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1.
Dr. Christopher R. Opie Dr. Hidetoshi Noda Prof. Dr. Masakatsu Shibasaki Dr. Naoya Kumagai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4648-4653
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. 相似文献
2.
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. 相似文献
3.
The solid-liquid interface motion of NaBi(WO4)2 (NBWO) melt crystal growth is observed in an in situ system, in which the whole processes of interface transition from fiat interface and cellular to dendrite are visualized. The spacing of the dendrite under smaller temperature gradient turns out to be larger than that under larger temperature gradient, which is found to be sensitive to the temperature distribution. The mechanism of dendrite growth of NBWO is studied based on the model of the growth units of anion coordination polyhedra. The { 001} face has two apex links, so it shows higher stability and has high growth rate and forms the arm of dendrite, whereas the {010} face has only one apex link, and thus shows relative slower growth rate and firstly forms the branches. 相似文献
4.
5.
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. 相似文献
6.
The visualization of flows in two dimensions by using planar laser light sheets is a commonly used technique. We extend this technique to three dimensions by rapidly scanning the laser light sheet to obtain a set of slices of the flow around a full span delta wing. The leading edge vortices, which are marked with smoke, are unburst by tangential blowing around the leading edges at angles of attack in excess of 25°. Since the measurement period is on the order of the smallest convective time scale, we obtain a virtually instantaneous set of planar cross sections of the flow. Software based on the marching cubes algorithm is used to stack the slices and reconstruct a three-dimensional surface of the smoke-seeded fluid. This surface, which corresponds to the vortices, clearly shows the qualitative effects of blowing on the delta wing flow. 相似文献
7.
Naoya Inazumi Shunzo Yamamoto Yoshimi Sueishi 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(1-2):33-39
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. 相似文献
8.
Chiaki Azuma Takao Mitsuboshi Kohei Sanui Naoya Ogata 《Journal of polymer science. Part A, Polymer chemistry》1980,18(3):781-797
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. 相似文献
9.
Masaru Kurihara Naoya Yoda 《Journal of polymer science. Part A, Polymer chemistry》1967,5(7):1765-1781
Fully aromatic polyquinazolinediones of high molecular weight were prepared by the cyclopolycondensation reaction of 4,4′-diamino-3,3′-biphenyldicarboxylic acid with aromatic diisocyanates. The poly(phosphoric acid) solution polymerization techniques yielded tractable poly(urea acid), which was converted to polyquinazolinediones by thermal cyclodehydration at 300–400°C. under reduced pressure. The polyquinazolinediones thus obtained have excellent thermal stability both in nitrogen and in air. The poly(urea acid) is soluble in dimethyl sulfoxide, and films can be cast from the polymer solution of poly(urea acid) (ηinh = 0.8 to 1.8). The films are made tough by being heated in nitrogen or under reduced pressure at 300–400°C. The polymerization mechanism of the cyclopolycondensation reaction was studied, and it was established that the polymerization proceeded through the formation of tractable poly(urea acid), Structure (I), of high molecular weight, followed by cyclodehydration, yielding poly(1,2-dihydro-2-imino-4H-3,1-benzoxazin-4-one), Structure (II). On subsequently being heated this undergoes intramolecular rearrangement along the polymer chain, giving the thermodynamically stable polyquinazolinedione, Structure (III). 相似文献
10.
Masayoshi Watanabe Tadashi Iida Kohei Sanui Naoya Ogata Tadahiko Kobayashi Zentaro Ohtaki 《Journal of polymer science. Part A, Polymer chemistry》1984,22(6):1299-1307
Novel polyamides that contain tetrathiafulvalene (TTF) moieties were synthesized by direct polycondensation of Δ2,2′ -bi-1,3-dithiole-4,4′(5′)-dicarboxylic acid with aromatic diamines in the presence of triphenylphosphine, hexachloroethane, and pyridine. Complexes of these polyamides with bromine were TTF cation radical () salts which resulted from the charge transfer of TTF moieties to bromine. The electrical conductivity of undoped polyamides increased with a decrease in diamine length. By doping the bromine the conductivity of the polyamides was enhanced by 3–5 orders of magnitude and reached 10?5–;10?9S cm?1. Maximum conductivity was observed at the doping ratio of [Br]/[repeat unit] < 1. The electrical conduction in the bromine complexes may be attributed to the hopping of odd electrons of between TTF moieties. 相似文献