Hydantoin and Its Derivatives

Avendaño, Carmen; Menéndez, J. Carlos

doi:10.1002/0471238961.0825040101220514.a01

Cited by 10 publications

(5 citation statements)

References 98 publications

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“…The hydantoin (2,4-imidazolidinone) moiety is an important medicinal core unit . As can be seen from the structure, it can be derivatized at several positions.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of 5,5-Dimethylhydantoin Chlorination: Monochlorination through a Dichloro Intermediate

Akdağ

Worley

Acevedo

et al. 2007

J. Chem. Theory Comput.

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The hydantoin moiety is an important pharmacore, and when halogenated, hydantoin derivatives act as excellent biocides. However, there have been no computational studies concerning the chlorination mechanism for the hydantoin moiety reported. Herein we describe a computational mechanistic study of the chlorination of 5,5-dimethylhydantoin (H) at the B3LYP/6-311+G(2d,p) level. Under a 1:1 molar ratio of hydantoin and a chlorinating agent (HOCl), conproportionation is calculated to be favorable to give the N1 monochloro derivative as the major predicted product, which is in agreement with experiment. Initial direct chlorination at the N1 position is prevented by a high kinetic barrier. The first step involves the deprotonation of the hydantoin moiety (at the N3 position) which is followed by a SN2 step transferring a chloronium ion (Cl(+)) from HOCl to the ionized hydantoin anion. A mechanism is proposed where the N3 nitrogen is chlorinated first followed by the N1 position to form the dichloro derivative. When CPCM solvation free energies (ΔG(solv)) were added to the gas-phase free energies (ΔG(gas)) along the SN2 reaction path, a sudden decrease in free energy was observed due to the incipient formation of the hydroxide ion. Explicit consideration of solvation within a box of 512 water molecules led to a much more gradual free energy change along the reaction path but a very similar free energy of activation.

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“…The hydantoin (2,4-imidazolidinone) moiety is an important medicinal core unit . As can be seen from the structure, it can be derivatized at several positions.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of 5,5-Dimethylhydantoin Chlorination: Monochlorination through a Dichloro Intermediate

Akdağ

Worley

Acevedo

et al. 2007

J. Chem. Theory Comput.

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“…On the other hand, according to the literature available, the hydantoins in aqueous solution can be hydrolyzed. In this process, in which ring-opening occurs to give the ureido acids as intermediate, which can hydrolyze to α-amino acids (Scheme 5), [62,63] , it was observed that the rate constant increase with increasing pH. [64][65][66][67][68] It suggests that the second process observed corresponds with the hydrolysis reaction of the 3-chlorohydantoin formed.…”

Section: Hydrolysis Of N-chloro-hydantoins Formedmentioning

confidence: 99%

N-Chlorination rate of five-membered heterocyclic nitrogen compounds

Pastoriza

Antelo

Amoedo

et al. 2016

J. Phys. Org. Chem.

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aThe kinetics of N-chlorination reaction of pyrrolidine, pyrrolidone, succinimide, 5,5,-dimethyloxazolidine-2,4-dione, 5,5-dimethylhydantoin and 1-hydroximethyl-5,5-dimethylhydantoin with HOCl in aqueous solution were studied at 25°C, constant ionic strength and under isolation conditions in a wide pH range. The set of compounds studied in this paper is characterized by having different functional groups and the same cyclic structure, consisting of a five-member ring with a nitrogen atom in the ring, which is susceptible to be chlorinated. This series of compounds covers nine pK a units, and the kinetic studies allow us to know, like, the presence of an amino, amide or imide group modify the reactivity of nitrogenous compound.Experimental data were fitted to the first-order kinetic equation. All reactions were found to be of first order in both HOCl and nitrogenous compound concentration. Kinetics studies demonstrate that some of these compounds are hydrolyzed in alkaline medium. In each case, reaction mechanism in agreement with the experimental results is proposed. The results were compared with other compounds with similar cyclic structure (2-oxazolidinone and proline).

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“…The chemistry of hydantoins attracted a considerable attention because of their importance in medicine and industry [116–117]. N-Nucleoside analogs with (thio)hydatantoin scaffold as a nucleobase mimic were also extensively investigated [118].…”

Section: Reviewmentioning

confidence: 99%

Multicomponent reactions in nucleoside chemistry

Koszytkowska‐Stawińska¹,

Buchowicz²

2014

Beilstein J. Org. Chem.

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SummaryThis review covers sixty original publications dealing with the application of multicomponent reactions (MCRs) in the synthesis of novel nucleoside analogs. The reported approaches were employed for modifications of the parent nucleoside core or for de novo construction of a nucleoside scaffold from non-nucleoside substrates. The cited references are grouped according to the usually recognized types of the MCRs. Biochemical properties of the novel nucleoside analogs are also presented (if provided by the authors).

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Hydantoin and Its Derivatives

Cited by 10 publications

References 98 publications

Mechanism of 5,5-Dimethylhydantoin Chlorination: Monochlorination through a Dichloro Intermediate

Mechanism of 5,5-Dimethylhydantoin Chlorination: Monochlorination through a Dichloro Intermediate

N-Chlorination rate of five-membered heterocyclic nitrogen compounds

Multicomponent reactions in nucleoside chemistry

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