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- W1989059332 abstract "Azacyclophane mit Ethylendiamin-Einheiten und offenkettige Analoga werden durch Umsetzungen u. a. mit Bromacetonitril und Reduktion dargestellt, ebenso feste Metallkomplexe der Zusammensetzung L · Cu4Cl8, L · Zn2Cl4, L · Ni6Cl12, · 8H2O, L · Co4(NO3)8 · 16 H2O (L = makrocyclisches Octaamin). Die Ethylendiamin-Systeme komplexieren in wäßriger Lösung z. B. Ni2⊕ und Cu2⊕ mit K ≃ 106 l/mol; Protonierung erfolgt nur an den primären NH2-Gruppen mit pK-Werten von 8.55 ± 0.1. Die Geschwindigkeitskonstanten des Acyltransfers von 2,4-Dinitro-1-naphthylacetat auf Stickstoff werden in Gegenwart von jeweils zur Hälfte protonierten Basen gemessen; nach Normalisierung pro Nucleophil verhalten sie sich wie 9.5:4.4:1, wenn man ein makrocyclisches Octaamin, ein offenkettiges Ethylendiamin-Analogon und N-Ethylanilin vergleicht. Während der Zusatz von Co2⊕ wenig RGK-Änderungen bewirkt, verlangsamt 1 Äquivalent Cu2⊕ pro makrocyclischer Ligand L die Reaktion um den Faktor ≈ 50. 1H- und 13C-NMR-Daten der neuen Verbindungen werden angegeben. Azamacrocycles with N-(Aminoalkyl) Side Chains: Syntheses, Metal Complexes, and Catalysis of Acyl Transfer Reactions Azacyclophanes containing ethylene diamine groups and open chain analogues are prepared e. g. by reactions with bromoacetonitrile and subsequent reduction. Metal complexes of the composition L · Cu4Cl8, L · Zn2Cl4, L · Ni6Cl12, · 8H2O, L · Co4(NO3)8 · 16 H2O, where L = macrocyclic ligand, are obtained in the solid form. In aqueous solutions the ethylenediamine systems show complexation constants e. g. with Ni2⊕ and Cu2⊕ of K 106 l/mol; protonation occurs only at the primary NH2 group with a pK of 8.55 ± 0.1. Rate constants of acyl transfer from 2,4-dinitro-1-naphthyl acetate to nitrogen are measured with amines which are half protonated; normalized for attack at one nucleophile they show ratios of 9.5:4.4:1 if one compares a macrocyclic octaamine, an open chain ethylenediamine analogue, and N-ethylaniline. The rates show little influence by Co2⊕, but a decrease of ≈ 50 upon addition of 1 equivalent of Cu2⊕ per macrocyclic ligand L. 1H and 13C NMR data for the new compounds are given." @default.
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- W1989059332 date "1986-09-01" @default.
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- W1989059332 title "Azamakrocyclen mitN-(Aminoalkyl)-Seitenketten: Synthesen, Metallkomplexe und Katalyse von Acyltransferreaktionen" @default.
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- W1989059332 doi "https://doi.org/10.1002/cber.19861190912" @default.
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