Metal-catalysed cleavage of carbon-carbon bonds

Reactions cleaving carbon-carbon bonds with the assistance of transition metals as the catalyst have provided various molecular transformations that are otherwise difficult to execute, opening a scenic avenue along organic synthesis. Construction of structural motifs like medium-sized carbocycles and chiral quaternary carbon centres have been set within an access of such paradoxical approaches in the past decade.     

Asymmetric Colliding-Pulse Mode-Locking in InGaAsP Semiconductor Lasers

Asymmetric colliding-pulse mode-locking was successfully demonstrated in an InGaAsP laser. This laser had a single saturable absorber section located partway along the cavity length, and showed mode-locking operation at harmonics of the cavity roundtrip frequency. The method verified that optical pulse repetition up to subterahertz rates can be generated with nearly 1-mm-long mode-locked InGaAsP lasers.     

Iridium-catalyzed enantioselective Pauson-Khand-type reaction of 1,6-enynes

Iridium-chiral diphosphine complex catalyzes an enantioselective intramolecular Pauson-Khand-type reaction to give various chiral bicyclic cyclopentenones. The enantioselective reaction proceeds more smoothly and enantioselectively under a lower partial pressure of carbon monoxide. Moreover, aldehyde can be used as a CO source in the enantioselective carbonylative coupling.     

Synthesis of 3‐Acyl‐4‐alkenylpyrrolidines by Platinum‐Catalyzed Hydrative Cyclization of Allenynes

A series of nitrogen‐tethered allenynes (‘5‐aza‐1,2‐dien‐7‐ynes’) 1 were transformed to the corresponding 3‐acyl‐4‐alkenylpyrrolidines 3 when treated with a catalytic amount of PtCl₂ in MeOH at 70°. Initial Pt‐promoted cyclization forms a nonclassical carbocationic intermediate. In contrast to the cycloisomerization in toluene, which produced the bicyclic cyclobutenes 2 , the intermediate is intercepted by addition of an oxygen nucleophile to achieve the formal hydrative cyclization.     

Influence of magnetoelastic effects on lattice vibrations in the ferromagnetic invar alloy Fe0.65Ni0.35

Neutron scattering measurements have been made of phonons in a Fe₆₅Ni₃₅ crystal at several temperatures. Marked softening of the [110] acoustic shear modes and a dip in the dispersion relation are found at low temperatures. Above the magnetic ordering temperature T_c, the frequency shift is removed completely, which suggests phonon perturbation by magnetoelastic coupling.     

Correction method for X-ray fluorescent determination of chromium in high-alloy steels and nickel-base alloys

Summary A new interelement correction method has been developed for the X-ray fluorescent determination of chromium in high-alloy steels and nickel-base alloys. The calibration equation which was derived from the JIS (Japanese Industrial Standards) model is applicable over wide ranges of compositions by preparation of only Fe-Cr binary standards.The new approach gave better accuracy than that based on Rasberry-Heinrich correction model. The accuracies (_d) were 0.08% for high-alloy steels and 0.14% for nickel-base alloys.

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Korrekturmethode für die röntgenfluorescenzspektrometrische Bestimmung von Chrom in hochlegierten Stählen und Nickellegierungen

Zusammenfassung Die Eich-Gleichung für das neue Korrekturverfahren wurde vom JIS-Modell (Japanese Industrial Standards) abgeleitet und ist über einen weiten Bereich von Zusammensetzungen durch Herstellung von lediglich binären Fe-Cr-Standards einsetzbar. Das beschriebene Verfahren bietet eine bessere Genauigkeit als die Methode nach dem Korrekturmodell von Rasberry-Heinrich. Sie betrug 0,08% für hochlegierte Stähle und 0,14% für Nickellegierungen.

     

Grain boundary relaxation phenomena in block and graft copolymers

Summary The grain boundary relaxation phenomena, which have been found in the mechanical relaxation of the cast films of a series ofgraft copolymers ofpoly(methyl acrylate) with styrene, are examined again, in order to understand its relaxation mechanism, by using some particular series of heterogeneous systems of two components having different interaction between the two phases and, subsequently, different grain boundary structure; i. e., two series of poly(vinyl acetate) filled with two types of carbon blacks having relatively high and low surface activities, respectively, a series ofmechanical mixtures ofpoly(vinyl acetate) with polystyrene, and a series of styrene-isoprene-styrene tri-block copolymers.The grain boundary relaxation phenomena are again detected for the series of the tri-block copolymers but definitely not for the series of the mechanical mixtures, suggesting that the grain boundary relaxation phenomena must arise not from the heterogeneous structures themselves but from characteristic arrangements of molecular chains at the boundary of the two phases. That is, there must be a considerably strong interaction between the two phases, and there exists an intermediate phase in which the polymer segments of soft component are rigidified while the other polymer segments of hard component are softened. In other words, there must be a cooperative motions of chain segments of the two components to produce a mechanical relaxation under a certain environmental condition, such as temperature and time scale of observation.

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Zusammenfassung Die Korngrenzenrelaxationsphänomene, die in der mechanischen Relaxation einer Serie von aus Graft-Copolymeren von Polymethylacrylat mit Styrol gefunden wurden, wurden erneut geprüft, um den Relaxations-mechanismus zu verstehen, unter Verwendung einer besonderen Serie von heterogenen Systemen zweier Komponenten, die verschiedene Wechselwirkungen zwischen den zwie Phasen besitzen und deshalb verschiedene Korgrenzenstrukturen. Das heißt, wir verwendeten zwei Serien von Polyvinylacetaten, gefüllt mit zwei Rußtypen von vergleichsweise hoher und niedriger Oberflächenaktivität, eine Serie von mechanischen Mischungen aus Polyvinylacetat mit Polystyrol und eine Serie von Styrol-Isopren-Dreiblockcopolymeren. Die Korngrenzenrelaxationsphänomene, wurden für die Serie der Dreiblockcopolymeren wiederum festgestellt, aber definitiv nicht für die Serie der mechanischen Mischungen. Das läßt vermuten, daß Korngrenzenrelaxation nicht von heterogenen Strukturen selbst, sondern von charakteristischen Anordnungen der molekularen Kette an der Grenze von zwei Phasen herrührt. Das heißt, es muß eine beträchtlich strenge Wechselwirkung zwischen den zwei Phasen bestehen, und es muß eine Zwischenphase existieren, in welcher die Polymersegmente der weichen Komponente versteift werden, während die anderen Polymersegmente der harten Komponente erweicht werden. Mit anderen Worten, es müssen cooperative Bewegungen von Kettensegmenten der zwei Komponenten vorhanden sein, um eine mechannische Relaxation unter gewissen Umgebungsbedingungenzuerzeugen, Umgebungsbedingungen wie Temperatur und Zeitskala der Beobachtungen.

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With 6 figures and 13 tables

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Presented at the 20th Annual Symposium on Rheology, Japan, Fukui, Oct. 18, 1972.