vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/achb.934RIHDQYvuzbiochemi-1287Research ArticleКРАТКИЕ СООБЩЕНИЯBRIEF COMMUNICATIONСинтез 1,3-пропанбис(дитиокарбамата) натрия и исследование его флотационных свойствSynthesis of sodium 1,3-propanebis(dithiocarbamate) and study of its flotation propertieshttps://orcid.org/0009-0003-3872-0572СахабутдиноваТ. Х.SakhabutdinovaT. Kh.

Сахабутдинова Татьяна Хамитовна - инженер-исследователь.

664074, Иркутск, ул. Лермонтова, 83

Tatiana Kh. Sakhabutdinova - Research Engineer

83, Lermontov St., Irkutsk, 664074

statyana411@gmail.comhttps://orcid.org/0000-0002-1921-0257ВчислоН. В.VchisloN. V.

Вчисло Надежда Викторовна - к.х.н., научный сотрудник.

664033, Иркутск, ул. Фаворского, 1

Nadezhda V. Vchislo - Cand. Sci. (Chemistry), Researcher, A.E. Favorsky Irkutsk Institute of Chemistry SB RAS,

1, Favorsky St., Irkutsk, 664033

vchislo@irioch.irk.ruhttps://orcid.org/0000-0003-4907-5612ВерочкинаЕ. А.VerochkinaE. A.

Верочкина Екатерина Александровна - к.х.н., научный сотрудник.

664033, Иркутск, ул. Фаворского, 1

Ekaterina A. Verochkina - Cand. Sci. (Chemistry), Researcher.

1, Favorsky St., Irkutsk, 664033

kleptsova84@mail.ruhttps://orcid.org/0000-0001-5293-5316ФедосееваВ. Г.FedoseevaV. G.

Федосеева Виктория Германовна - научный сотрудник,

664033, Иркутск, ул. Фаворского, 1

Victoria G. Fedoseeva – Researcher.

1, Favorsky St., Irkutsk, 664033

vic_yol@mail.ruhttps://orcid.org/0000-0002-5356-0349БурдоновА. Е.BurdonovA. E.

Бурдонов Александр Евгеньевич - к.т.н., доцент, доцент.

664074, Иркутск, ул. Лермонтова, 83

Aleksandr E. Burdonov - Cand. Sci. (Engineering), Associate Professor, Associate Professor.

83, Lermontov St., Irkutsk, 664074

burdonovae@ex.istu.eduhttps://orcid.org/0000-0001-7817-7816РозенцвейгИ. Б.RozentsveigI. B.

Розенцвейг Игорь Борисович - д.х.н., доцент, заведующий лабораторией, заместитель директора по научной работе, Иркутский институт химии им. А.Е. Фаворского СО РАН, профессор Иркутский ГУ.

664003, Иркутск, ул. Карла Маркса, 1

Igor B. Rozentsveig - Dr. Sci. (Chemistry), Associate Professor, Head of the Laboratory, Deputy Director for Research, A.E. Favorsky Irkutsk Institute of Chemistry SB RAS, Professor Irkutsk SU.

1, Karl Marx St., Irkutsk, 664003

i_roz@irioch.irk.ruИркутский национальный исследовательский технический университетРоссияIrkutsk National Research Technical UniversityRussian FederationИркутский институт химии им. А.Е. Фаворского СО РАНРоссияA.E. Favorsky Irkutsk Institute of Chemistry SB RASRussian FederationИркутский институт химии им. А.Е. Фаворского СО РАН; Иркутский государственный университетРоссияA.E. Favorsky Irkutsk Institute of Chemistry SB RAS; Irkutsk State UniversityRussian Federation202430092024143428435Copyright © Сахабутдинова Т.Х., Вчисло Н.В., Верочкина Е.А., Федосеева В.Г., Бурдонов А.Е., Розенцвейг И.Б., 20242024Сахабутдинова Т.Х., Вчисло Н.В., Верочкина Е.А., Федосеева В.Г., Бурдонов А.Е., Розенцвейг И.Б.Sakhabutdinova T.K., Vchislo N.V., Verochkina E.A., Fedoseeva V.G., Burdonov A.E., Rozentsveig I.B.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/1287

