1,3-Diiodo-5,5-dimethylhydantoin—An efficient reagent for iodination of aromatic compounds

Chaikovskii, V. K.; Филимонов, В. Д.; Функ, А. А.; Skorokhodov, V. I.; Огородников, В. Д.

doi:10.1134/s1070428007090060

Cited by 21 publications

(10 citation statements)

References 6 publications

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“…Detailed GC-MS study on the products of reactions of compound I with TIG-H 2 SO 4 , DIH-H 2 SO 4 , and NIS-H 2 SO 4 showed ( Table 1) that the use of stoichiometric amounts of the reagents (calculated on the active iodine) does not ensure complete conversion of I (Table 1, run nos. 1-3), and 30-35% of the initial compound remains unchanged.A similar conversion of other substrates at the same reagent-to-substrate ratio was noted by us previously [3][4][5][6]. Approximately similar selectivities were observed in the iodination with TIG-H 2 SO 4 and DIH-H 2 SO 4 .…”

supporting

confidence: 78%

“…A similar conversion of other substrates at the same reagent-to-substrate ratio was noted by us previously [3][4][5][6]. Approximately similar selectivities were observed in the iodination with TIG-H 2 SO 4 and DIH-H 2 SO 4 .…”

supporting

confidence: 78%

“…In the iodination with common iodinating systems, the reactivity and selectivity may be evaluated using the reaction with toluene as an example [2]. However, the procedure based on determination of the ratio of o-and p-iodotoluenes cannot be applied to reactions with superelectrophilic iodinating systems [3][4][5][6], which lead to the formation of a mixture of polyiodotoluenes containing mostly tri-and tetraiodo derivatives. Therefore, to estimate the selectivity of superelectrophilic iodinating systems we compared the compositions of products formed in the iodination of o-nitrotoluene (I) with reagents generated by dissolution of 1,3,4,6-tetraiodoglycoluril (TIG), 1,3-diiodo-5,5-dimethylhydantoin (DIH), and N-iodosuccinimide (NIS) in sulfuric acid [3,5,6] (Scheme 1).…”

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Evaluation of the reactivity and regioselectivity of superelectrophilic iodinating systems

2009

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Iodination of o-nitrotoluene in H 2 SO 4 or CF 3 SO 3 H at 0°C with compounds having a nitrogeniodine bond leads to the formation of isomeric mono-and diiodo derivatives whose ratio differs from the statistical value. The reaction of nitrobenzene with 2 equiv of N-I reagents in trifluoromethanesulfonic acid at 0°C takes less than 1 min and yields 79-85% of m-iodonitrobenzene. The electrophilic reactivity of the iodinating agents was estimated by quantum-chemical methods.The rate of electrophilic substitution reactions in the aromatic series and isomeric composition of the products are largely determined by the electrophile nature. In keeping with the Brown selectivity relationship, stronger electrophiles exhibit lower intramolecular selectivity in substitution reactions in the benzene ring [1]. The most reactive electrophiles give rise to a mixture of regioisomers whose ratio approaches statistical value. In the iodination with common iodinating systems, the reactivity and selectivity may be evaluated using the reaction with toluene as an example [2]. However, the procedure based on determination of the ratio of o-and p-iodotoluenes cannot be applied to reactions with superelectrophilic iodinating systems [3][4][5][6], which lead to the formation of a mixture of polyiodotoluenes containing mostly tri-and tetraiodo derivatives. Therefore, to estimate the selectivity of superelectrophilic iodinating systems we compared the compositions of products formed in the iodination of o-nitrotoluene (I) with reagents generated by dissolution of 1,3,4,6-tetraiodoglycoluril (TIG), 1,3-diiodo-5,5-dimethylhydantoin (DIH), and N-iodosuccinimide (NIS) in sulfuric acid [3, 5, 6] (Scheme 1).Traditional methods for the determination of the reactivity and regioselectivity of iodinating systems by analysis of the iodination products of nitroarene I cannot be used, for nitrotoluenes do not undergo iodination by common methods at 0°C. Detailed GC-MS study on the products of reactions of compound I with TIG-H 2 SO 4 , DIH-H 2 SO 4 , and NIS-H 2 SO 4 showed ( Table 1) that the use of stoichiometric amounts of the reagents (calculated on the active iodine) does not ensure complete conversion of I (Table 1, run nos. 1-3), and 30-35% of the initial compound remains unchanged.A similar conversion of other substrates at the same reagent-to-substrate ratio was noted by us previously [3][4][5][6]. Approximately similar selectivities were observed in the iodination with TIG-H 2 SO 4 and DIH-H 2 SO 4 . In the reaction with N-iodosuccinimide, the fraction of 4-iodo-2-nitrotoluene (II) was slightly larger than the fraction of 6-iodo-2-nitrotoluene (III), but the substrate conversion was lower.The reactions in the presence of 2 equiv of the iodinating agents (Table 1, run nos. 4-6) are characterized by appreciably reduced para-selectivity. However,

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confidence: 78%

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confidence: 78%

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confidence: 99%

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Evaluation of the reactivity and regioselectivity of superelectrophilic iodinating systems

2009

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“…Several years later, Chaikovskii and collaborators22 observed that if DIH was treated with conc. sulphuric acid, both of the two N bonded iodine atoms were removed from DIH, leading them to propose the formation of iodine hydrogen sulphate (HOSO 2 OI) 8 , as the pre‐iodination species, see Scheme .…”

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“…As a reference, we reproduced the experiment by Chaikovskii and collaborators22 with DIH in conc. sulphuric acid to achieve the expected UV‐profile indicating the I 3 + ion (entry 1 of Table 2).…”

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confidence: 99%

Fast Halogenation of Some N‐Heterocycles by Means of N,N′‐Dihalo‐5,5‐dimethylhydantoin

Sandtorv¹,

Bjørsvik²

2013

Adv Synth Catal

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An instantaneous, selective and high-yielding halogenation process is reported. The method operates with imidazoles, pyrazoles, and indoles under benign reaction conditions. The developed process involves the use of N,N'-dihalo-5,5-dimethylhydantoins (halo = chlorine, bromine, iodine) as halogenation reagents that are activated by catalytic quantities of a strong Brønsted acid. Moreover, the halogenation process is switchable to produce either the mono-or di-halogenated products. Issues related to the reaction mechanism are investigated and a proposal for a reaction mechanism is disclosed.

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Aromatic Halogenation

Larock

Zhang

2017

Comprehensive Organic Transformations

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1,3-Diiodo-5,5-dimethylhydantoin—An efficient reagent for iodination of aromatic compounds

Cited by 21 publications

References 6 publications

Evaluation of the reactivity and regioselectivity of superelectrophilic iodinating systems

Evaluation of the reactivity and regioselectivity of superelectrophilic iodinating systems

Fast Halogenation of Some N‐Heterocycles by Means of N,N′‐Dihalo‐5,5‐dimethylhydantoin

Aromatic Halogenation

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