Amination of benzylic C-H bonds by arylazides catalyzed by CoII-porphyrin complexes: A synthetic and mechanistic study was written by Ragaini, Fabio;Penoni, Andrea;Gallo, Emma;Tollari, Stefano;Li Gotti, Claudia;Lapadula, Marta;Mangioni, Enrica;Cenini, Sergio. And the article was included in Chemistry – A European Journal in 2003.Computed Properties of C14H12N2 This article mentions the following:
CoII-porphyrin complexes catalyze the reaction of aromatic azides (ArN3) with hydrocarbons that contain a benzylic group (ArR1R2CH) to give the corresponding amines (ArR1R2C-N-HAr). When at least one of the R substituents is hydrogen, the catalytic reaction proceeds further to give the imine ArRC:NAr in good yields. The reaction mechanism has been investigated. The reaction proceeds through a reversible coordination of the arylazide to the CoII-porphyrin complex. This unstable adduct can either react with the hydrocarbon in the rate-determining step or decompose by a unimol. mechanism to afford a putative “nitrene” complex, which reacts with more azide, but not with the hydrocarbon, to afford the byproduct diaryldiazene. The kinetics of the catalytic reaction have been investigated for a range of azides and substituted toluenes. Aryl azides with electron-withdrawing substituents react at a faster rate and a good correlation is found between the log(k) and the Taft parameters. On the other hand, an excellent correlation between the logarithm of the rate for substituted toluenes relative to that of toluene and a radical parameter (σJJ) alone was found, with no significant contribution by polar parameters. An explanation has been proposed for this anomalous effect and for the very high isotopic effect (kH/kD = 14) found. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Computed Properties of C14H12N2).
4-(Benzylamino)benzonitrile (cas: 10282-32-3) belongs to nitriles. Nitrile carbon shifts are in the range of 115â?25 ppm whereas in isonitriles the shifts are around 155â?65 ppm. Nitrile groups in organic compounds can undergo a variety of reactions depending on the reactants or conditions. A nitrile group can be hydrolyzed, reduced, or ejected from a molecule as a cyanide ion.Computed Properties of C14H12N2
Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts