Show/Hide Menu
Hide/Show Apps
Logout
Türkçe
Türkçe
Search
Search
Login
Login
OpenMETU
OpenMETU
About
About
Open Science Policy
Open Science Policy
Communities & Collections
Communities & Collections
Help
Help
Frequently Asked Questions
Frequently Asked Questions
Guides
Guides
Thesis submission
Thesis submission
MS without thesis term project submission
MS without thesis term project submission
Publication submission with DOI
Publication submission with DOI
Publication submission
Publication submission
Supporting Information
Supporting Information
General Information
General Information
Copyright, Embargo and License
Copyright, Embargo and License
Contact us
Contact us
Mechanism of 5,5-dimethylhydantoin chlorination: Monochlorination through a dichloro intermediate
Date
2007-11-01
Author
Akdağ, Akın
Acevedo, Orlando
Mckee, Michael L.
Metadata
Show full item record
This work is licensed under a
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License
.
Item Usage Stats
91
views
0
downloads
Cite This
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 S(N)2 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 (AG(solv)) were added to the gas-phase free energies (AG(gas)) along the S(N)2 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.
Subject Keywords
Physical and Theoretical Chemistry
,
Computer Science Applications
URI
https://hdl.handle.net/11511/57330
Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
DOI
https://doi.org/10.1021/ct7001804
Collections
Department of Chemistry, Article
Suggestions
OpenMETU
Core
Regioselective Synthesis of Benzo[h][1,6]- naphthyridines and Chromenopyrazinones through Alkyne Cyclization
Hoplamaz, Emre; KESKİN, SELBİ; Balcı, Metin (Wiley, 2017-03-17)
A regioselective approach to the synthesis of benzo[h][1,6]-naphthyridine and chromenopyrazinone derivatives was developed. The synthetic route to benzo[h][1,6]naphthyridines involves the N-propargylation of aromatic aminobenzaldehydes, followed by reaction with propargylamine in the presence of DBU (1,8-diazabicyclo[5.4.0] undec-7ene). For the synthesis of chromenopyrazine and chromeno-pyrazinone derivatives, the acetonitrile group was introduced to salicylaldehyde derivatives, and a DBU-promoted cyclizati...
Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran
Schrauben, Joel N.; Akdağ, Akın; Wen, Jin; Havlas, Zdenek; Ryerson, Joseph L.; Smith, Millie B.; Michl, Josef; Johnson, Justin C. (American Chemical Society (ACS), 2016-05-26)
Two isomers of both the lowest excited singlet (S-1) and triplet (T-1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such "excitation isomerism" is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properti...
Aminophosphine-palladium(II) complexes: Synthsesis, structure and applications in Suzuki and Heck cross-coupling reactions
AYDEMİR, MURAT; BAYSAL, AKIN; ŞAHİN, Ertan; Gumgum, Bahattin; Özkar, Saim (Elsevier BV, 2011-11-30)
Reaction of furfurylamine with 1 or 2 equivalents of PPh2Cl in the presence of Et3N, proceeds under anaerobic conditions in thf to give furfuryl-2-(N-diphenylphosphino)amine, Ph2PNHCH2-C4H3O, 1 and furfuryl-2-(N,N-bis(diphenylphosphino)amine), (Ph2P)(2)NCH2-C4H3O, 2, respectively. The reactions of 1 and 2 with MCl2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or Pt(CH3)(2)(cod) yield complexes [M(Ph2PNHCH2-C4H3O)(2)Cl-2] (M= Pd 1a, Pt 1b), [Pt(Ph2PNHCH2-C4H3O)(2)(CH3)(2)] (1c), and [M((Ph2P)(2) NCH2-C4H3O)Cl...
Study of asymmetric aldol and Mannich reactions catalyzed by proline-thiourea host-guest complexes in nonpolar solvents
Demir, Ayhan Sıtkı; BAŞÇEKEN, SİNAN (Elsevier BV, 2013-04-30)
A proline-thiourea host-guest complex has been described as a good catalyst for asymmetric reactions such as aldol and Mannich reactions. High stereoselectivities were obtained under optimal conditions. Thiourea was observed to have an important effect on the reactivity and selectivity, even in an unconventional nonpolar reaction medium and without the need to utilize low temperatures. This proline-thiourea host-guest system has the ability to participate in a hydrogen bonding network.
Synthesis of ferrocenyl pyrazoles by the reaction of (2-formyl-1-chlorovinyl)ferrocene with hydrazines
Zora, Metin (Elsevier BV, 2007-10-15)
Synthesis of ferrocenyl-substituted pyrazoles via the reaction between (2-formyl-1-chlorovinyl)ferrocene and hydrazine derivatives is described. Depending upon the substitution pattern of hydrazine, the reaction affords 1-alkyl/aryl-5-ferrocenylpyrazoles and/or 1-alkyl/ aryl-3-ferrocenylpyrazoles. The reaction appears to be general for a variety of hydrazine derivatives.
Citation Formats
IEEE
ACM
APA
CHICAGO
MLA
BibTeX
A. Akdağ, O. Acevedo, and M. L. Mckee, “Mechanism of 5,5-dimethylhydantoin chlorination: Monochlorination through a dichloro intermediate,”
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
, pp. 2282–2289, 2007, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/57330.