堀 一繁

type:Article 大阪教育大学・教職実践演習ミニ講座「理科の実験・観察における安全」(2019年度)の受講者の「理科実験における危険予測力」のルーブリック評価について報告する。このミニ講座は,理科の実験・観察を安全に行うために必要な知識と,それを支える理論的根拠や経験知を学ぶための授業(全5回)で構成されている。本稿で報告する授業実践では,酸・塩基の中和実験(高校化学基礎)を撮影・編集した動画の中に現れる危険な行為や兆候を受講者に発見させる。そして,そのような危険な行為・兆候を受講者がどの程度発見できたかを,ルーブリック評価表を用いて数値化することにより,各受講者の理科実験における危険予測力を定量評価する。 This paper reports an evaluation of safety management capability in science experiments. In the present study, safety management capability in science experiments is evaluated through a rubric score of a practice to find indications of danger in a science laboratory that appear in a video in which an experiment on neutralization of acids and bases is conducted in a first grade high school chemistry class. The practice is assigned to prospective teachers (fourth grade students in Osaka Kyoiku University) in a class of a course held in 2019 to learn how to safely conduct scientific experiments and observations. A rubric score of the practice can be a measure of safety management capability in science experiments.

Partially overlapped dicarbazolophanes exhibit a planar chirality. In this study, C-2-symmetrical [3.3](3,9)dicarbazolophane derivatives (CZ1-CZ3) have been optically resolved by preparative chiral high-performance liquid chromatography for the first time. In their circular dichroism (CD) spectra, moderate Cotton effects (CEs) were observed for their L-1(b) and L-1(a) transitions (vertical bar Delta epsilon vertical bar = 10-12 and 51-57 M-1 cm(-1), respectively), while intense CEs were notified in their B-1 transitions (vertical bar Delta epsilon vertical bar = 156-216 M-1 cm(-1)), absorption dissymmetry (g(abs)) factors being in orders of 10(-2). Circularly polarized luminescence spectrum was also obtained for cyanamide derivative CZ1, with a comparative luminescence dissymmetry (g(lum)) factor of 0.013. A computational investigation was applied to address the factors for such remarkable chiroptical responses in these dicarbazolophanes of planar chirality. Absolute configurations were unambiguously determined by the comparison of experimental and theoretical CD spectra, which was affirmed by the X-ray crystal structural analysis of enantiomerically pure sulfonamide derivative CZ2.

type:Article 大阪教育大学・教職実践演習ミニ講座「理科の実験・観察における安全」(2018年度)より,ICT教材を活用した授業実践について報告する。この講座では,理科の実験・観察を安全に行うために必要な知識を習得し,それを支える理論的根拠や経験知についてもディスカッションを通して深く理解することを目的としている。本稿にて報告する授業実践では,酸・塩基の中和実験(高校化学基礎)を撮影・編集した動画をICT教材として用い,実験時に事故を誘発し得る危険な兆候を察知する練習を行った。そして,そのような危険な兆候として,実験中の生徒の立ち位置・姿勢が悪いこと,実験卓上の整理整頓の不徹底等を見出した。 A course to learn how to safely conduct scientific experiments and observations is offered for prospective teachers (fourth grade students in Osaka Kyoiku University). This paper reports a practice in a class consisting of the course held in 2018. A video material is edited as an ICT teaching material, in which an experiment on neutralization of acids and bases is conducted in a first grade high school chemistry class. The practice in this report is aided by the ICT teaching material. The prospective teachers in the class are trained to find indications of danger in the laboratory through the video material.

A series of aniline-based fluorophores were newly synthesized. To increase their fluorescence quantum yields, it was particularly important to substitute 3,3,3-trifluoroprop-1-enyl (TFPE) groups next to the amino group to benefit from an extended pi-electron delocalization. Among these, 5-CN-2-TFPE-aniline was found to behave as an excellent fluorophore with a reasonable fluorescence quantum yield of 0.89 even in aqueous solution. L-Alanine peptide, a nonfluorescent analogue of 5-CN-2-TFPE-aniline, was synthesized and successfully employed as an enzyme probe to detect aminopeptidase N activity.

