Redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes

Берберова, Н. Т.; Shinkar, E. V.; Smolyaninov, I. V.; Пащенко, К. П.

doi:10.1134/s0012500815120058

Cited by 13 publications

(5 citation statements)

References 7 publications

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“…However, in this study our attempts to functionalize Q by hydrogen sulfide in acetonitrile or hexane resulted in the formation of 3,5‐CatH 2 , inorganic polysulfanes, and sulfur. Previously we have considered the electrosyntheses (direct or mediator) of organosulfur compounds based on the reaction of H 2 S with alkenes, cycloalkanes in polar solvents with the production of alkanethiols or aliphatic di‐ and polysulfides [14b–d] . The catechol/quinone couple also used as redox‐mediator in the synthesis of S‐functionalized hydrocarbons, however the unsymmetrical sulfides were not observed.…”

Section: Resultsmentioning

confidence: 99%

“…In turn, we have considered the possibility of applying hydrogen sulfide as thiolation agent in the reaction with sterically hindered o ‐benzoquinone. It was previously found that the electrochemical activation of H 2 S in the presence of alkenes (cycloalkenes) leads to the formation of (cyclo‐)alkanethiols (RSH) under conditions of direct or mediator electrosynthesis [14a–b] . Along with the electrochemical activation, hydrogen sulfide can be oxidized by 3,5‐di‐ tert ‐butyl‐ o ‐benzoquinone ( Q ) [15] .…”

Section: Introductionmentioning

confidence: 99%

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New One‐Pot Synthesis of Catechol Thioethers Based on H₂S and Unsaturated Hydrocarbons

et al. 2020

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New one‐pot synthesis of catechol thioethers based on the reaction between H2S, 3,5‐di‐tert‐butyl‐o‐benzoquinone and unsaturated hydrocarbons was developed. This synthetic approach allows to produce target compounds in the media of alkenes or alkynes via an activation of H2S by 3,5‐di‐tert‐butyl‐o‐benzoquinone at room temperature. The method consists in sequential thiolation of an unsaturated hydrocarbon and a sterically hindered o‐benzoquinone. The reaction makes it possible to use hydrogen sulfide as a source of the sulfur atom in the synthesis of biologically active organosulfur compounds. Antioxidant activity of synthesized thioethers in CUPRAC‐test, induced oxidation of DNA or glutathione was determined. The proposed synthetic way is more effective than the synthesis of catechol thioethers via Michael addition of thiols because the formation of disulfide by‐products is reduced. In this study the application of available and cheap reagents such as hydrogen sulfide, alkenes, or alkynes to prepare sterically hindered catechols with thioether group was established.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

New One‐Pot Synthesis of Catechol Thioethers Based on H₂S and Unsaturated Hydrocarbons

et al. 2020

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“…Previous results on the use of redox, microwave and chemical activation of hydrogen sulfide (alkanethiols) showed a significant increase in their reactivity when in interaction with organic compounds in acetonitrile (dichloromethane) [40][41][42][43][44]. An important difference between the methods developed by us for the synthesis of organic sulfur derivatives is the mild process conditions compared to traditional approaches (thermolysis, radiolysis, photolysis, catalysis by metals or their complexes) required for the radical initiation of hydrocarbon reactions with hydrogen sulfide and thiols [45][46][47][48][49][50].…”

Section: Discussion Of Resultsmentioning

confidence: 99%

Logical-Information Model of Energy-Saving Production of Organic Sulfur Compounds from Low-Molecular Sulfur Waste Fuel Oil

