Electronic structure of nitrogen–chlorine bonds in some compounds studied by NQR spectroscopy and DFT calculations

Полещук, О. Х.; Makiej, K.; Ostafin, M.; Nogaj, B.

doi:10.1002/mrc.851

Cited by 7 publications

(3 citation statements)

References 15 publications

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“…For T4 , the amide nitrogen has a charge of −0.51 (for Cl, it is 0.18) and the amine nitrogen has a charge of −0.50 (Cl has 0.08). This polarization agrees with a literature report . Moreover, the Wiberg bond orders are consistent with the bond lengths.…”

Section: Resultssupporting

confidence: 92%

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The Stabilities of N−Cl Bonds in Biocidal Materials

Akdağ

Okur

McKee

et al. 2006

J. Chem. Theory Comput.

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N-halamine chemistry has been a research topic of considerable importance in these laboratories for over two decades. N-halamine compounds are useful in preparing biocidal materials. There are three N-Cl moieties available in cyclic N-halamine compounds: imide, amide, and amine. The stabilities toward the release of free halogen have been experimentally shown to decrease in the order amine > amide > imide. In this work, this generalization has been tested theoretically at the level of B3LYP/6-31+G(d) and using the conductor-like polarizable continuum aqueous solvation model with UAKS cavities. Excellent accord was observed between theory and experiment. It was also found that the imide and amide N-halamine stabilities on hydantoin rings could be reversed with substitution patterns at the 5 position.

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Section: Resultssupporting

confidence: 92%

“…This polarization agrees with a literature report. 18 Moreover, the Wiberg bond orders are consistent with the bond lengths. As a result, the imide bond is more polarized than the amide, which is more polarized than the amine.…”

Section: Resultssupporting

confidence: 58%

The Stabilities of N−Cl Bonds in Biocidal Materials

Akdağ

Okur

McKee

et al. 2006

J. Chem. Theory Comput.

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“…Our interest was piqued by a report by Nagao and Katagiri published in 1991 29. These authors correctly predicted that compounds possessing N–Cl bonds with smaller 35 Cl nuclear quadrupole resonance (NQR) frequencies than that of trichloroisocyanuric acid30,31 (TCCA 2 , 58.902 MHz29,32) ought to suffer chlorination by action of the latter. In their report, DCDMH 3 ( 35 Cl NQR ν = 55.960 and 53.639 MHz) was prepared from the corresponding dimethylhydantoin by action of TCCA 29.…”

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confidence: 99%

A simple and expedient method for the preparation of N-chlorohydantoins

Whitehead

Staples

Borhan

2009

Tetrahedron Letters

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A simple and efficient methodology for the preparation of N-chlorinated hydantoins is presented. These versatile chlorenium sources were isolated in high yield after a simple recrystallization. Among the ten examples are the first chiral N-chlorohydantoins.N-chlorinated hydantoins (e.g., 1) are important and versatile chlorinating agents that have found use in a range of synthetic operations. The prototypical example, 1,3-dichloro-5,5-dimethylhydantoin (DCDMH 3), has been employed as a chlorine source for the α-chlorination of acetophenones 1 and 1-aryl-2-pyrazolin-5-ones, 2 for the preparation of chlorohydrin derivatives of corticosteroids, 3 for the benzylic chlorination of 2-methylpyrazine, 4 and for the selective chlorination of a heavily functionalized quinolone derivative en route to the antibiotic In the latter case, DCDMH was found to be a milder, more selective reagent than sulfuryl chloride. Researchers at Schering Plough exploited the enhanced reactivity of DCDMH relative to NCS to improve upon the large-scale preparation of Davis' oxaziridine. 6,7 Moreover, DCDMH was employed to trap an enolate resulting from the attack of dimethylzinc onto an α,β-unsaturated ketone, thus generating an α-chloro-β-methyl ketone functionality en route to a building block of Amphotericin B. 8 DCDMH has been employed as an oxidant for a number of transformations including the halodeboronation of aryl boronic acids, 9 the oxidation of urazoles to provide triazolinediones, 10 the microwave-assisted cleavage of oximes, 11 the preparation of dialkyl chlorophosphates, 12 and as a terminal oxidant in the Sharpless asymmetric aminohydroxylation reaction. 13,14 The compound can also serve as a mild oxidant in the presence of wet silica gel in the sodium nitrite-mediated nitration of phenols 15 and in the preparation of N-nitrosoamines. 16 Furthermore, DCDMH has emerged as the reagent of choice for the activation, prior to loading, of silyl linkers for solid-phase organic synthesis. [17][18][19][20] Finally, DCDMH has been used as an oxidative activator of an iridium catalyst employed for the asymmetric hydrogenation of substituted quinolines. 21 Other uses of DCDMH include employment as redox titrants in nonaqueous media, 22 and as a cheap yet safe disinfectant and bactericide for municipal water sources. 23 N-chlorinated hydantoins have also received attention from the pharmacological community. The myriad of adverse side-effects associated with hydantoin-based drugs such as the anticonvulsant Dilantin and the aldose reductase inhibitor Sorbinil have been attributed to N-chloro metabolites generated in vivo via chlorination by myeloperoxidase and hydrogen peroxide. There are two classical methods for the preparation of N-chlorinated hydantoins. One approach involves passing chlorine gas through an aqueous alkaline solution of hydantoin. 27 The toxicity and reactivity of elemental chlorine make this approach somewhat undesirable. The second method involves treatment of the hydantoin with an aqueous sodium hypochlorite ...

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