The Role of Iodine and Pyridine Bases in the Electrocatalytic Oxidation of Alcohols Mediated by 4-AcNH-TEMPO

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Abstract

The role of iodine, pyridine bases and nitroxyl radical (NR) – 4-AcNH-TEMPO in the electro oxidative transformation of alcohols to carbonyl compounds in a two-phase environment CH2Cl2/NaHCO3 (aq.) has been studied. Using the CV method, it was established that the iodide ion in a weakly alkaline medium (pH 8.6) is oxidized to active forms of iodine (I2 and I+), which are terminal oxidizers for NR capable of being converted into oxoammonium cations (OС), necessary for the oxidation of alcohol. Spectrophotometrically it has been established that pyridine bases are capable of stabilizing I2 and/or I+ in the form of [PyI2], [PyI]+ complexes, the formation of which occurs predominantly in the organic phase. Stabilized forms of iodine effectively convert NR into OC at the interface. The formation of a catalytic complex between OС and a pyridine base occurs in the aqueous phase. CV studies have shown that the rate of NR-mediated alcohol oxidation increases up to 4 times in the presence of a pyridine base, in contrast to the oxidative transformation without a pyridine base. This proves the advantages of the NR/pyridine base catalytic system and the role of the pyridine base as a promoter in the inderect electrooxidation of alcohols.

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E. N. Shubina

Don State Technical University

Email: kashparova2013@mail.ru
Russian Federation, Rostov-on-Don

V. P. Kashparova

Platov South Russian State Polytechnic University

Author for correspondence.
Email: kashparova2013@mail.ru
Russian Federation, Novocherkassk

Ya. A. Ricker

Don State Technical University

Email: kashparova2013@mail.ru
Russian Federation, Rostov-on-Don

D. V. Steglenko

Southern Federal University

Email: kashparova2013@mail.ru
Russian Federation, Rostov-on-Don

I. Yu. Zhukova

Don State Technical University; Platov South-Russian State Polytechnic University

Email: iyuzh@mail.ru
Russian Federation, Rostov-on-Don; Novocherkassk

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2. Fig. 1. CBA of SU electrode: 1 - 0.5 M NaHCO3 (pH 8.6); 2 - 0.5 M NaHCO3 + 4-AcNH-TEMPO (10-3 mol); 3 - 0.5 M NaHCO3 + KI (2 · 10-3 mol). CBA of Pt electrode: 4 - 0.5 M NaHCO3 + KI (2 · 10-3 mol). Electrolyte temperature - 25°C; potential sweep rate - 0.01 V/s.

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3. Scheme 1. Single-reactor indirect electrocatalytic oxidation of alcohols

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4. Fig. 2. CBA of SU electrode: 1 - 0.5 M NaHCO3 (pH 8.6); 2 - 0.5 M NaHCO3 + KI (2 · 10-3 mol); 3 - 0.5 M NaHCO3 + KI (2 · 10-3 mol) + Py (0. 2 · 10-3 mol); 4 - 0.5 M NaHCO3 + KI (2 · 10-3 mol) + Py (0.4 - 10-3 mol); 5 - 0.5 M NaHCO3 + KI (2 · 10-3 mol) + Py (0.6 · 10-3 mol). Electrolyte temperature - 25°C; potential sweep rate - 0.01 V/s.

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5. Fig. 3. Electronic absorption spectra in H2O: (a) 1 - 10-3 M iodine; 2 - 10-3 M Py; 3-10-3 M 2,6-Lut; 4 - 10-3 M Collid; (b) mixtures: 1 - 10-3 M iodine + 10-3 M Py; 2 - 10-3 M iodine + 10-3 M 2,6-Lut; 3 - 10-3 M iodine + 10-3 M Collid.

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6. Fig. 4. Electronic absorption spectra in CH2Cl2: (a) 1 - 10-3 M I2; 2 - 10-3 M Py; 3 - 10-3 M 2,6-Lut; 4 - 10-3 M Collid; (b) mixtures: 1 - 10-3 M I2 + 10-3 M Py; 2 - 10-3 M I2 + 10-3 M 2,6-Lut; 3 - 10-3 I2 + 10-3 M Collid.

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7. Fig. 5. Electronic absorption spectra: (a) in H2O: 1 - 0.2 · 10-3 M 4-AcNH-TEMPO; 2 - 0.2 · 10-3 M 4-AcNH-TEMPO + 10-3 M I2; 3 - 10-3 Py + 10-3 M I2; 4 - 0.2 · 10-3 M 4-AcNH-TEMPO + 10-3 M I2 + 10-3 M Py; (b) in CH2Cl2: 1 - 0.2 · 10-3 M 4-AcNH-TEMPO; 2 - 0.2 · 10-3 4-AcNH-TEMPO + 10-3 M I2; 3 - 10-3 M Py + 10-3 M I2; 4 - 0.2 · 10-3 M 4-AcNH-TEMPO + 10-3 M I2 + 10-3 M Py.

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8. Fig. 6. CBA of SU electrode: 1 - 0.5 M NaHCO3 (pH 8.6); 2 - 0.5 M NaHCO3 + 1-octanol (50 - 10-3 mol); 3 - 0.5 M NaHCO3 + Py (10-3 mol); 4 - 0. 5 M NaHCO3 + 4-AcNH-TEMPO (10-3 mol); 5 - 0.5 M NaHCO3 + 4-AcNH-TEMPO (10-3 mol) + 1-octanol (50 · 10-3 mol). Electrolyte temperature - 25°C; potential sweep rate - 0.01 V/s.

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9. Fig. 7. CBA of SU electrode: 1 - 0.5 M NaHCO3 (pH 8.6); 2 - 0.5 M NaHCO3 + 4-AcNH-TEMPO (10-3 mol); 3 - 0. 5 M NaHCO3 + 4-AcNH-TEMPO (10-3 mol) + Py (10-3 mol); 4 - 0.5 M NaHCO3 + 4-AcNH-TEMPO (10-3 mol) + Py (10-3 mol) + 1-octanol (50 · 10-3 mol). Electrolyte temperature - 25°C; potential sweep rate - 0.01 V/s.

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