Разработка и выбор подходящего реагента для эффективной флотации имеет важное значение в процессе обогащения руд. Дитиокарбаматы представляют класс органических соединений, которые широко используются в качестве реагентов-собирателей при флотации руд. В работе проведен аналитический обзор по методам получения данного класса соединений. Зафиксировано, что основным методом получения солей дитиокарбаматов является взаимодействие первичных или вторичных аминов с сероуглеродом (CS2) в присутствии гидроксида калия или натрия. Основной целью работы являлся синтез 1,3-пропанбис(дитиокарбамата) натрия и исследование его флотационных свойств при обогащении золотосодержащих сульфидных руд. Коллективом авторов был предложен простой и эффективный метод синтеза 1,3-пропанбис(дитиокарбамата) натрия, подтверждено его строение с использованием физико-химических методов (инфракрасная спектроскопия, спектроскопия ядерного магнитного резонанса 1H, 13С). В результате комплекса исследований было установлено, что совместное использование бутилового ксантогената калия и диалкилдитиофосфата натрия (БТФ-1552) с 1,3-пропанбис(дитиокарбаматом) натрия приводит к повышению эффективности извлечения целевого компонента до 81,63% и увеличению его содержания в концентрате до 7 г/т. Также было показано, что комбинация 1,3-пропанбис(дитиокарбамата) натрия с бутиловым ксантогенатом калия позволяет достичь эффективности извлечения 80,51% и содержания ценного компонента в концентрате до 6,5 г/т при низком содержании золота в хвостах флотации 0,07 г/т. Предложенный метод синтеза и результаты флотационных испытаний золотосодержащей руды представляют интерес для дальнейших исследований в области органического синтеза и практического применения.

Development and selection of a suitable reagent for efficient flotation is of great importance for ore beneficiation processes. Dithiocarbamates represent a class of organic compounds that are widely used as reagent-collectors in ore flotation. In this work, we conducted an analytical review of the methods currently used for obtaining this class of compounds and established the main method for obtaining dithiocarbamate salts to be the interaction of primary or secondary amines with carbon disulfide (CS2) in the presence of potassium or sodium hydroxide. The aim of the reviewed work was to synthesize sodium 1,3-propanebis(dithiocarbamate), as well as to study its flotation properties in the beneficiation of gold-bearing sulfide ores. A simple and effective method for sodium 1,3-propanebis(dithiocarbamate) synthesizing was proposed. Its structure was confirmed using physicochemical methods (infrared spectroscopy, 1H, 13C nuclear magnetic resonance spectroscopy). A set of studies found that the combined use of potassium butyl xanthate and sodium dialkyl dithiophosphate (BTF-1552) with sodium 1,3-propanebis(dithiocarbamate) led an increase in the efficiency of extraction of the target component of up to 81.63%, as well as an increase in its content in the concentrate of up to 7 g/t. In addition, the combination of sodium 1,3-propanebis(dithiocarbamate) with potassium butyl xanthate was shown to enable an extraction efficiency of 80.51%, as well as a valuable component content in the concentrate of up to 6.5 g/t with a low gold content in flotation tailings of 0.07 g/t. The proposed synthesis method and the results of flotation tests of gold-bearing ores are of interest for further research in the field of organic synthesis and practical application.

