All Non-Carbon B3NO2 Exotic Heterocycles: Synthesis,Dynamics, and Catalysis

The B₃NO₂ six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B₃NO₂ ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation.     

Electroneutrality coupling of electron transfer at an electrode surface and ion transfer across the interface between thin-layer of 1-octyl-3-methylimidazolium bis(perfluoroalkylsulfonyl)imide covering the electrode surface and an outer electrolyte solution.

The electrode reaction of decamethylferrocene (DMFc) dissolved in a thin layer of a room-temperature molten salt (RTMS), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N) or 1-octyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide (C8mimC2C2N), on a self-assembled monolayer-modified gold electrode is coupled with the ion transfer across the interface between the RTMS and the outer aqueous solution (W) to give a voltammogram whose shape resembles a voltammogram of a simple one-electron transfer process. The electroneutrality of the RTMS layer during the oxidation of DMFc to decamethylferricenium ion is maintained by the concomitant dissolution of C8mim+ ion from the RTMS phase to the W phase, and the reduction of decamethylferricenium ion to DMFc is accompanied by the transfer of either C1C1N- or C2C2N- from RTMS to W. The midpoint potential of the voltammogram varies with the concentration of the salt in the aqueous phase, C8mimCl or LiCnCnN (n = 1 or 2), in a Nernstian manner, showing that the phase-boundary potential between the RTMS and the W is controlled by the partition of these ions. Although the phase-boundary potential across the RTMS / W interface is Nernstian with respect to the ions common to both phases at the equilibrium, the polarization at the RTMS / W interface under current flow distorts the shape of the voltammograms, resulting in a wider peak separation in the voltammogram.     

A two step algorithm for solving a large scale semi-definite logit model

This paper proposes a two step algorithm for solving a large scale semi-definite logit model, which is appreciated as a powerful model in failure discriminant analysis. This problem has been successfully solved by a cutting plane (outer approximation) algorithm. However, it requires much more computation time than the corresponding linear logit model. A two step algorithm to be proposed in this paper is intended to reduce the amount of computation time by eliminating a certain portion of the data based on the information obtained by solving an associated linear logit model. It will be shown that this algorithm can generate a solution with almost the same quality as the solution obtained by solving the original large scale semi-definite model within a fraction of computation time.     

A characteristic effect of pressure on inclusion complexation of phenothiazine dyes with p-sulfonatocalix[6]arene in a room-temperature ionic liquid

The inclusion complexation of p-sulfonatocalix[6]arene (Calix-S6) with three kinds of phenothiazine dyes was studied spectrophotometrically in a mixture of a room-temperature ionic liquid [bmim]BF₄ (1-butyl-3-methylimidazolium tetrafluoroborate) and ethanol. We have determined the association constants of Calix-S6 with phenothiazine dyes under external static pressure up to 767 bar in the [bmim]BF₄-ethanol and alcohol-water mixtures. With increasing external pressure, the inclusion equilibrium in the alcohol-water mixtures was shifted to the dissociation side. Conversely, the inclusion equilibrium of methylene blue (MB) and azure A (AA) in the ionic liquid mixture was shifted to the association side. From the analysis of the pressure effects, the reaction volumes ΔV for inclusion complexation were estimated as −7 to 9 cm³ mol⁻¹ in the [bmim]BF₄-ethanol mixture and 20–32 cm³ mol⁻¹ in the alcohol-water mixtures. Based on the results, we have suggested that there is a competing complexation between the included dye and [bmim]BF₄ molecules in the ionic liquid.     

Synthesis and properties of polydiene and polypentenamer having formyl or hydroxymethyl groups and their photosensitive derivatives

cis-1,4-Polybutadiene and polypentenamer having pendant functional groups such as formyl, aldoxime, hydroxymethyl, or cinnamoyloxymethyl groups have been prepared, and some of their properties were investigated in terms of structural effect on physical properties of these polymers. cis-1, 4-Polybutadiene and polypentenamer having a different content of formyl group were prepared by the hydroformylation reaction with rhodium catalyst under mild conditions. The pendant formyl group was reduced to a hydroxymethyl group by using various reducing agents such as sodium borohydride or sodium trimethoxyborohydride which were effective to avoid a crosslinking reaction among the formyl groups. Glass transition temperature of polypentenamer having hydroxymethyl groups increased with increasing the content of the hydroxymethyl groups in the polymer. Cinnamoyl group was introduced into the polypentenamer having hydroxymethyl groups by reacting with cinnamoyl chloride so as to prepare a photosensitive rubber. The relationships between the photosensitivity of the cinnamoylated polypentenamer and the mobility of polymer main chains have been elucidated. A linear relationship between the photodimerization rate constant and the difference between ultraviolet (UV) irradiation temperature and the glass transition temperature of the polymer was found. It has become apparent that the photosensitivity of cinnamoylated polypentenamer can be estimated by the glass transition temperature of the original polymer, UV irradiation temperature, activation energy of the dimerization, and γ, which is a coefficient of the relationship between the photosensitive group concentration and the glass transition temperature of the polymer.     

A new stereoselective synthesis of 2-subsdtituted 1,3-bis(trimethylsilyl)propene derivatives and their conversion to cyclopentane and cyclohexane derivatives

Ester $\text{2}$ on treatment with sodium salt of sulfone or sulfoxide afforded 2-substituted 1,3-bis(trimethylsily)propene $\text{3}$ in good yield, from which cyclopentane and cyclohexane derivatives bearing a trimethylsilyl group in the molecules were synthesized.