et al. 2020

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A logical-informational model of energy resource-efficient chemical technology for the utilization of hydrogen sulfide and low molecular alkanethiols, which are toxic and difficult to remove sulfur components of residual fuel (fuel oil), is proposed. Based on the IDEF1 methodology and existing knowledge about the technological processes of the demercaptanization of various hydrocarbon raw materials (oils, gas condensates), a scheme for the production of organic sulfur compounds from sulfur waste extracted from fuel oil has been modeled. For a sufficiently complete removal of hydrogen sulfide and low molecular weight alkanethiols, energy- and resource-saving stages of the technological process have been developed, which are implemented by ultrasonic and/or magnetic treatment of fuel oil. It is proposed to use the combined action of two alternative methods of processing fuel oil to increase the efficiency of cleaning fuel oil from sulfur components. For the first time, an approach has been developed to utilize unwanted sulfuric impurities contained in fuel oil by involving electric and microwave synthesis in green technological processes, to obtain practically useful organic sulfur compounds with biological activity. It is shown that the use of one-electron oxidant thiols and hydrogen sulfide in organic media leads to the synthesis of organic disulfides and elemental sulfur. Indirect (with the use of mediators) electrosynthesis contributes to the cyclic conduct of the technological process, an increase in efficiency and a decrease in energy consumption compared to the direct (on electrodes) initiation of sulfur components.

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“…In addition, cycloalkyldisulfides can be formed during the thiolation of inert cycloalkanes via the indirect activation of hydrogen sulfide by redox mediators. 38,39 Unsymmetrical disulfides can be obtained by the anodic activation of trisulfides in the presence of alkenes under the action of RSS + as a sulfenylation agents. 40 Electrolysis of a mixture of symmetrical disulfides at alternating current leads to S-S bond metathesis and a wide range of heterodimers.…”

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confidence: 99%

Redox-Mediated and Microwave-Assisted Thiol Activation: Two Approaches to Unsymmetrical Disulfides Synthesis

Burmistrova

Galustyan²,

Smolyaninov³

et al. 2022

J. Electrochem. Soc.

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Two approaches to synthesis of unsymmetrical disulfides based on different types of thiol activation, namely, an electrochemical method in the presence of a redox mediator and a microwave irradiation, were discussed. The mediated electrosynthesis procedures were carried out by the oxidative coupling of thiols or by the thiol-disulfide exchange in the presence of redox pairs – substituted o-aminophenol/o-iminobenzoquinone. It has been established that the formation of unsymmetrical disulfides under electrochemical conditions occurs as a result of both the oxidative coupling of sulfur-centered radicals, and a redox-mediator promoted thiol-disulfide exchange which led to a high yield of heterodimeric products (89–99%). The microwave-assisted synthesis made it possible to obtain the target products with yields of 13–86% depending on different irradiation parameters such as power, temperature, and irradiation duration. However, this method requires a rigorous selection of conditions for each reaction and is therefore inferior to the electrochemical approach.

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Redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes

Cited by 13 publications

References 7 publications

New One‐Pot Synthesis of Catechol Thioethers Based on H₂S and Unsaturated Hydrocarbons

New One‐Pot Synthesis of Catechol Thioethers Based on H₂S and Unsaturated Hydrocarbons

Logical-Information Model of Energy-Saving Production of Organic Sulfur Compounds from Low-Molecular Sulfur Waste Fuel Oil

Redox-Mediated and Microwave-Assisted Thiol Activation: Two Approaches to Unsymmetrical Disulfides Synthesis

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Redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes

Cited by 13 publications

References 7 publications

New One‐Pot Synthesis of Catechol Thioethers Based on H2S and Unsaturated Hydrocarbons

New One‐Pot Synthesis of Catechol Thioethers Based on H2S and Unsaturated Hydrocarbons

Logical-Information Model of Energy-Saving Production of Organic Sulfur Compounds from Low-Molecular Sulfur Waste Fuel Oil

Redox-Mediated and Microwave-Assisted Thiol Activation: Two Approaches to Unsymmetrical Disulfides Synthesis

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Product

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New One‐Pot Synthesis of Catechol Thioethers Based on H₂S and Unsaturated Hydrocarbons

New One‐Pot Synthesis of Catechol Thioethers Based on H₂S and Unsaturated Hydrocarbons