флотацияфлотационные реагентыдитиокарбаматысинтеззолотоflotationflotation reagentsdithiocarbamatessynthesisgoldReferencesAjiboye T.O., Ajiboye T.T., Marzouki R., Onwudiwe D.C. The versatility in the applications of dithiocarbamates // International Journal of Molecular Sciences. 2022. Vol. 23, no. 3. P. 1317. DOI: 10.3390/ijms23031317.Ajiboye T.O., Ajiboye T.T., Marzouki R., Onwudiwe D.C. The versatility in the applications of dithiocarbamates. International Journal of Molecular Sciences. 2022;23(3):1317. DOI: 10.3390/ijms23031317.Kaul L., Süss R., Zannettino A., Richter K. The revival of dithiocarbamates: from pesticides to innovative medical treatments // iScience. 2021. Vol. 24, no. 2. P. 102092. DOI: 10.1016/j.isci.2021.102092.Kaul L., Süss R., Zannettino A., Richter K. The revival of dithiocarbamates: from pesticides to innovative medical treatments. iScience. 2021;24(2):102092. DOI: 10.1016/j.isci.2021.102092.Viola-Rhenals M., Patel K.R., Jaimes-Santamaria L., Wu G., Liu J., Dou Q.P. Recent advances in Antabuse (Disulfiram): the importance of its metal-binding ability to its anticancer activity // Current Medicinal Chemistry. 2018. Vol. 25, no. 5. P. 506–524. DOI: 10.2174/0929867324666171023161121.Viola-Rhenals M., Patel K.R., Jaimes-Santamaria L., Wu G., Liu J., Dou Q.P. Recent advances in Antabuse (Disulfiram): the importance of its metal-binding ability to its anticancer activity. Current Medicinal Chemistry. 2018;25(5):506-524. DOI: 10.2174/0929867324666171023161121.Kurian J.K., Peethambaran N.R., Mary K.C., Kuriakose B. Effect of vulcanization systems and antioxidants on discoloration and degradation of natural rubber latex thread under UV radiation // Journal of Applied Polymer Science. 2000. Vol. 78, no. 2. P. 304–310. DOI: 10.1002/1097-4628(20001010)78:2<304::AIDAPP100>3.0.CO;2-G.Kurian J.K., Peethambaran N.R., Mary K.C., Kuriakose B. Effect of vulcanization systems and antioxidants on discoloration and degradation of natural rubber latex thread under UV radiation. Journal of Applied Polymer Science. 2000;78(2):304-310. DOI: 10.1002/1097-4628(20001010)78:2<304::AIDAPP100>3.0.CO;2-G.Cvek B., Dvorak Z. Targeting of nuclear factor-κB and proteasome by dithiocarbamate complexes with metals // Current Pharmaceutical Design. 2007. Vol. 13, no. 30. P. 3155–3167. DOI: 10.2174/138161207782110390.Cvek B., Dvorak Z. Targeting of nuclear factor-κB and proteasome by dithiocarbamate complexes with metals. Current Pharmaceutical Design. 2007;13(30):3155-3167. DOI: 10.2174/138161207782110390.Бурдонов А.Е., Вчисло Н.В., Верочкина Е.А., Розенцвейг И.Б. Синтез новых производных ксантогенатов и дитиокарбаматов и их применение в процессах обогащения // Известия вузов. Прикладная химия и биотехнология. 2023. Т. 13. N 2. С. 160–171. DOI: 10.21285/2227-2925-2023-13-2-160-171. EDN: PNMZLC.Burdonov A.E., Vchislo N.V., Verochkina E.A., Rozentsveig I.B. Synthesis of new dithiocarbamate and xanthate complexes and their application in enrichment processes. Proceedings of Universities. Applied Chemistry and Biotechnology. 2023;13(2):160-171. DOI: 10.21285/2227-2925-2023-13-2-160-171. EDN: PNMZLC.Campanale C., Triozzi M., Ragonese A., Losacco D., Massarelli C. Dithiocarbamates: properties, methodological approaches and challenges to their control // Toxics. 2023. Vol. 11, no. 10. P. 851. DOI: 10.3390/toxics11100851.Campanale C., Triozzi M., Ragonese A., Losacco D., Massarelli C. Dithiocarbamates: properties, methodological approaches and challenges to their control. Toxics. 