1,4-Dehydrogenation with a Two-Coordinate Cyclic (Alkyl)(amino)silylene

Cyclic (alkyl)(amino)silylene (CAASi) 1 has been found to successfully dehydrogenate 1,4-dihydroaromatic compounds containing various substituents to afford the corresponding aromatic compounds. The observed high substrate generality proves 1 to be a potential 1,4-dehydrogenation reagent for organic compounds. For the reaction with 9,10-dimethyl-9,10-dihydroanthracene, silylene 1 activated not only benzylic C−H bonds but also aromatic C−H bonds to yield a silaacenaphthene derivative, which is an unprecedented reaction of silylenes. The results of the experimental and computational study of the reaction of CAASi 1 with 9,10-dihydroanthracene and 1,4-cyclohexadiene are consistent with the notion that 1,4-dehydrogenation with CAASi 1 proceeds mainly through a stepwise hydrogen-abstraction mechanism.     

Cover Feature: Fluoroalkyl Sulfoximines for Versatile Photocatalytic Radical Fluoroalkylations (Chem. Rec. 9/2023)

Fluoroalkyl sulfoximines, which serve as electron-accepting fluoroalkyl radical sources, are easy-to-handle, solid, and bench-stable chemicals. Fluoroalkyl radicals can be generated from sulfoximine reagents using strong one-electron injectors, such as a highly reducing photoredox catalyst in the excited state. Our group has developed photocatalytic radical di- and mono-fluoromethylation and α-monofluoroalkylation of olefins with the corresponding fluoroalkyl sulfoximines. In this personal account, appropriate combinations of fluoroalkyl sulfoximines and photoredox catalysts, leading to successful radical fluoroalkylation, have been discussed.     

Prediction of soil reaction forces on a moldboard plow surface

Using mathematical models, approximate trajectories of soil furrow subslices were determined and the forces occurring on the moldboard surface were calculated. The various components of the normal force along the trajectory line of the middle section of the furrow slice were analysed in relation to the velocity of plowing operation and the curvature of the path. The soil reaction forces encountered by the share portion of the plow were also determined by a model which used the method of trial wedges to determine the angle of the failure surface with the horizontal. The sum of the calculated forces was compared with that obtained by actual plowing experiments performed in the laboratory.     

Several contributions to soil compactibility induced by cyclic loading test

To investigate the soil compactibility during the cyclic loading, three different kinds of paddy field soils were prepared so as to clarify interrelationships among stress amplitude ratio, bulk density, soil water content and pore water pressure. The presetting values of specimen include the soil water content(percent dry basis) and bulk density of 25% d.b. and 1.1 Mg/m³ respectively. The relation between the number of cyclic loading and axial strain exhibited an asymptotically increasing trend, converging toward a specific value for each experimental condition. Possible effect caused by elastic–plastic characteristics could be recognized, when axial strain for 0.5 Hz excitation becomes greater than the one of 1.0 Hz under same stress amplitude ratio. When the stress amplitude ratio took 0.1, the absolute value of axial strain of 0.5 Hz was greater than the one of 1.0 Hz, whereas its decreasing trend was recognized in the sequence of silt, clay and silty sand. The qualitative relations between pore water pressure and number of cyclic loading were also examined to scrutinize the effect of effective water pressure to the soil compactibility.     

Triaxial force measurement at specific positions on a soil-cutting blade

In order to create a mathematical model of a soil-cutting blade, it is necessary to understand thoroughly the behavior of a soil slice and its interaction with the blade surface. The triaxial force transducer was developed to serve as one of the various tools to verify the proposed mathematical model. The prototype model transducer was fabricated, calibrated and tested with a soil slice on a flat cutting blade. The calibration results have indicated high sensitivity and the capability of simultaneous measurement in three directions. As a technological refinement, the detecting part of this triaxial force transducer was tapered to solve the problem of soil clogging in the opening clearance. Furthermore, the effects of the clearance configurations between the bore on the soil-cutting blade and the detecting part which is embedded in this bore were investigated to determine the most desirable configuration. The comparative results indicated that by tapering both the detecting part and the bore, the tangential stress measurement gained the highest value, and provided the most satisfactory condition for three-dimensional stress management.     

On the rate of convergence of solutions in free boundary problems via penalization

The rate of convergence of approximate solutions via penalization for free boundary problems are concerned. A key observation is to obtain global bounds of penalized terms which give necessary estimates on integrations by the nonlinear adjoint method by L.C. Evans.     

Limit theorems for the pre-averaged Hayashi–Yoshida estimator with random sampling

We will focus on estimating the integrated covariance of two diffusion processes observed in a nonsynchronous manner. The observation data is contaminated by some noise, which possibly depends on the time and the latent diffusion processes, while the sampling times also possibly depend on the observed processes. In a high-frequency setting, we consider a modified version of the pre-averaged Hayashi–Yoshida estimator, and we show that such a kind of estimator has the consistency and the asymptotic mixed normality, and attains the optimal rate of convergence.     

Evaluation of low-dose irradiation on microbiological quality of white carrots and string beans

The minimally processed food provided the consumer with a product quality, safety and practicality. However, minimal processing of food does not reduce pathogenic population of microorganisms to safe levels. Ionizing radiation used in low doses is effective to maintain the quality of food, reducing the microbiological load but rather compromising the nutritional values and sensory property. The association of minimal processing with irradiation could improve the quality and safety of product. The purpose of this study was to evaluate the effectiveness of low-doses of ionizing radiation on the reduction of microorganisms in minimally processed foods. The results show that the ionizing radiation of minimally processed vegetables could decontaminate them without several changes in its properties.     

Alternating copolymers of hexafluoroisobutylene with vinyl trifluoroacetate and vinyl pentafluorobenzoate

Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r₁ (HFIB) = 0, r₂ (VPFB) = 0.373, and r₁r₂ = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB‐co‐VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average T_gs of HFIB‐co‐VTFA and HFIB‐co‐VPFB were 52 and 71 °C, respectively. From these results, the T_g of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 °C, which may be useful in the assessment of T_gs of HFIB copolymers with other vinyl monomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

New Synthetic Method for Bicyclic Compounds Through a Sequence of Ene-Type Chlorination,Palladium Catalyzed Dehydrochlorination,and Intramolecular Diels-Alder Reaction

A sequence of ene-type chlorination, palladium catalyzed dehydrochlorination, and the intramolecular Diels-Alder reaction afforded a new method for conversion of prenyl derivatives into bicyclic compounds.