Ion-molecular reactions of free phenylium ions, generated by tritium β-decay with group V–VII elements

Щепина, Н. Е.; Nefedov, V.D.; Toropova, M.; Аврорин, В. В.; Lewis, S. B.; Mattson, Bruce

doi:10.1016/s0040-4039(00)00854-6

Cited by 18 publications

(13 citation statements)

References 16 publications

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“…Since nucleogenic phenyl cations are free, steric effects (especially from offending solvent molecules) become unimportant. We have observed this fact in our synthesis of previously unknown tetraphenylammonium compounds [23]. Moreover, during classical electrophilic reaction on heterocyclic system deactivation of pyridine ring takes place due to the protonation of nitrogen atom by strong acids used for these reactions [24].…”

Section: Resultsmentioning

confidence: 92%

Pathways of ion–molecular interactions of nucleogenic phenyl cations with the nucleophilic centers of picolines

Щепина

Аврорин

Бадун

et al. 2012

Organic and Medicinal Chemistry Letters

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BackgroundThe nuclear-chemical method brought unique opportunity for synthesis of unknown and hardly available organic compounds. Presence of tritium labeling allows one-step preparation of radioactive markers for the investigation of chemical and biological processes.MethodsThe ion–molecular reactions of nucleogenic phenyl cations with 4-picoline have been carried out. The phenyl cations were generated by spontaneous tritium β-decay within the tritium-labeled benzene. Both additions to the nitrogen and substitutions about the aromatic ring were able to be studied simultaneously.ResultsUnusual substitutions on both the α- and β-positions of the ring system have been revealed.ConclusionBy unknown direct phenylation of nitrogen atom tritium-labeled N-phenylpicolinium derivatives, perspective biological markers have been synthesized.

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Section: Resultsmentioning

confidence: 92%

Pathways of ion–molecular interactions of nucleogenic phenyl cations with the nucleophilic centers of picolines

Щепина

Аврорин

Бадун

et al. 2012

Organic and Medicinal Chemistry Letters

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“…Shchepina et al generated phenyl cations through the β-decay of hexatritium benzene 69 which reacted in solution with tertiary amines (Scheme 13). 70 An isotopically labeled tetraphenylammonium salt was accessible by this method, but it was obtained only in 6% yield and the product underwent further decay producing additional byproducts. In addition, labeled N-methyl-N,N,N-triphenylammonium iodide and N,N-dimethyl-N,N-diphenylammonium iodide were prepared in 7% and 25% yield, respectively.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Strategies for the Synthesis of N-Arylammonium Salts

Arava

Diesendruck

2017

Synthesis

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The N-arylation of tertiary amines to provide sp3 quaternary ammonium salts is a challenge in organic chemistry. To date, no general method for such arylations has been established. Here, we summarize a variety of strategies that have been tested, starting with harsh nucleophilic aromatic substitutions, through to the use of copper catalysis and the application of strong electrophiles, such as phenyl cations and benzynes. The achievements and limitations of each method are summarized, and the challenges yet to be met in the synthesis of charged ammonium compounds are described.1 Introduction2 Alkylation of Anilines: The Menshutkin Reaction3 Arylations3.1 Nucleophilic Aromatic Substitutions by Tertiary Amines3.2 Preparation of N-Arylpyridinum Salts from Zincke and Pyrylium Salts3.3 Arylations Using Phenyl Cations3.4 Copper-Catalyzed Arylation of N-Heteroarenes3.5 Benzynes as Aryl Electrophiles4 Conclusions and Perspective

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“…Protonated di-n-butyl sulfate also undergoes a gas phase rearrangement reaction via an ion-neutral intermediate to form a [C 8 H 17 ] + alkyl cation with concomitant loss of a H 2 SO 4 . 86 Tritium beta-decay has been used to generate free phenylium ions and study their ion-molecule reactions with halobenzenes 87 and organic derivatives of nitrogen and phosphorus. 88 This technique allows the products of these reactions to be analyzed via thin layer chromatography.…”

Section: A Carbocation Ion-molecule Reactionsmentioning

confidence: 99%

“…86 Tritium beta-decay has been used to generate free phenylium ions and study their ion-molecule reactions with halobenzenes 87 and organic derivatives of nitrogen and phosphorus. 88 This technique allows the products of these reactions to be analyzed via thin layer chromatography. Two pathways for interaction of the phenylium ion with the halobenzenes PhX were found: addition to the lone pair of the halogen to form halonium ions, Ph 2 X + , or substitution on the aromatic ring.…”

Section: A Carbocation Ion-molecule Reactionsmentioning

confidence: 99%

Untitled

O’Hair

2001

Annu. Rep. Prog. Chem., Sect. B

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Ion-molecular reactions of free phenylium ions, generated by tritium β-decay with group V–VII elements

Cited by 18 publications

References 16 publications

Pathways of ion–molecular interactions of nucleogenic phenyl cations with the nucleophilic centers of picolines

Pathways of ion–molecular interactions of nucleogenic phenyl cations with the nucleophilic centers of picolines

Strategies for the Synthesis of N-Arylammonium Salts

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