Electrochemical and Quantum Chemical Study of Reactivity of Orthophthalaldehyde with Aliphatic Primary Amines

0462367 - ÚFCH JH 2017 RIV US eng J - Článek v odborném periodiku
Donkeng Dazie, Joel - Liška, Alan - Ludvík, Jiří
Electrochemical and Quantum Chemical Study of Reactivity of Orthophthalaldehyde with Aliphatic Primary Amines.
Journal of the Electrochemical Society. Roč. 163, č. 9 (2016), G127-G132. ISSN 0013-4651. E-ISSN 1945-7111
Grant CEP: GA ČR GA13-21704S
Institucionální podpora: RVO:61388955
Klíčová slova: electrochemistry * quantum chemical study * amines
Kód oboru RIV: CG - Elektrochemie
Impakt faktor: 3.259, rok: 2016

The reactivity of orthophthalaldehyde (OPA) with primary amines is a base for broad application of OPA: in the determination of
amino acids, in medicine as a disinfection agent and in organic synthesis, therefore the detailed knowledge of the mechanism is of
interest. The electrochemical reducibility of OPA was utilized for the investigation of its reactivity with eight aliphatic primary amines
which could be separated into four types. Based on the electrochemical monitoring, the apparent reaction rates were evaluated. It
was found that the reaction rate essentially depends on the substitution at the α-carbon atom of the amine. The quantum chemical
computations revealed that the reaction rate well corresponds with the Hirshfeld and NBO atomic charges on the α-carbon atom.
Because of the strong hydration of OPA in aqueous solutions, the reaction was performed both in aqueous solutions (pH 9–10) as
well as in diethyl ether. For the identification of intermediates and products, NMR, MS and X-ray crystal structure analyses have
been used. Besides the expected isoindolin-1-one main products, the phthalimide derivative as a side product was observed and a
new type of the conjugate product has been found and identified. The plausible reaction pathway was proposed.
Trvalý link: http://hdl.handle.net/11104/0261848