Abstract
A kinetic study of the mechanism of the nitrosation of dimethylamine (DMA) by propyl nitrite (PrONO) in basic media to yield N-nitrosodimethylamine (NDMA) has found the rate equation to be
where [DMA] and [PrONO] are total concentrations. At 298.2 K andI=0.25M,k 2=(6.59±0.13)·10−2 M −1 s−1 andK 1=(1.16±0.07)·10−11 M.
The observed influence of ionic strength, the kinetic results obtained in water/tetrahydrofuran mixtures and in heavy water (k H/k D=2.09), and the value of ΔS # (−158 JK−1 mol−1) suggest that the nitrosating agentPrONO attacks the free amine to create a tetracentric transition state and that this is the rate controlling step of the reaction.
Experiments carried out with other nitrite esters have shown there to be a correlation satisfyingTaft's equation between their structure and their reactivity withDMA (ρ*=3.89), which allows the rate constant for nitrous acid to be calculated.
Zusammenfassung
Die kinetischen Untersuchungen der Nitrosierung von Dimethylamin (DMA) mit Propylnitrit (PrONO) in basischem Medium ergab für den Mechanismus der Bildung von N-Nitrosodimethylamin (NDMA) folgende Geschwindigkeitsgleichung:
wobei [DMA] und [PrONO] totale Konzentrationen darstellen. Bei 298.2 K undI=0.25M gilt:k 2=(6.59±0.13)·10−2 M −1 s−1 undK 1=(1.16±0.07)· 10−11 M.
Der beobachtete Einfluß der Ionenstärke, die kinetischen Resultate in Wasser/Tetrahydrofuran-Mischungen und in schwerem Wasser (k H/k D=2.09), und der Wert von ΔS #(−158 J K−1 mol−1) legen nahe, daß das nitrosierende AgensPrONO das freie Amin unter Ausbildung eines tetrazentrischen Übergangszustandes angreift, wobei dies der geschwindigkeitsbestimmende Schritt der Reaktion ist.
Experimentelle Daten mit anderen Nitritestern zeigten eine gute Korrelation zurTaft-Gleichung. Mit einem Wert von ρ*=3.89 fürDMA erhält man eine Beziehung zwischen Struktur und Reaktivität, die es erlaubt, die Geschwindigkeitskonstante für Salpetrige Säure zu errechnen.
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Casado, J., Castro, A., Lorenzo, F.M. et al. Kinetic studies on the formation of N-nitroso compounds XI. Nitrosation of dimethylamine by nitrite esters in aqueous basic media. Monatsh Chem 117, 335–344 (1986). https://doi.org/10.1007/BF00816527
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DOI: https://doi.org/10.1007/BF00816527