Catalyst-free biphasic oxidation of Thiophenes in continuous-flow


A mild and practical oxidation process of thiophene derivatives in continuous-flow has been developed. The oxidant phase consists of mCPBA and acetonitrile, which formed an immiscible liquid-liquid segmented flow with the fuel phase. In the oxidation of thiophenes, high yields of sulfone could be realized with only 10 min of residence time in the microreactor. The oxidant phase can be separated with the fuel phase with a continuous membrane separator, rendering it a clean and potentially scalable method to facilitate fuel refining.

This is a preview of subscription content, access via your institution.

Scheme 1
Fig. 1


  1. 1.

    Fox EB, Liu Z-W, Liu Z-T (2013) Ultraclean fuels production and utilization for the twenty-first century: advances toward sustainable transportation fuels. Energy Fuel 27:6335–6338

    CAS  Article  Google Scholar 

  2. 2.

    Ho TC (2004) Deep HDS of diesel fuel: chemistry and catalysis. Catal Today 98:3–18

    CAS  Article  Google Scholar 

  3. 3.

    Röthlisberger A, Prins R (2005) Intermediates in the hydrodesulfurization of 4,6-dimethyl-dibenzothiophene over Pd/γ-Al2O3. J Catal 235:229–240

    Article  Google Scholar 

  4. 4.

    Ishihara A, Wang D, Dumeignil F, Amano H, Qian EW, Kabe T (2005) Oxidative desulfurization and denitrogenation of a light gas oil using an oxidation/adsorption continuous flow process. Appl Catal A Gen 279:279–287

    CAS  Article  Google Scholar 

  5. 5.

    Desai LV, Malik HA, Sanford MS (2006) Oxone as an inexpensive, safe, and environmentally benign oxidant for C−H bond oxygenation. Org Lett 8:1141–1144

    CAS  Article  Google Scholar 

  6. 6.

    Cravotto G, Garella D, Carnaroglio D, Gaudino EC, Rosati O (2012) Solvent-free chemoselective oxidation of thioethers and thiophenes by mechanical milling. Chem Commun 48:11632–11634

    CAS  Article  Google Scholar 

  7. 7.

    Yu B, Liu A-H, He L-N, Li B, Diao Z-F, Li Y-N (2012) Catalyst-free approach for solvent-dependent selective oxidation of organic sulfides with oxone. Green Chem 14:957–962

    CAS  Article  Google Scholar 

  8. 8.

    Jereb M (2012) Highly atom-economic, catalyst- and solvent-free oxidation of sulfides into sulfones using 30% aqueous H2O2. Green Chem 14:3047–3052

    CAS  Article  Google Scholar 

  9. 9.

    Duarte TAG, Pires SMG, Santos ICMS, Simões MMQ, Neves MGPMS, Cavaleiro AMV, Cavaleiro JAS (2016) A Mn(iii) polyoxotungstate in the oxidation of organosulfur compounds by H2O2 at room temperature: an environmentally safe catalytic approach. Catal Sci Technol 6:3271–3278

    CAS  Article  Google Scholar 

  10. 10.

    Timko MT, Wang JA, Burgess J, Kracke P, Gonzalez L, Jaye C, Fischer DA (2016) Roles of surface chemistry and structural defects of activated carbons in the oxidative desulfurization of benzothiophenes. Fuel 163:223–231

    CAS  Article  Google Scholar 

  11. 11.

    Camurlu P, Durak T, Balan A, Toppare L (2011) Electronic and optical properties of dibenzothiophen-S,S-dioxide and EDOT based conducting polymers. Synth Met 161:1898–1905

    CAS  Article  Google Scholar 

  12. 12.

    Tang N, Jiang Z, Li C (2015) Oxidation of refractory sulfur-containing compounds with molecular oxygen catalyzed by vanadoperiodate. Green Chem 17:817–820

    CAS  Article  Google Scholar 

  13. 13.

    Kamata K, Sugahara K, Kato Y, Muratsugu S, Kumagai Y, Oba F, Hara M (2018) Heterogeneously catalyzed aerobic oxidation of sulfides with a BaRuO3 nanoperovskite. ACS Appl Mater Interfaces 10:23792–23801

    CAS  Article  Google Scholar 

  14. 14.

    Akwi FM, Watts P (2018) Continuous flow chemistry: where are we now? Recent applications, challenges and limitations. Chem Commun 54:13894–13928

    CAS  Article  Google Scholar 

  15. 15.

    Gemoets HPL, Su Y, Shang M, Hessel V, Luque R, Noël T (2016) Liquid phase oxidation chemistry in continuous-flow microreactors. Chem Soc Rev 45:83–117

    CAS  Article  Google Scholar 

  16. 16.

    Colomer JP, Traverssi M, Oksdath-Mansilla G (2020) Oxidation of organosulfur compounds promoted by continuous-flow chemistry. J Flow Chem 10:123–138

    CAS  Google Scholar 

  17. 17.

    Rahimi M, Shahhosseini S, Movahedirad S (2017) Continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process: an efficient diesel treatment by injection of the aqueous phase. Ultrason Sonochem 39:611–622

    CAS  Article  Google Scholar 

  18. 18.

    Laudadio G, Straathof NJW, Lanting MD, Knoops B, Hessel V, Noël T (2017) An environmentally benign and selective electrochemical oxidation of sulfides and thiols in a continuous-flow microreactor. Green Chem 19:4061–4066

    CAS  Article  Google Scholar 

  19. 19.

    Noguchi T, Hirai Y, Kirihara M (2008) Highly selective 30% hydrogen peroxideoxidation of sulfides to sulfoxides using micromixing. Chem Commun 26:3040–3042

    Article  Google Scholar 

  20. 20.

    Piscopo CG, Voellinger L, Schwarzer M, Polyzoidis A, Bošković D, Loebbecke S (2019) Continuous flow desulfurization of a model fuel catalysed by titanium functionalized UiO-66. ChemistrySelect 4:2806–2809

    CAS  Article  Google Scholar 

  21. 21.

    Ogunlaja AS, Walmsley RS, du Sautoy C, Torto N, Tshentu ZR (2013) Development of a continuous flow system for the oxidative desulfurization of refractory organosulfur compounds in hydrotreated diesel. Energy Fuel 27:7714–7723

    CAS  Article  Google Scholar 

Download references


This work was supported in part by the National Natural Science Foundation of China (grant 21872068) and the Fundamental Research Funds for the Central Universities (grant 0205-14380182).

Author information




S.W. and Y.P. carried out the experiments and analysis, and contributed equally to this work. All authors read and approved the final manuscript.

Corresponding authors

Correspondence to Zheng Zhou or Xiao Wang.

Ethics declarations

Conflict of interest

The authors declare no conflict of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material


(DOCX 2037 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Wang, S., Patehebieke, Y., Zhou, Z. et al. Catalyst-free biphasic oxidation of Thiophenes in continuous-flow. J Flow Chem 10, 597–603 (2020).

Download citation


  • Thiophene
  • Continuous-flow oxidation
  • Desulfurization
  • Liquid fuel
  • Biphasic oxidation