Electrolytic reduction of azidochalcones

Cathodic reduction of -azidochalcones under slightly protic conditions proves to be an excellent method for a selective conversion of the azido function to an amino group without affecting other reducible parts of the molecules. The amino-propenones retain theZ-configuration about the C=C-bond of the starting material, whereas N-acetyl derivatives, obtained under mildly acetylating conditions, are partially isomerised. The low reduction potential of N,N-diacetyl-enamines of this type prevents their direct one step synthesis by electrolysis of azidochalcones under strongly acetylating conditions. The voltammetric behaviour of the azides and their reduction pathway is discussed.

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Elektrolytische Untersuchungen an Vinylaziden, 6. Mitt.Elektrolytische Reduktion von Azidochalkonen

Zusammenfassung Die kathodische Reduktion von -Azidopropenon erweist sich als ausgezeichneter Weg, um selektiv zu Enaminen zu gelangen, ohne (wie chemische Reduktionsmittel) auch andere Gruppierungen anzugreifen. Durch die Kontrolle von Protonierungs- bzw. Acetylierungsschritten lassen sich die stabileren N-Acetylamine erhalten. Das niedrig liegende Reduktionspotential der N,N-Diacetylamino-propenone verhindert, daß sie in einer Einstufensynthese bei der Reduktion der Azidochalkone unter stark acylierenden Bedingungen erhältlich sind. Das voltammetrische Verhalten der Azide und ihr Reaktionsweg bei der kathodischen Reduktion werden diskutiert.

     

Orientor field equations in Banach spaces

This paper focuses on the interplay between seminormality requirements and convergence hypotheses on trajectories in the lower closure theorems for orientor field equations. With the use of a weak form of seminormality, called the intermediate property (Q*), we obtain lower closure theorems (and thereby closure theorems) for orientor field equations in Banach spaces, under the assumption of strong convergence of some coordinates of the trajectories, while only weak convergence is assumed in the others. In the Euclidean case, this requirement of property (Q*) is further reduced to mere Kuratowski property (K), under the usual growth-type conditions. Finally, in the appendix, property (Q*) is investigated in detail.This research has been partially supported by Research Project AFOSR-71-2122 at the University of Michigan, Ann Arbor, Michigan.     

Remarks on lower semicontinuity and lower closure

In the context of a recent geometric condition of Cesari, used in the reduction of seminormality requirements in lower closure theorems, this paper shows that the existence of a strongly convergent selection from the sequence of orientor fields, under Kuratowski property (K), is adequate to guarantee lower closure theorems. This generalization is justified through examples. Several related remarks are made.This work was done in the framework of Research Project AFOSR-71-2122 at the University of Michigan, Ann Arbor, Michigan. The author wishes to thank Professor L. Cesari for helpful discussions during the writing of this paper.     

Cathodic synthesis of 2-amino-2-propene-1-ones electrolytical studies on vinylazides,VII

The cathodic preparation of enamino ketones from enazidoketones has been generalised to include heteroaromatic and aliphatic derivatives. Mechanistically the role of different sites of protonation, either on N¹ of the N₃-group or on carbonyl depending on electrolysis potential and acid strength, apparent by product distribution, is clarified. Aldehydic groups are preferentially reduced compared to the vinylazide part. Purely aliphatic azidoketones yield conjugated dienes under reductive acetylation, which might be useful for cycloaddition reactions.Die kathodische Synthese von Enaminoketonen aus ungesättigten Azidoketonen wurde auf heteroaromatisch substituierte und auf rein aliphatische Derivate übertragen. Zum Reduktionsmechanismus wurde der Einfluß verschiedener Stellen der Protonierung (am N¹ der N₃-Gruppe bzw. an der Carbonylgruppe), abhängig von Potential und Säurestärke, untersucht. Aldehydische Gruppen als weitere funktionelle Gruppen im Enazid werden leichter als die Vinylazide reduziert. Die rein aliphatischen Enazidoketone ergeben bei reduktiver Acylierung konjugierte Diene.

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Elektrolytische Untersuchungen an Vinylaziden, 7. Mitt.: Kathodische Synthese von 2-Amino-2-propen-1-onen

     

Some observations concerning the direct titration of nitrite with cerium(IV)

Direct titration of nitrite with cerium (IV), with ferroin as indicator, is shown to give satisfactory results if the acidity is kept between 0.033 and 0.055M at the end-point. Loss of nitrous acid owing to volatilization and decomposition is discussed. From 10 to 60 mg of sodium nitrite can be estimated with a standard deviation of 5 mug and an average error of 0.2%.