Electrochemical amination of unsaturated and aromatic compounds

Abstract

The mechanism and synthetic perspectives of an indirect cathodic amination of unsaturated and aromatic substrates are considered. The influence of experimental conditions on the state and reactivity of the aminating reagent in solution is studied. The key role of the electrolyte acidity and redox properties of the reagents and intermediates in the obtained isomeric composition and the yield of the amination products is demonstrated.

UV Photolysis of Chloramine and Persulfate for 1,4-Dioxane Removal in Reverse-Osmosis Permeate for Potable Water Reuse

“…Recombination of this radical and its eventual oxidation can produce N 2 gas (reactions 12 and 13). A small amount of nitrate was produced throughout the experiment, possibly due to the reaction between NH 2 Cl and nitrite or H 2 O. , Organic nitrogen was likely the degradation products from the interaction of NH 2 • and NHCl • with 1,4-D. − Another possible pathway is that dissolved O 2 reacts with NH 2 • , forming intermediate products NH 2 O 2 • , which reacted with other radicals such as SO 4 •– , HO • , and Cl • to form nitrate . The formation of NO 2 • from nitrate photolysis subsequently resulted in the formation of organic nitrogen. − …”

Recent Advances in the Electrochemical Reduction of Substrates Involving N−O Bonds

“…Lysitin and co‐workers used hydroxylamine (Scheme , 23b ) as a reagent for the amination of aromatic compounds . They successfully aminated anisole ( 23a ), benzene, chlorobenzene, and anilines . In all cases, strong acidic conditions were mandatory for the reactions to take place.…”

Efficiency of electrochemical amination of anisole in aqueous-organic solutions of 4 M H2SO4

“…Mechanism of the electrochemical amination of the anisole in aqueous and aqueous organic electro lytes including diluted H 2 SO 4 can be represented by the set of equations [3]: cathode: (1) which allows controlling the efficiency of the substitution by Ti(III) regeneration rate without any changes of the electrolyte content is a main difference of electrochemical amination from chemical one. In chemi cal amination [1,2], the addition of commercial Ti(III) solution to the emulsion or solution of anisole decreases molar ratio H 2 SO 4 : H 2 O and concentration of organic solvent and therefore increases the contribution of the reaction (5) into termination of amino radical intermedi ates.…”

“…Second, the dependencies of the potential of mercury cathode obtained at 40 and 15°C showed that in acetic acid the decrease of the temperature promotes the decrease of the charge required for finishing the target electrochemical process (see figure). Change of the potential of the mercury cathode during the electrolysis of the system Ti(IV)-NH 2 OH-anisole in the electrolytes containing acetic acid (1, 2) and acetoni trile (3,4) at 15 (1,4) and 40°C (2,3).…”

“…In aqueous and aqueous-organic solutions of diluted sulfuric acid, cation radical amination of aro matic substrates activated toward electrophilic agents results in formation of appropriate monoamino deriv atives [1][2][3]. For chemical functionalization of above substrates with the salts of transient metals and hydroxylamine or with hydroxylamine O sulfoacid, the yield of primary amines to the source of amino radicals does not exceed 40% [1].…”