7144-44-7Relevant articles and documents
Ambident ethyl N-nitrosocarbamate anion: Experimental and computational studies of alkylation and thermal stability
Benin, Vladimir,Kaszynski, Piotr,Radziszewski, J. George
, p. 14115 - 14126 (2007/10/03)
Alkylation of N-nitrosourethane tetrabutylammonium salt (2-Bu4N) with four electrophiles (Mel, Etl, i-Prl, and PhCH2Br) was studied by 1H NMR in CD2Cl2 and CD3CN solutions. The ratio of the three regioisomers N-alkyl-N-nitrosourethane 3, azoxy 4, and O-alkyldiazotate 5 was practically independent of solvent but dependent on the nature of the electrophile. The anion 2 and O-alkyl derivative 5 are thermally unstable and decompose to ethyl carbonates 9 and 10, respectively, with a first-order rate constant (2-Bu4N: k = 18.5 ± 0.1 × 10-5 S-1; 5b (R = Et): k = 1.77 ± 0.02 × 10-5 s-1; 5d (R = PhCH2): k = 4.78 ± 0.08 × 10-5 s-1 at 35 °C in CD2Cl2). Further kinetic measurements gave activation parameters for the decomposition of 2 (Ea = 24.2 ± 0.3 kcal/mol and In A = 30.9 ± 0.1). Gas-phase calculations at the MP2(fc)/6-31+G(d)//MP2(fc)/6-31G(d) level showed that the alkylation of 2 involves the lone electron pairs of the N-N-O atoms, and the calculated activation energies correspond well to the observed ratio of regioisomers 3-5. The theoretical analysis of the decomposition processes supports a concerted mechanism with a four-center transition state in the first step for all four compounds. The calculated activation energy order (2 5 3 4) is consistent with the observed order of stability. Decomposition of 2 and 5 is a unimolecular process, giving carbonates 9 and 10 in a single step. In contrast, rearrangement of 3 and 4 leads to alkyl diazonium ions. A detailed theoretical analysis indicates that the rate-determining step for thermal decomposition of 2 is the loss of molecular nitrogen, while in 5 it is the trans-cis isomerization process. The nonconcerted process involving homolytic cleavage of the O-N bond in 5 was found to be significantly less favorable.