<p>小学校の若手教員を対象にした理科研修のプログラムとして，課題探究型のグループワークを実施した．同じ容器に入った正体の分からない5種類の水を，8種類の候補の中から同定するという課題に，情報の収集・整理，予想・仮説の立案，実験計画の立案，実験の実施，考察，発表のためのポスター制作まですべて，4名からなる班のメンバーの協力により取り組んだ．最後にポスターセッション形式の発表と，ルーブリックによる相互評価を行った．事後アンケートの結果から，受講者らはこのプログラムを通じて，集団での学び合いの有効性について体験的に理解したことが伺えた．一方，発表ポスターと相互評価の結果からは，科学的なものの見方や考え方に関して班ごとの到達度に幅があることが明らかになった．</p>

New donor-acceptor (D-A) and donor-acceptor-donor (D-AD) systems with carbazole and benzophenone moieties as donor and acceptor, respectively, have been synthesized. Photolumi-nescence quantum yields of D-A and D-A-D molecules in thin film were 76 and 73%, respectively. Solution-processed organic light-emitting diodes containing these D-A and D-A-D molecules as emitters showed the maximum external quantum efficiencies of 6.9 and 10.4% with a peak wavelength of 520 and 521 nm, respectively.

A series of novel mono- and bis[(9-alkylcarbazol-3-yl) methyl]acrylamides were synthesized and their radical polymerization was investigated. Emissions of bis(carbazolyl) acrylamide polymers were extended to longer wavelengths compared with those of the corresponding mono(carbazolyl) polymers, indicating the existence of interchromophoric interaction between carbazole moieties. Ionization potentials of the polymers by photoelectron yield spectroscopy showed that donor ability of the biscarbazolyl polymer was higher than that of the monocarbazolyl polymer.

Diarylethene derivatives, 1c and 1d, having carrier mobilization sites have been synthesized. Their photochromic properties are examined both in solution and in thin film. Current voltage characteristics at photostationary state of 1c and 1d showed drastic current increase compared with the corresponding open-ring isomers 1c and 1d, respectively.

Tris-bridged [3.3.n](3,6,9)carbazolophanes 1n (n=3-6), which are appropriate model compounds for fully overlapped exeimer in carbazole chromophore, have been synthesized and characterized by NMR, X-ray, absorption and fluorescence spectra; 1n showed excimeric fluorescence, whose emission maxima strongly depended on the angles and distances between carbazole rings. Copyright © 2009 The Chemical Society of Japan.

Intermoiety electronic interactions in the singlet and triplet excimer states of triply bridged [3.3.n](3,6,9)carbazolophanes ([3.3.n]Cz, n = 3-6) were studied by emission and transient absorption measurements. In these [3.3.«]Cz molecules, the dihedral angle and the separation distance r between fully overlapped two carbazole rings change systematically from nearly parallel (n = 3, r = 3.35 Å)o oblique (n = 6, r = 4.03 Å). In rigid glass at 77 K, [3.3.n]Cz (n = 3, 4) (r < 4 Å) exhibited red-shifted and structureless excimer fluorescence and phosphorescence while [3.3.n]Cz (n = 5, 6) (r > 4 Å) exhibited monomer-like vibrational fluorescence and phosphorescence. In solution at 130 K, all [3.3.n]Cz molecules exhibited an excimeric fluorescence band while [3.3.5]Cz still exhibited monomer-like phosphorescence. Transient absorption spectra measured at 294 K exhibited local excitation and charge-transfer bands for all [3.3.n]Cz molecules in the excited singlet and triplet states, suggesting that not only singlet but also triplet excimers of carbazole are formed at room temperature. Furthermore, the singlet-triplet energy gap decreased with the decrease in n, suggesting that electrons are effectively delocalized over the two carbazole moieties. These findings showed that both singlet and triplet excimers of carbazole are formed with a separation distance shorter than about 4 Åand are most stable in the parallel-sandwich structure and that the configurational mixing between exciton resonance and charge resonance states plays an essential role in the formation of singlet and triplet excimers of carbazole. © 2007 American Chemical Society.

Cyanamide- and oxa-bridged [3.n](3,9)carbazolophanes 1n and 2n (n = 4 and 5) were synthesized. X-ray analysis of 14 and 2s revealed that carbazole rings are taken to be partially overlapped geometry. Electronic spectra of 1n and 1n (n = 4 and 5) showed the existence of transannular π-π electronic interaction between two carbazole rings, whereas fluorescence of these carbazolophanes indicated monomer-like emission. Copyright © 2007 The Chemical Society of Japan.

Asymmetric epoxidation of (E)-chalcone with alkaline hydrogen peroxide by novel chiral phase-transfer catalysts (chiral PTCs) with quaternary ammonium salts of azacrown ether proceeded in high yield and good enantioselectivity. Remarkably, this reaction depended on the length of the carbon chain on the nitrogen atom with the chiral PTCs and on the bulk of the base. © 2006 Elsevier Ltd. All rights reserved.

