1,2,5-Thiadiazole 2-oxides: selective synthesis, structural characterization, and electrochemical properties

Konstantinova, Lidia S.; Knyazeva, Ekaterina A.; Obruchnikova, Natalia V.; Vasilieva, Nadezhda V.; Irtegova, Irina G.; Nelyubina, Yulia V.; Bagryanskaya, I. Yu.; Shundrin, Leonid A.; Sosnovskaya, Zhanna Yu.; Zibarev, Andrey V.; Ракитин, Олег А.

doi:10.1016/j.tet.2014.06.096

Cited by 26 publications

(18 citation statements)

References 59 publications

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“…Previously, it was found that DFT calculations at the (U)B3LYP/6‐31+G(d) level of theory perform well for the first adiabatic EA (EA ad ) of various π‐heterocyclic compounds including polyfluorinated, as well as for hfc constants of their RAs . Therefore, the same functional was used in the present work.…”

Section: Resultsmentioning

confidence: 98%

Electrochemical properties and radical anions of carbocycle-fluorinated quinoxalines and their substituted derivatives

Shundrin

Irtegova

Vasilieva

et al. 2016

J. Phys. Org. Chem.

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Electrochemical reduction (ECR) and oxidation (ECO) of 5,6,7,8‐tetrafluoroquinoxaline (1) and its derivatives bearing various substituents R (7‐H (2), 7,8‐H2 (3), 6‐CF3 (4), 6‐Cl (5), 5,7‐Cl2 (6), 5‐NH2 (7), 6‐OCH3 (8), 6,7‐(OCH3)2 (9), 6,7,8‐(OCH3)3 (10), 5,6,7,8‐(OCH3)4 (11), 6‐OCH3,7‐N(CH3)2 (12), 6‐N(CH3)2 (13), 6,7‐(N(CH3)2)2 (14), 5,6,7‐(N(CH3)2)3 (15), and 7,8‐cyclo‐(=CF‐CF = CF‐CF=) (16)) in the carbocycle have been studied by cyclic voltammetry in MeCN. For 1–4 and 7–15, the first reduction peaks have been found to be 1‐electron and reversible, thus corresponding to the formation of their radical anions (RAs), which are long lived at 295 K except those of 4–6 and 15, 16. Irreversible hydrodechlorination has been observed for 5 and 6 at the first step of their ECR confirmed by EPR detection of corresponding RAs of 2 and 5,7‐H2 derivative of 1 (17) at the next steps. Electrochemically generated RAs of 1–3, 7–14, and 17 have been characterized in MeCN by EPR spectroscopy together with DFT calculations at the (U)B3LYP/6‐31 + G(d) level of theory using PCM to describe the solvent. A noticeable alternation of spin density on the –NCCN– moiety of quinoxaline has been observed for all RAs possessing R‐substitution asymmetry. The comparative electron‐accepting ability of 1–15 has been analyzed in terms of their experimental reduction peak potentials and the (U)B3LYP/6‐31 + G(d)‐calculated gas‐phase first adiabatic electron affinities (EAs). The differences in electron transfer solvation energies for 1–15 have been evaluated on the basis of ECR peaks' potentials and calculated gas‐phase EAs. The ECO of 1–5 and 7–14 has been found to be irreversible.

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Section: Resultsmentioning

confidence: 98%

Electrochemical properties and radical anions of carbocycle-fluorinated quinoxalines and their substituted derivatives

Shundrin

Irtegova

Vasilieva

et al. 2016

J. Phys. Org. Chem.

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“…Thus, treatment of dioximes with S 2 Cl 2 in MeCN leads to 2‐oxides of the target thiadiazoles at 5 °C and to thiadiazoles at room temperature. Further treatment of the oxides with S 2 Cl 2 and pyridine in MeCN at room temperature gives thiadiazoles (Scheme ) …”

Section: Synthesismentioning

confidence: 99%

Synthesis and Applications of 5‐Membered Chalcogen‐Nitrogen π‐Heterocycles with Three Heteroatoms

Ракитин

Zibarev

2018

Asian J Org Chem

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The recent progress in the synthesis of the title heterocycles exemplified by closed-and open-shell 1,2,5chalcogenadiazoles, 1,2,3-dichalcogenazoles and their hybrids (chalcogens: S, Se, and Te), and in actual or potential applications of these compounds in materials science and biomedicine, is discussed. The synthetic importance of the chalcogen exchange, both direct and indirect, is emphasized, as well as the significance of the heavier chalcogen derivatives in the design and synthesis of smart molecular materials.[a] Prof. Scheme 1.Representative examples of 1,2,5-chalcogenadiazoles and 1,2,3dichalcogenazoles including Appel and Herz cations and Herz radicals.

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“…In our study we use both traditional building blocks reviewed previously by us and by other authors and extended list of donor groups that includes some new previously unexplored fragments. Based on our recent investigations and the works of other researchers 7,[14][15][16][17][18][19][20][21][22][23][24] six variants of A-fragments (A-block) which have showed good characteristics were selected for the present study: [1,2,5]thiadiazolo [3,4-c] [3,4-c]pyridazine. The general formula for these derivatives is represented in Scheme 1.…”

Section: Building Blocks For D-a-π-a Featured Organic Sensitizersmentioning

confidence: 99%

Design and theoretical study of D–A–pi–A' organic sensitizers with [1,2,5]oxa-, thia- or selenadiazoloazine fragment

Потемкин¹,

Bol’shakov²,

Safiullin³

et al. 2017

Arkivoc

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A theoretical study and design of novel sensitizers based on D-A-π-A concept is fulfilled. The study shows a key role of central A-block for wavelength in UV-Vis spectra. Chalcogen of higher period as well as additional nitrogen in central A-block provide a noticeable red shift. The maximum wavelengths are observed for aliphatic/alicyclic D-blocks. The maximum oscillator strengths are observed for the planar D-block and increase along with its charge. Structure-spectral property relationships of sensitizers are studied using CRAQC (Correlation and Regression Analysis of Quantum Calculations). A method for chromophore determination is invented.

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1,2,5-Thiadiazole 2-oxides: selective synthesis, structural characterization, and electrochemical properties

Cited by 26 publications

References 59 publications

Electrochemical properties and radical anions of carbocycle-fluorinated quinoxalines and their substituted derivatives

Electrochemical properties and radical anions of carbocycle-fluorinated quinoxalines and their substituted derivatives

Synthesis and Applications of 5‐Membered Chalcogen‐Nitrogen π‐Heterocycles with Three Heteroatoms

Design and theoretical study of D–A–pi–A' organic sensitizers with [1,2,5]oxa-, thia- or selenadiazoloazine fragment

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