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Title: Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [2]
  1. Department of Radiology, School of Medicine, Washington University in Saint Louis, Saint Louis MO USA
  2. Department of Chemistry, University of Illinois at Urbana-Champaign, Champaign IL USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401796
Grant/Contract Number:
SC0008432
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Labelled Compounds and Radiopharmaceuticals
Additional Journal Information:
Journal Volume: 60; Journal Issue: 9; Related Information: CHORUS Timestamp: 2017-10-20 17:43:09; Journal ID: ISSN 0362-4803
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Zhou, Dong, Kim, Sung Hoon, Chu, Wenhua, Voller, Thomas, and Katzenellenbogen, John A. Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors. United Kingdom: N. p., 2017. Web. doi:10.1002/jlcr.3519.
Zhou, Dong, Kim, Sung Hoon, Chu, Wenhua, Voller, Thomas, & Katzenellenbogen, John A. Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors. United Kingdom. doi:10.1002/jlcr.3519.
Zhou, Dong, Kim, Sung Hoon, Chu, Wenhua, Voller, Thomas, and Katzenellenbogen, John A. 2017. "Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors". United Kingdom. doi:10.1002/jlcr.3519.
@article{osti_1401796,
title = {Evaluation of aromatic radiobromination by nucleophilic substitution using diaryliodonium salt precursors},
author = {Zhou, Dong and Kim, Sung Hoon and Chu, Wenhua and Voller, Thomas and Katzenellenbogen, John A.},
abstractNote = {},
doi = {10.1002/jlcr.3519},
journal = {Journal of Labelled Compounds and Radiopharmaceuticals},
number = 9,
volume = 60,
place = {United Kingdom},
year = 2017,
month = 6
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 14, 2018
Publisher's Accepted Manuscript

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  • The characteristics of aromatic nucleophilic substitution with activation by the iminium group in the iminium derivatives of p-alkoxy- and p-halogenobenzaldehydes were investigated. They are determined by the concurrent addition of the nucleophilic agents at the C=N multiple bond. The activating effect of the iminium group depends on the nature of the leaving group, the solvent, the substituent in the benzene ring, and the nature and concentration of the protonating agent. The action of heat on p-methoxybenzylidenemethylamine with a tenfold excess of methylamine hydrochloride in a 30% alcohol solution of methylamine at 150/degree/C for 40 h leads to substitution of themore » methoxymethylamino group with a yield of 90%.« less
  • This paper presents a kinetic study of reactions of pentafluorobenzene derivatives C/sub 6/F/sub 5/YR with sodium methylate and piperidine; also, values of omega /SUB p/ have been determined for the substituents RY in the polyfluorinated benzene ring. These values are in satisfactory agreement with values obtained for these substituents in a study of dissociation reactions of phenols and nucleophilic substitution reactions in a series of mono-substituted halobenzenes.
  • The polycondensation of polyhaloarenes with sodium sulfide in a medium of dipolar aprotic solvents provides the most widespread method for the synthesis of polyarylene sulfides. The authors have established that the presence of the solid phase Na/sub 2/S x 9H/sub 2/O is not sufficient condition for the initiation of the polycondensation of polyhaloarenes with sodium sulfide, and the authors showed that the initiation of this reaction under homogeneous conditions is possible. For the case of hexafluorobenzene by means of /sup 19/F NMR spectroscopy the authors established the formation of disubstituted products in its reaction with a blue solution of Na/submore » 2/S x 9H/sub 2/O in 1-methyl-2-pyrrolidinone. For the investigation the authors used recrystallized Na/sub 2/S x 9H/sub 2/O, freshly distilled solvents, and chromatographically pure polyhaloarenes. The /sup 19/F NMR spectra were determined on a JEOL FX-900 spectrometer with a working frequency for /sup 19/F of 84.25 MHz (internal standard C/sub 6/F/sub 6/, delta -162.9 ppm relative to CFCl/sub 3/).« less
  • The reaction mechanism of nucleophilic aromatic substitution of 1-chloro-2,4-dinitrobenzene by glutathione (as modeled by a thiomethoxide ion) in the gas phase and in solution was elucidated using ab initio molecular orbital theory in combination with a continuum solvent model at the HF/6-31G*, HF/6-31+G{sup **}, and MP2/6-31+G{sup **} levels of theory. Two ion-molecule complexes were located in the gas phase at the HF level, but only one exits at the MP2/6-31+G{sup **} level, while neither exits in aqueous solution. In aqueous solution, there is a large free energy barrier and C-S bond formation is the rate-determining step, which is in agreementmore » with experimental observation. The calculated free energy barrier (30.2 kcal/mol) and the HF/6-31+G{sup **} level of theory seems to be in good agreement with experiment (23.8 kcal/mol), while the MP2/6-31+G{sup **} barrier is too low, indicating that the MP2/6-31+G{sup **} level of theory probably overestimates the stability of the transition state for C-S bond formation. Implications for the mode of action of gluatathione S-transferases (GSTs) and a related enzyme are discussed in light of the results of the current study. 40 refs., 5 figs., 3 tabs.« less
  • 1,1,1-Trimethylhydrazinium iodide, TMHI, has been shown to be a novel vicarious nucleophilic substitution aminating reagent. It can be used to obtain isomers not produced by reaction with other nucleophilic aminating reagents. It is easily prepared from 1,1-dimethylhydrazine, or directly from hydrazine. Further studies on the use of TMHI and related quaternary hydrazines as nucleophlic aminating reagents are in progress. 1 tab.