Cathodic reductions of cyanopyridines in liquid ammonia

Brown, O.R.; Butterfield, R.J.

doi:10.1016/0013-4686(82)80093-5

Cited by 10 publications

(15 citation statements)

References 6 publications

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“…Voltammetric studies of 2-, 3-and 4-cyanopyridine in liquid ammonia showed that 2-and 4-cyanopyridine both give a reversible one-electron reduction to a persistent anion radical whereas the reduction of 3-cyanopyridine proceeds irreversibly in an overall one-electron process with the product postulated to be a dimer [6]. The stability of the anion radical of 4-cyanopyridine has been confirmed in studies with DMF or acetonitrile as solvent [7][8][9][10][11].…”

Section: Introductionmentioning

confidence: 86%

Reversible dimerization of anion radicals: Studies of two cyanopyridines

Macı́as-Ruvalcaba

Evans

2011

Journal of Electroanalytical Chemistry

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Section: Introductionmentioning

confidence: 86%

Reversible dimerization of anion radicals: Studies of two cyanopyridines

Macı́as-Ruvalcaba

Evans

2011

Journal of Electroanalytical Chemistry

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“…The cyclic voltamogram gave a single pair of reversible peaks, clearly indicating that 1 does not form a dianion. Though dianion formation is important in the decyanation of some cyanopyridines [36,37].…”

Section: Molecular Orbital Electron Spin Density Calculation Of 6-phementioning

confidence: 99%

The photochemistry of 6‐phenanthridinecarbonitrile II. The physical and photophysical properties

Vittimberga

Sears

2001

Journal of Heterocyclic Chem

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The physical and photophysical properties of 6-phenanthridinecarbonitrile (1) have been examined. We previously reported that when 1 is irradiated in aqueous 2-propanol, three products are formed [3]. These include dimethyl-6-phenanthridinylcarbinol (2), phenanthridine (3) and 6,6'-biphenanthridine (4). Phenanthridinyl radical is formed in neutral media by hydrogen atom abstraction from an alcohol molecule by an excited state of 1 in a monophotonic process. The presents of acid effectively quenches all photochemical behavior. These products may all be explained assuming in-cage and out-of-cage reactions. The free spin value, g e , was determined at 125 K and found to be 2.0043 which is close to the theoretical value for that of a free electron. The total emission spectrum of 1 at 77 K shows a fluorescence maximum at 378 nm and a much weaker phosphorescence maximum at 502 nm which represented less than 3% of the total emission. When benzophenone is added to the reaction mixture, the triplet state of 1 is populated, but photosensitized product formation does not occur. The result supports a singlet reactive state. When cis/transpiperylene is added to the reaction mixtures, it quenches the fluorescence of 1. The fluorescence quantum yield (Φ f ) was found to be 0.227 in neat 2-propanol. The addition of water causes an increase in Φ f and a decrease in the Pk a of the medium. The excited state lifetime (τ) was determined in neat 2-propanol, using oxygen quenching, and found to be 3.4 ns. This number increased with increasing water concentration. The photoreactive state of 1 appears to be its π,π* singlet state making its behavior more like that of the corresponding hydrocarbon parent.

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“…Volke and Skála performed polarographic reduction of the cyanopyridines on dropping mercury electrode, and found that 4-CP and 2-CP were reduced to the corresponding aminomethylpyridines [9]. The reduction of cyanopyridines was also investigated by other electrochemical methods, including cyclic voltammetry (CV) and controlled potential coulometry [10]. It was concluded that the primary products were the respective radical anions [10].…”

Section: Introductionmentioning

confidence: 98%

“…The reduction of cyanopyridines was also investigated by other electrochemical methods, including cyclic voltammetry (CV) and controlled potential coulometry [10]. It was concluded that the primary products were the respective radical anions [10].…”

Section: Introductionmentioning

confidence: 99%

“…They are also employed as model molecules in interfacial electrochemistry for the investigations of bonding and/or coordination on metal surfaces [9][10][11][12][13][14][15][16][17]. Volke and Skála performed polarographic reduction of the cyanopyridines on dropping mercury electrode, and found that 4-CP and 2-CP were reduced to the corresponding aminomethylpyridines [9].…”

Section: Introductionmentioning

confidence: 99%

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