressions for the thermal diffusivity and some upper and lower bounds.