Summary
The kinetics of the nitrosation of piperidine by propyl,iso-propyl, butyl,iso-butyl,sec-butyl, andtert-butyl nitrites in 0.1M NaOH and of the hydrolysis of the nitrite esters were studied spectrophotometrically by monitoring the absorbance of the nitrites at 381 nm. The observed correlation between logk 2 and σ* (ρ*=4.5) shows the reaction to proceedvia electrophilic attack by the nitrites; the existence of an isokinetic relationship suggests a single mechanism for the whole series. Comparison of the relative reactivities of the alkyl nitrites (primary>secondary>tertiary) with characteristic parameters of theirR groups (vertical ionization potentials and heats of formation ofR +) suggests that these reactions are orbital controlled. All hydrolysis reactions were slower than the corresponding aminolysis reactions. This is attributed to a retardation of the former reaction by unfavourable interactions between the lone pairs of the nucleophile and the nitroso nitrogen atom.
Zusammenfassung
Die Kinetik der Nitrosierung von Piperidin durch Propyl-,iso-Propyl-, Butyl-,iso-Butyl-,sec-Butyl- undtert-Butylnitrit sowie die Hydrolyse der entsprechenden Nitritester wurde in alkalischem Medium (NaOH, 0.1M) spektrophotometrisch (γ=381 nm) untersucht. Die beobachtete Relation zwischen logk 2 und σ* (ρ*=4.5) zeigt, daß die Reaktion durch nucleophile Attacke des Amines erfolgt. Die Existenz einer isokinetischen Relation läßt einen einheitlichen Mechanismus für die gesamte untersuchte Serie vermuten. Aus dem Vergleich der gefundenen Reaktivitätssequenzen für die Alkylnitrite (primär>sekundär>tertiär) mit den strukturellen Parametern ihrer ResteR (Ionisationspotentiale, Bildungswärme vonR +) schließen wir, daß die untersuchten Reaktionen orbitalkontrolliert verlaufen. In allen Fällen wurde bei gleichen Bedingungen eine im Vergleich zur Aminolyse entsprechend langsamere Hydrolyse beobachtet. Der Unterschied ist einer ungünstigen Wechselwirkung zwischen den einsamen Elektronenpaaren der Nucleophile und des Stickstoffatoms der NO-Gruppe während der Reaktion mit der OH−-Gruppe zuzuschreiben.
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García-Santos, P., Calle, E., González-Mancebo, S. et al. Kinetics of the aminolysis and hydrolysis of alkyl nitrites: Evidence for an orbital controlled mechanism. Monatsh Chem 127, 997–1003 (1996). https://doi.org/10.1007/BF00807570
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DOI: https://doi.org/10.1007/BF00807570