The photophysical properties of a series of triply bridged [3.3.n](3,6,9)carbazolophanes ([3.3.n]Cz, n = 3, 4, 5, 6) were studied as a model compound for a fully overlapped carbazole excimer. In these [3.3.n]Cz molecules, a plane angle of the two carbazole moieties changed systematically from nearly parallel to oblique, with increases in the length of the methylene chain n bridging at the 9-position of each carbazole ring. Absorption bands of [3.3.n]Cz showed the blue-shift and the splitting for 1La ←1A and 1Lb ← 1A transition bands of the reference carbazole monomer, respectively. These spectral changes in [3.3.n]Cz were explained by Kasha's molecular exciton theory with the distance r and dihedral angle θ between the carbazole moieties in the ground state. In both liquid and glass matrixes, [3.3.n]Cz showed intramolecular excimer emission. The emission peak wavelength changed from 409 nm (n = 6) to 480 nm (n = 3) depending on r in the ground state. The dependence of the peak wavelength on r clearly showed that relative configurations of carbazole moieties in the ground state were preserved even in the excimer states. The smaller radiative rate of the excimer emission than the reference monomer was explained by the dimer symmetry of [3.3.n]Cz. © 2005 American Chemical Society.

The acyl group of an α-aryl-β-keto ester was readily transferred to N-, O-, and S-nucleophiles. The transacylation from arylated diethyl 3-oxoglutarate to amines led to unsymmetrical malonic acid amide esters in high yields. The present reaction proceeded under mild conditions without formation of detectable byproducts. Only simple experimental manipulations were required. This reaction was also found to be sensitive to steric factors, which enabled the chemoselective monoacylation of diamines and amino alcohols without any modifications such as protection.

As a first example of carbazole-acceptor cyclophane, carbazole- terephthalate cyclophane 1a was prepared. The structure of 1a was characterized by 1H NMR and X-ray analysis. Absorption spectrum of 1a showed the existence of transannular π-π electronic interaction and little charge transfer interaction. Fluorescence spectrum of 1a in THF exhibited intramolecular exciplex emission around 525 nm.

3-Methyl-5-nitropyrimidin-4(3H)-one readily reacts with carbonyl compounds to produce three kinds of ring transformations. The nitropyrimidinone behaves as the synthetic equivalent of activated diformylamine affording 3,5-difunctionalized 4-pyridones, 4,5-disubstituted pyrimidines and functionalized 4-aminopyridines. It also behaves like α-nitro-formylacetic acid to give 5,6-disubstituted 3-nitro-2-pyridones.

Aminolysis of nitroisoxazolone affords unsymmetrical 1,1-diamino-2-nitroethenes and carbamoylamidoximes with simple experimental manipulations.

Asymmetric decomposition of isoxazolidine derivatives under catalysis by optically active palladium(II) complexes was examined. When racemic ethyl cis-2,5-dimethyl-5-phenyl- isoxazolidine-3-carboxylate (cis-la) was treated with a catalytic amount of [Pd(MeCN)2{(S)-TolBINAP}](BF4)2 in CH2Cl2 for 60 h, optically active substrate was recovered with 99% ee and in 48% yield. The highest selectivity was achieved on treatment of racemic ethyl trans-2,4-dimethyl-5,5-di-phenylisoxazolidine-3-carboxylate, to give the optically active substrate in 74% yield with 35% ee. The kf/ks value of this reaction reaches as high as 732. For this decomposition, each substrate should have both a methyl group on the 2-position and an alkoxycarbonyl group on the 3-position of the isoxazolidine ring. The enantioselectivities of the recovered substrates were influenced not only by the other substituent groups on the 4- and 5-positions but also by the geometrical structures of the substrates. © Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

[2.2]Paracyclo(3,6)carbazolophane (1a) and [2.2](1,4)-naphthaleno(3,6)carbazolophane (1b) were prepared. The structures of 1a and 1b were characterized by 1H NMR. X-ray analysis of 1a revealed that the carbazole ring extremely deviates from the conjugated plane. Electronic spectra of 1a and 1b showed the broadening and bathochromic shift compared with the references.

2,3-Disubstituted 2,3-dihydro-6-nitro-1H-[1,4]-diazepines are prepared with easy experimental manipulations from formylated nitroenamine, which behaves as the synthetic equivalent of nitromalonaldehyde usable in organic media.

