Formation of Stable Free Radicals on Electroreduction of N-Alkylpyridinium Salts

Schwarz, W.; Kosower, Edward M.; Shain, Irving.

doi:10.1021/ja01475a045

Cited by 65 publications

(27 citation statements)

References 1 publication

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“…Measuring the UV-Vis spectrum of this blue solution, we found that there were two absorption peaks at 600 and 395 nm, respectively (Fig. 2) which agreed with the results of previous reports [4,10]. Thus, it can be concluded that this blue solution contained a cation-free radical with the following structure.…”

Section: The Impact Of Membranesupporting

confidence: 89%

The electrochemical reaction of methyl pyridinium chloride in acetonitrile

Lin

Wang

Wan

1987

Journal of the Chinese Institute of Engineers

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The electrochemical reduction of methyl pyridinium chloride (MPCl) in an acetonitrile solvent system was studied. O r results show that, after a cathodic reduction, MPCl can continuously be oxidized at the anode to form 1, l'-dimethyl-4, 4´-bipyridinium dichloride (DMPCl). The effects of current density, temperature and MPCl concentration on the yield of DMPCl were also determined. Finally, the possible reaction mechanism of the reduction of MPCl was deduced.

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Section: The Impact Of Membranesupporting

confidence: 89%

The electrochemical reaction of methyl pyridinium chloride in acetonitrile

Lin

Wang

Wan

1987

Journal of the Chinese Institute of Engineers

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“…[52] In duplexes labeled with both Py-dU and DMA-dU, secondary ET from DMA to Py þ =dU À should produce the DMA þ =Py=dU À ET product that is expected to live significantly longer than Py þ =dU À . [44,[53][54][55] A straightforward way of positioning an electron trap in the DNA major groove is to attach covalently an easily reducible subunit to the 5position of uridine. In addition to the syntheses of four pyridinyl-dU nucleosides, this paper also reports the synthesis of four pyridiniumyl-dU nucleoside traps.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 5-(Pyridinyl and Pyridiniumyl)-2′-Deoxyuridine Nucleosides: Reversible Electron Traps for Dna

Gaballah

Netzel

2002

Nucleosides, Nucleotides and Nucleic Acids

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The desire to produce reversible electron traps for direct, room temperature studies of excess electron transport in DNA duplexes and hairpins motivated our efforts first to link pyridines to 2'-deoxyuridine (pyridinyl-dU) and then to convert these new conjugates into pyridiniumyl-dU nucleosides. Base sensitivity studies presented here rule out general use of bipyridinediiumyl compounds, but show that pyridiniumyl compounds are suitable for use under the strand cleavage and base deprotection procedures required for automated solid-phase oligonucleotide synthesis. This paper presents the synthesis of four 5'-O-DMT-protected 5-(N-methylpyridiniumyl)-dU conjugates using either ethynyl or ethylenyl linkers to join the pyridiniumyl and dU subunits.

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“…The yield based on the amount af Py+ present prior to electrolysis was 71%. Assuming a mechanism involving 1.5 electrons per pyridinium species (2), this corresponds to a current efficiency of 98%. Similar results were obtained for the reduction of a 0.093 mM solution of Py+ in 0.1M TBAP-acetonitrile and also for a 0.97 mM solution of Py+ in 0.251VI lithium perchlorate-acetonitrile.…”

Section: Resultsmentioning

confidence: 99%

“…Our results, which show dimer formation occurs at th e first wave and more rapidly at the second wave (1), seem consistent with the idea that the dimer is, in both cases, formed by attack of the anion on the pyridinium ion, and that it is the disproportionation of Py" into Py+ and Py-that makes the rate of dimer formation at the first wave slower than at the second. The dimerization of Py" with subsequent formation of PQ+' has been shown to occur readily in polar solvents such as water (2,3). However, in nonpolar solvents such as n-heptane (3) and dimethoxyethane (8), Py' is r~latively stable.…”

Section: Vol 129 No 12mentioning

confidence: 99%

Controlled Potential Coulometry of 4‐Cyano‐1‐Methylpyridinium Ion in Acetonitrile

Webber

Osteryoung

1982

J. Electrochem. Soc.

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The electrochemical reduction of 4-cyano-l-methylpyridinium ion in acetonitrile has been studied using controlled potential coulometry in conjunction with d-c polarography and u.v.-visible spectroscopy. In our previous polarographic study, the pyridinyl radical formed at the potential of the first wave was found to be stable, whereas the anion formed at the second wave could react with the parent pyridinium ion to form a dimer. On the longer time scale of coulometry, both anion and radical form this dimer, which subsequently loses two cyanide groups to yield the Paraquat dication. If the reduction potental is set at the first wave, the Pa.raquat dication is then further reduced to the radical cation by the pyridinyl radical in solution. Reduction at the second wave causes the Paraquat dication to be reduced even further to the neutral bipyridyl. The nature of the intermediate dimer is discussed. It seems quite possible that disproportionation of the pyridinyl radical to pyridinium ion and anion may be a step in the dimerization of the pyridinyl radicals.

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Formation of Stable Free Radicals on Electroreduction of N-Alkylpyridinium Salts

Cited by 65 publications

References 1 publication

The electrochemical reaction of methyl pyridinium chloride in acetonitrile

The electrochemical reaction of methyl pyridinium chloride in acetonitrile

Synthesis of 5-(Pyridinyl and Pyridiniumyl)-2′-Deoxyuridine Nucleosides: Reversible Electron Traps for Dna

Controlled Potential Coulometry of 4‐Cyano‐1‐Methylpyridinium Ion in Acetonitrile

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