Cerium ammonium nitrate-catalyzed aerobic oxidative coupling of dithiocarbamates: facile synthesis of thioureas and bis(aminothiocarbonyl)disulfides

Li, Tiantian; Song, Xianghai; Wang, Meishuang; Ma, Ning

doi:10.1039/c4ra04628e

Cited by 11 publications

(7 citation statements)

References 96 publications

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“…The carbonic acid solution resulting from dissolved carbon dioxide dissociates hydrogen ions to increase the amount of dimethyl dithiocarbamic acid and at the same time form sodium bicarbonate and sodium carbonate. Then, hydrogen peroxide reacts with dimethyl dithiocarbamic acid to give corresponding thiyl radicals which dimerize to generate the final product of disulfide thiuram. Although the acidity of carbonic acid is weaker than that of dimethyl dithiocarbamic acid and diethyl dithiocarbamic acid (Table ), the fast generation of solid TMTD promotes the reaction to proceed smoothly.…”

Section: Resultsmentioning

confidence: 99%

Green Synthesis of Thiuram Disulfides with CO₂ as an Acid Agent for Sustainable Development

Wang

Deng

et al. 2018

Ind. Eng. Chem. Res.

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A green synthesis method for the oxidation of sodium dialkyldithiocarbamate to the corresponding thiuram disulfides was developed in the presence of CO2 as the neutralizing agent, H2O2 as the oxidant, and water as the solvent. The method could provide much greener reaction conditions, convert CO2 to a relatively high-quality product without H2SO4 consumption, and obtain high yields and purity of products. The effects of CO2 flow rate, reaction temperature, concentration, dropping speed, and excess degree of hydrogen peroxide, as well as the concentration of sodium dimethyldithiocarbamate, were investigated. By HPLC-MS detection of the mother liquor, it was found that the organic byproducts of this oxidation process were the hydrolysis product of TMTD (tetramethyl thiuram disulfide), sodium dimethylcarbamothioate, and the peroxidation product of sodium dimethyldithiocarbamate, sodium (dimethylamino)(thioxo)methanesulfonate, which have been rarely proven experimentally by previous work. These byproducts were generated in the latter stage of the oxidation process. Therefore, possible chemical reactions of this synthesis process were proposed. On the basis of these reactions, a 0.6 stoichiometric hydrogen peroxide dosage was added, the mother liquor was recycled, and no organic byproduct was found after five stages of recycling. As a result, the discharge of wastewater was greatly reduced. Tetraethyl thiuram disulfide was also synthesized by this method to demonstrate its universality.

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Section: Resultsmentioning

confidence: 99%

Green Synthesis of Thiuram Disulfides with CO₂ as an Acid Agent for Sustainable Development

Wang

Deng

et al. 2018

Ind. Eng. Chem. Res.

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“…1‐Benzyl‐3‐cyclohexylthiourea (6 ha) : Beige solid, m.p. 108–109 °C (water; ref [81] . 89–90 °C); 1 H‐NMR: (500 MHz, CDCl 3 , ref [82] …”

Section: Methodsmentioning

confidence: 99%

“…108-109°C (water; ref. [81] 89-90°C); 1 H-NMR: (500 MHz, CDCl 3 , ref. [82] [83] 94°C); 1 H-NMR: (500 MHz, CDCl 3 , mixture of E/Z isomers, ref [83] ) δ 7.38À 7.30 (m, 5H), 6.01 (bs, 1H), 5.86 (bs, 1H), 4.78À 4.77 (m, 2H), 1.39 (s, 9H) ppm.…”

Section: -Benzyl-3-(4-methoxyphenyl)thiourea (6 Ga)mentioning

confidence: 99%

Chromatography‐Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

et al. 2020

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The development of a new three-component chromatographyfree reaction of isocyanides, amines and elemental sulfur allowed us the straightforward synthesis of thioureas in water. Considering a large pool of organic and inorganic bases, we first optimized the preparation of aqueous polysulfide solution from elemental sulfur. Using polysulfide solution, we were able to omit the otherwise mandatory chromatography, and to isolate the crystalline products directly from the reaction mixture by a simple filtration, retaining the sulfur in the solution phase. A wide range of thioureas synthesized in this way confirmed the reasonable substrate and functional group tolerance of our protocol.

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“…The first oxidation step can most probably be assigned to the formation of a thiuramdisulfide, a product which is readily formed by dithiocarbamate oxidation (Scheme 3a). [25,26] The electrochemical oxidation of dithiocarbamates has been reported previously by Lieder, who discussed the electrochemical formation of dithiocarbamoyl radicals followed by dimerization to the thiuramdisulfide (EC mechanism). [27] As potential products of further oxidation, tri-and thetrathian ions have been reported in the previous literature (Scheme 3b).…”

Section: Resultsmentioning

confidence: 93%

Alkali Metal Dithiocarbamato Carboxylates (DTCCs) – Synthesis, Properties, and Crystal Structures

et al. 2021

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A series of alkali metal salts of dithiocarbamate‐substituted carboxylate (DTCC) anions were prepared by reaction of the parent amino acids with carbon disulfide and an alkali metal hydroxide. The target compounds, which were isolated in anhydrous form or as hydrates, were extensively characterized by elemental analyses, IR and NMR spectroscopy, thermal analyses, cyclic voltammetry, and single‐crystal X‐ray diffraction. The isolated compounds are more or less hygroscopic and display a varying dehydratization and decomposition behavior upon heating. The assumed degradation of the DTCC scaffold was found to depend on the substitution pattern as well as on the alkali metal counterion, and covers a range between 200 and 340 °C. In aqueous solution, the DTCC anions show irreversible electrochemical oxidations, where the corresponding redox potentials are governed by the substitution pattern of the nitrogen atom. Single‐crystal structural analyses of sodium and potassium derivatives revealed that these compounds exist as two‐ or three‐dimensional coordination polymers in the solid state, with the alkali‐metal ions adopting typical irregular coordination environments with coordination numbers of six or higher.

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Cerium ammonium nitrate-catalyzed aerobic oxidative coupling of dithiocarbamates: facile synthesis of thioureas and bis(aminothiocarbonyl)disulfides

Cited by 11 publications

References 96 publications

Green Synthesis of Thiuram Disulfides with CO₂ as an Acid Agent for Sustainable Development

Green Synthesis of Thiuram Disulfides with CO₂ as an Acid Agent for Sustainable Development

Chromatography‐Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

Alkali Metal Dithiocarbamato Carboxylates (DTCCs) – Synthesis, Properties, and Crystal Structures

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Cerium ammonium nitrate-catalyzed aerobic oxidative coupling of dithiocarbamates: facile synthesis of thioureas and bis(aminothiocarbonyl)disulfides

Cited by 11 publications

References 96 publications

Green Synthesis of Thiuram Disulfides with CO2 as an Acid Agent for Sustainable Development

Green Synthesis of Thiuram Disulfides with CO2 as an Acid Agent for Sustainable Development

Chromatography‐Free Multicomponent Synthesis of Thioureas Enabled by Aqueous Solution of Elemental Sulfur

Alkali Metal Dithiocarbamato Carboxylates (DTCCs) – Synthesis, Properties, and Crystal Structures

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Green Synthesis of Thiuram Disulfides with CO₂ as an Acid Agent for Sustainable Development

Green Synthesis of Thiuram Disulfides with CO₂ as an Acid Agent for Sustainable Development