Why Hypochlorous Acid Chlorinates Amines Rather than Hydroxylates Them (CROSBI ID 626736)
Prilog sa skupa u zborniku | sažetak izlaganja sa skupa | međunarodna recenzija
Podaci o odgovornosti
Šakić, Davor ; Tandarić, Tana ; Vrček, Valerije
engleski
Why Hypochlorous Acid Chlorinates Amines Rather than Hydroxylates Them
Reactions of hypochlorous acid (HOCl) with ammonia, (di)methylamine, and heterocyclic amines have been studied computationally in the gas phase and aqueous medium. Different oxidation pathways are possible in the gas phase, and only one is experimentally detected in aqueous solution. N-chlorination pathway is prohibitively expensive in the gas phase (deltaGcalc > 250 kJ/mol), yet N-chloramines are readily detected in aqueous medium. N- hydroxylation is more feasible process in the gas phase, while in aqueous medium is much less preferred. We have found that the explicit solvent effects are crucial for determination of reaction mechanism in aqueous medium. Water molecules play important catalytic role in N- chlorination reaction, by facilitating the hydrogen-atom transfer between amines and HOCl. The planar structural motif, which includes HOCl, amine and two reactive water molecules, has been calculated as the most stable configuration for up to 9 explicit water molecules. In case of N-hydroxylation reaction, water molecules are not directly involved in the O-transfer process. The linear structural motif has been found as the most preferable configuration, in which all water molecules contribute in building the first hydration shell, and participate as reaction spectators only. Catalytic effect of explicit water molecules, observed for N-chlorination of amines, has not been calculated for N- hydroxylation process.
amine ; hocl ; mechanism
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Podaci o prilogu
165-165.
2015.
objavljeno
Podaci o matičnoj publikaciji
15th European Symposium of Organic Reactivity, Book of Abstracts
Reiner Harges
Kiehl:
Podaci o skupu
15th European Symposium of Organic Reactivity
poster
31.08.2015-04.09.2015
Kiel, Njemačka