New methods for functionalization of 1-methyl-2-quinolone (MeQoe) skeleton are provided. The reaction of 1-methyl-3,6,8-trinitro-2-quinolone (TNQ) with amines affords quinolone dimer 1 and 6,8-dinitroquinolone (6,8-DNQ). Dimerization predominantly proceeds at room temperature, and denitration takes place under heated and diluted conditions. We also provide a plausible mechanism for these reactions on the basis of structure-reactivity relationship of amines. © 2002 Elsevier Science Ltd. All rights reserved.

The title compounds are readily available by ring transformation of nitropyrimidinone with active methylene compounds in the presence of ammonium acetate. © 2002 The Royal Society of Chemistry.

Polyfunctionalized pyrrole 6 is synthesized in the ring transformation of N-hydroxy-3,5-dinitro-4-pyridone 4 with enolate 2 derived from diethyl 3-oxogulutarate. The present reaction proceeds with C-N transfer from 4 to 2, which is hitherto unknown manner in similar reactions using dinitropyridone series.

A novel synthetic procedure for 3-nitro-2-pyridone derivatives (2) is provided, which includes the ring transformation of 1,3-dinitroquinolizin-4-one (3) with ketones in the presence of ammonium acetate.

New BINOL-derived ligands, 3,3′-bis(2-oxazolyl)-1,1′-bi-2-naphthols (BINOL-Box), bearing chiral bis-oxazoline at the 3,3′-carbons, were synthesized from commercially available 1,1′-bi-2-naphthol (BINOL). With the new ligands obtained, we found that asymmetric 1,3-dipolar cycloaddition reaction of N-benzylidenebenzylamine N-oxide (2) to 3-((E)-2-butenoyl)-1,3-oxazolidin-2-one (1) was catalyzed by BINOL-Box-scandium complexes to give isoxazolidine 3 in high yield with high diastereo- and enantioselectivity. For example, the reaction of 1 with 2 catalyzed by a 6 mol% (S,R)-7d and 5 mol% Sc(OTf)3 complex proceeded to give the endo-3 as the major diastereomer with an endo:exo ratio of 97:3 and 87% ee of the endo-product in the presence of 4 Å molecular sieves. Interestingly, the absolute configuration of the major product was changed according to the kind of additive used. © 2000 Elsevier Science S.A. All rights reserved.

Chiral phosphinepalladium(II)-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrones to α,β-unsaturated carboxylic acid derivatives has been investigated. In the presence of a catalytic amount of [Pd(NCMe)2{(S)-tolbinap}](BF4)2 [TolBINAP = 2,2'-bis(di-p- tolylphosphino)-1,1'-binaphthyl], the reaction of 3-alkenoyl-1,3-oxazolidin- 2-ones as dipolarophiles and N-substituted N-benzylidenenitrones has been successfully performed to give isoxazolidine derivatives in high yields with high enantioselectivities. For example, 3-((2,5-dimethyl-3- phenylisoxazolidin-4-yl)carbonyl)-1,3-oxazolidin-2-one was obtained from the reaction of N-benzylidenemethylamine N-oxide and 3-crotonoyl-1,3-oxazolidin- 2-one in 89% yield with 60% endo selectivity and 91% ee of the endo isomer. The cycloaddition of N-benzylidenebenzylamine N-oxide and 3-crotonoyl-1,3- oxazolidin-2-one afforded 3-((2-benzyl-5-methyl-3-phenylisoxazolidin-4- yl)carbonyl)-1,3-oxazolidin-2-one in 94% yield with 93% endo selectivity and 89% ee of the endo isomer. Remarkably, the endo/exo selectivity of the products depended on the N-substituent group of the nitrones. These selectivities were explained using molecular modeling.

The 1,3-dipolar cycloadditions of enol ethers as electron-rich olefins with C-phenyl-N-alkyl nitrones proceeded smoothly in the presence of easy handling palladium(II) catalysts under mild conditions to give isoxazolidines in good yield.

The intramolecular nucleophilic addition of 2-allylphenol was catalyzed by RuCl3·nH2O/AgOTf-PPh3-Cu(OTf) 2 to afford 2,3-dihydro-2-methylbenzofuran in good yield, while 2-(3-butenyl)-phenol was converted to 3,4-dihydro-2(2H)-methylbenzopyran.

Asymmetric 1,3-dipolar cycloaddition of nitrone 2 to olefin 1 was catalyzed by chiral phosphine-palladium complexes to give isoxazolidine 3 in high yield with high enantioselectivity up to 91% ee.