86475-51-6Relevant academic research and scientific papers
C-Azidodiazirines in the SRN1 Reaction of Azide Ion with Arylchlorodiazirines. Further Insights into Reaction Mechanism
Creary, Xavier
, p. 7700 - 7708 (2007/10/02)
Mixtures of arylchlorodiazirines and sodium azide in DMSO form visible charge transfer complexes.Irradiation of these solutions with fluorescent room light leads to SRN1 displacement of chloride and the transient formation of C-azidodiazirines.Relative reactivity studies (using competition experiments) show that nitro-substituted arylchlorodiazirines are substantially more reactive than other arylchlorodiazirines.This is attributed to facile electron transfer in the propagation cycle, involving the nitro-substituted aromatic ring.C-Azidodiazirines can be isolatedin solution and spectroscopically characterized when the SRN1 reaction is initiated by addition of catalytic amounts of the sodium salt of 2-nitropropane.These azidodiazirines readily decompose at room temperature by first order processes to give molecular nitrogen and benzonitriles.Solvent and substituent effects on decomposition rates are minimal.Computational studies on potential intermediate carbenes in the decomposition of azidodiazirines have been carried out at the HF/6-31-G* level.Singlet α-azidocarbenes RCN3, where R = NH2, OH, F, vinyl, phenyl, and CH3, are energy minima at this computational level.Isodesmic calculations show that the azido group is comparable to OH in its carbene stabilizing ability.Subsequent loss of N2 from α-azidocarbenes, leading to nitriles, is a highly exothermic process (126 kcal when R = vinyl and 128 kcal when R = phenyl).
MECHANISM OF THE REACTION OF 3,5-DINITROBENZONITRILE WITH SODIUM METHOXIDE IN METHANOL.
Abe
, p. 1206 - 1213 (2007/10/02)
The reaction of 3,5-dinitrobenzonitrile in a methanolic solution containing a low sodium-methoxide concentration has been reinvestigated. The final product has been found to be methoxy (3,5-dinitrophenyl)methanimine, which is produced by a catalytic reaction. The reaction mechanism has been presented for the formation of the Meisenheimer complexes and the final product in the reaction system. The rate and thermodynamic stabilites for their formation have been discussed on the basis of the LUMO coefficients of 3,5-dinitrobenzonitrile and from the relative potential energies of their formation respectively, considering also the solvent effects.