2023;11(10):851. DOI: 10.3390/toxics11100851.Bala V., Gupta G., Sharma V.L. Chemical and medicinal versatility of dithiocarbamates: an overview // Mini-Reviews in Medicinal Chemistry. 2014. Vol. 14, no. 14. P. 1021–1032. DOI: 10.2174/1389557514666141106130146.Bala V., Gupta G., Sharma V.L. Chemical and medicinal versatility of dithiocarbamates: an overview. Mini Reviews in Medicinal Chemistry. 2014;14(14):1021-1032. DOI: 10.2174/1389557514666141106130146.Duan Y.-C., Zheng Y.-C., Li X.-C., Wang M.-M., Ye X.-W., Guan Y.-Y., et al. Design, synthesis and antiproliferative activity studies of novel 1,2,3-triazole–dithiocarbamate–urea hybrids // European Journal of Medicinal Chemistry. 2013. Vol. 64. P. 99–110. DOI: 10.1016/j.ejmech.2013.03.058.Duan Y.-C., Zheng Y.-C., Li X.-C., Wang M.-M., Ye X.-W., Guan Y.-Y., et al. Design, synthesis and antiproliferative activity studies of novel 1,2,3-triazole–dithiocarbamate– urea hybrids. European Journal of Medicinal Chemistry. 2013;64:99-110. DOI: 10.1016/j.ejmech.2013.03.058.Sheef A.F. A method for maintaining Phytomonas sepedonica in culture to long periods without transfer // Phytopathology. 1943. Vol. 33, no. 4. P. 300–332.Sheef A.F. A method for maintaining Phytomonas sepedonica in culture to long periods without transfer. Phytopathology. 1943;33(4):300-332.He X.-Y., Lu L., Qiu J., Zou P., Yu F., Jiang X.-K., et al. Small molecule fusion inhibitors: Design, synthesis and biological evaluation of (Z)-3-(5-(3-benzyl-4-oxo-2thioxothiazolidinylidene)methyl)-N-(3-carboxy-4-hydroxy) phenyl-2,5-dimethylpyrroles and related derivatives targeting HIV-1 gp41 // Bioorganic & Medicinal Chemistry. 2013. Vol. 21, no. 23. P. 7539–7548. DOI: 10.1016/j.bmc.2013.04.046.He X.-Y., Lu L., Qiu J., Zou P., Yu F., Jiang X.-K., et al. Small molecule fusion inhibitors: Design, synthesis and biological evaluation of (Z)-3-(5-(3-benzyl-4-oxo-2thioxothiazolidinylidene)methyl)-N-(3-carboxy-4-hydroxy) phenyl-2,5-dimethylpyrroles and related derivatives targeting HIV-1 gp41. Bioorganic & Medicinal Chemistry. 2013;21(23):7539-7548. DOI: 10.1016/j.bmc.2013.04.046.Harrison J.J., Turner R.J., Ceri H. A subpopulation of Candida albicans and Candida tropicalis biofilm cells are highly tolerant to chelating agents // FEMS Microbiology Letters. 2007. Vol. 272, no. 2. P. 172–181. DOI: 10.1111/j.1574-6968.2007.00745.x.Harrison J.J., Turner R.J., Ceri H. A subpopulation of Candida albicans and Candida tropicalis biofilm cells are highly tolerant to chelating agents. FEMS Microbiology Letters. 2007;272(2):172-181. DOI: 10.1111/j.1574-6968.2007.00745.x.Xu L., Tong J., Wu Y., Zhao S., Lin B.-L. A computational evaluation of targeted oxidation strategy (TOS) for potential inhibition of SARS-CoV-2 by disulfiram and analogues // Biophysical Chemistry. 2021. Vol. 276. P. 106610. DOI: 10.1016/j.bpc.2021.106610.Xu L., Tong J., Wu Y., Zhao S., Lin B.-L. A computational evaluation of targeted oxidation strategy (TOS) for potential inhibition of SARS-CoV-2 by disulfiram and analogues. Biophysical Chemistry. 2021;276:106610. DOI: 10.1016/j.bpc.2021.106610.Karimov A., Taslimi P., Orujova A., Mammadova K., Kısa D., Farzaliyev V., et al. Design, synthesis, characterization and biological activities of novel S-(acyloxy) butyl-N,N-diethyldithiocarbamate compounds // ChemistrySelect. 2023. Vol. 8, no. 18. P. e202300286. DOI: 10.1002/Slct.202300286.Karimov A., Taslimi P., Orujova A., Mammadova K., Kısa D., Farzaliyev V., et al. Design, synthesis, characterization and biological activities of novel S-(acyloxy)butyl-N,Ndiethyldithiocarbamate compounds. ChemistrySelect. 2023;8(18):e202300286. DOI: 10.1002/slct.202300286.Trawally M., Demir-Yazıcı K., Dingiş-Birgül S.İ., Kaya K., Akdemir A., Güzel-Akdemir Ö. Dithiocarbamates and dithiocarbonates containing 6-nitrosaccharin scaffold: Synthesis, antimycobacterial activity and in silico target prediction using ensemble docking-based reverse virtual screening // Journal of Molecular Structure. 2023. Vol. 1277. P. 134818. DOI: 10.1016/j.molstruc.2022.134818.Trawally M., Demir-Yazıcı K., Dingiş-Birgül S.İ., Kaya K., Akdemir A., Güzel-Akdemir Ö. Dithiocarbamates and dithiocarbonates containing 6-nitrosaccharin scaffold: Synthesis, antimycobacterial activity and in silico target prediction using ensemble docking-based reverse virtual screening. Journal of Molecular Structure. 2023;1277:134818. DOI: 10.1016/j.molstruc.2022.134818.Soyka M., Roesner S. New pharmacological approaches for the treatment of alcoholism // Expert Opinion on Pharmacotherapy. 2006. Vol. 7, no. 17. P. 2341–2353. DOI: 10.1517/14656566.7.17.2341.Soyka M., Roesner S. New pharmacological approaches for the treatment of alcoholism. Expert Opinion on Pharmacotherapy. 2006;7(17):2341-2353. DOI: 10.1517/14656566.7.17.2341.Singh A.N., Srivastava S., Jainar A.K. Pharmacotherapy of chronic alcoholism: a review // Drugs of Today. 1999. Vol. 35, no. 1. P. 27–33. DOI: 10.1358/dot.1999.35.1.522944.Singh A.N., Srivastava S., Jainar A.K. Pharmacotherapy of chronic alcoholism: a review. Drugs of Today. 1999;35(1):27-33. DOI: 10.1358/dot.1999.35.1.522944.Ma X., Hu Y., Zhong H., Wang S., Liu G., Zhao G. A novel surfactant S-benzoyl-N,N-diethyldithiocarbamate synthesis and its flotation performance to galena // Applied Surface Science. 2016. Vol. 365. P. 342–351. DOI: 10.1016/j.apsusc.2016.01.048.Ma X., Hu Y., Zhong H., Wang S., Liu G., Zhao G. A novel surfactant S-benzoyl-N,N-diethyldithiocarbamate synthesis and its flotation performance to galena. Applied Surface Science. 2016;365:342-351. DOI: 10.1016/j.apsusc.2016.01.048.Liu S., Liu G., Zhong H., Yang X. The role of HABTC’s hydroxamate and dithiocarbamate groups in chalcopyrite flotation // Journal of Industrial and Engineering Chemistry. 2017. Vol. 52. P. 359–368. DOI: 10.1016/j.jiec.2017.04.015.Liu S., Liu G., Zhong H., Yang X. The role of HABTC’s hydroxamate and dithiocarbamate groups in chalcopyrite flotation. Journal of Industrial and Engineering Chemistry. 2017;52:359-368. DOI: 10.1016/j.jiec.2017.04.015.Liu S., Dong Y., Xie L., Liu G., Zhong H., Zeng H. Uncovering the hydrophobic mechanism of a novel dithiocarbamate-hydroxamate surfactant towards galena // Chemical Engineering Science. 2021. Vol. 245. P. 116765. DOI: 10.1016/j.ces.2021.116765.Liu S., Dong Y., Xie L., Liu G., Zhong H., Zeng H. Uncovering the hydrophobic mechanism of a novel dithiocarbamate-hydroxamate surfactant towards galena. Chemical Engineering Science. 2021;245:116765. DOI: 10.1016/j.ces.2021.116765.Katritzky A.R., Tarr R.D., Heilmann S.M., Rasmussen J.K., Krepski L.R. Synthesis and characterization of poly([3H]-thiazole-2-thione)s // Journal of Polymer Science, Part A: Polymer Chemistry. 1987. Vol. 25, no. 12. P. 3205–3214. DOI: 10.1002/pola.1987.080251203.Katritzky A.R., Tarr R.D., Heilmann S.M., Rasmussen J.K., Krepski L.R. Synthesis and characterization of poly([3H]-thiazole-2-thione)s. Journal of Polymer Science, Part A: Polymer Chemistry. 1987;25(12):3205-3214. DOI: 10.1002/pola.1987.080251203.

The authors declare that there are no conflicts of interest present.