Design, preparation and application of the semicarbazide-pyridoyl-sulfonic acid-based nanocatalyst for the synthesis of pyranopyrazoles

www.nature.com/scientificreports OPEN Design, preparation and application of the semicarbaz ide‑pyridoyl‑sulfonic acid‑based nanocatalyst for the synthesis of pyranopyrazoles Masoumeh Beiranvand & Davood Habibi* A novel, efficient, and recoverable nanomagnetic catalyst bearing the semicarbazide linkers, namely, Fe3O4@SiO2@OSi(CH2)3-N(3-pyridoyl sulfonic acid)semicarbazide (FSiPSS) was designed, synthesized and characterized by the use of various techniques such as FT‐IR, EDX, elemental mapping analysis, XRD, SEM, TEM, TGA/DTA, BET, and VSM. Then, the catalytic capability of the novel prepared nanomagnetic FSiPSS catalyst was successfully investigated in the synthesis of diverse pyranopyrazoles through a one-pot four-component condensation reaction of ethyl acetoacetate, hydrazine hydrate, aromatic aldehydes, and malononitrile or ethyl cyano-acetate by the help of ultrasonication in very short reaction time, good to high yields and easy work-up (Fig. 1). Semicarbazide (SEM) is a derivative of urea or hydrazine that possess several important functions in medicinal and health-related issues. SEM motifs constitute the core structures of several drugs and herbicides such as nitrofurazone, tolazamide, laromustine, cafenstrole, and diflufenzopyr1–3. In addition, SEM is applied in food as a marker to detect the illegal usage of the banned antibiotic n itrofurazone4. They also reveal a stabilizing effect on the liquid crystalline state of chloroplast membrane lipids, and some are known as surfactants. Another report exhibited that SEMs are also applied as stabilizing agents in the polymer i ndustry5. Also, magnetic nanoparticles (MNPs) are receiving increasing interest due to their widespread applications in various fields. MNPs have many advantages in organic chemistry, (1) MNPs are accessible; (2) the stability of catalyst linkages leads to the use of more environmentally friendly solvents than homogeneous catalysis; (3) simple separation by an external magnetic field; (4) the fabrication of MNPs is generally simple, scalable, safe, cost-effective and controllable; (5) catalyst leaching is usually lower than other material-supported catalysts6. Many reports on MNPs nanoparticles have appeared over during years7–11. Among different types of MNPs, aluminum and iron oxide have large advantages such as low cost, extensive availability, thermal stability, and considerable adsorption c apacity12. In particular, iron oxide nanoparticles (IONPs), which belong to the ferrimagnetic class of magnetic materials, are wildly applied in the fields of biomedicine and bioengineering due to their ease of surface modification, synthesis, and low toxicity. Magnetite (Fe3O4) and maghemite (γ-Fe2O3) and mixed ferrites (MFe2O4 where M=Co, Mn, Ni, or Zn) are the three main forms of iron oxide-based nanoparticles13–16. To prevent the aggregation of MNPs and also enhancement their stability of them, usually, a layer of silica is coated on the s urface17. Fe3O4 coated with silica was often used as the support of metal and nonmetal catalysts18–21. Magnetic nanomaterials are more efficient adsorbents than active carbon, graphene oxide (GO), and zeolitebased adsorbents due to their ease of removal of contaminants from wastewater employing an applied magnetic field but also their advantageous surface charge and redox activity characteristics. The incorporation of magnetic nanomaterials with adsorbents such as W O3, TiO2, ZnO, and GO decreases the rapid recombination of photoinduced electron holes and improves the photocatalysis potential of these materials. On the other hand, magnetic nanomaterials can a synergistic effect with biosorbents. Biosorbents possess efficient adsorption capacity to eliminate polluters, and high abundance and therefore help diminish ecological and environmental p roblems22,23. Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran. *email: davood. Scientific Reports | (2022) 12:14347 | https://doi.org/10.1038/s41598-022-18651-5 1 Vol.:(0123456789) www.nature.com/scientificreports/ Figure 1.  Synthesis of diverse pyranopyrazoles by the FSiPSS nano-catalyst. O OEt EtO NHNH2 Solvent free r.t., 5 h NCO + Si OEt EtO Si N N O OEt N H OEt N H TEOS H2O/EtOH NH3, rt, 12 h Ligand A Fe3O4 SiO2 Fe3O4@SiO2 Fe3O4 Toluene, Reflux, 24 h SiO2 O O O N N H Si r.t., CH2Cl2 Fe3O4 SiO2 N H H N O Fe3O4@SiO2@OSi(CH2)3 -N(3-pyridoyl)semicarbazide SO3H N O ClSO2OH O Ligand A O Fe3O4 H N O O O Si N H N H Cl H N O Fe3O4@SiO2@OSi(CH2)3-N(3-pyridoyl sulfonic acid)semicarbazide Figure 2.  Synthesis of the FSiPSS nano-catalyst. Among iron oxide magnetic nano-particles, sulfonic acid-functionalized magnetic nanoparticles, known as the recoverable solid strong acid, have attracted much attention due to economically important and environmentally benign features24. In addition, pyranopyrazoles (six-membered oxygen-containing heterocycles) have received considerable attention due to the wide range of biological activities such as anti-cancer, anti-leishmanial, antimicrobial, antiinflammatory, lactamase inhibitor, etc.25–28. Three-component (3-CR) or four-component (4-CR) reactions are often used for the synthesis of pyranopyrazoles29. Several methods have been established for their synthesis using copper-immobilized ionic liquid30, N-methylmorpholine N-oxide and silver oxide (Ag2O)31, isonicotinic acid32, cetyltrimethylammonium chloride (CTACl)33, [bmim]BF434, choline chloride-urea deep eutectic s olvent35, bael fruit ash (BFA)-catalyst36, P2O5/SiO2 or H 3PO4/Al2O337, Nd-salen Schiff base complex immobilized mesoporous silica38, uncapped S nO2 quantum dots (QDs)39, sodium c itrate40, trityl c arbocation41, CeO2/ZrO242, saccharose43, per-6-amino-β-cyclo-dextrin (per-6-ABCD)44, 2-carboxy-N,N-diethylethan-aminium acetate45, cinchona alkaloid46, 4CzIPN/Ni0-metallaphotoredox47, sodium ascorbate48 and Meglumine49. In this paper and following our interests to present new and efficient protocols for the synthesis of biological valuable structures by the use of nanomagnetic catalysts50–54, we would like to report the rational design, synthesis, and characterization of the novel FSiPSS nano-catalyst (Fig. 2). Scientific Reports | Vol:.(1234567890) (2022) 12:14347 | https://doi.org/10.1038/s41598-022-18651-5 2 www.nature.com/scientificreports/ Ar-CHO X = CN, CO2Et NC 3 O H3C 4 X O 1 OEt FSIPSS catalyst EtOH, 40 °C, Ultrasonic H3C N NH2NH2 2 Ar N H CN + O 5(a-n) 14 examples CH2Ph CO2Et H3C NH2 N N H O NH 5o 1 example Figure 3.  Synthesis of pyranopyrazoles. Then, the FSiPSS nano-catalyst was used as an efficient heterogeneous catalyst for the synthesis of pyranopyrazoles via a one-pot four-component condensation reaction of ethyl acetoacetate 1, hydrazine hydrate 2, aromatic aldehydes 3, and malononitrile or ethyl-cyano-acetate 4 under ultrasonic conditions (Fig. 3). Experimental General. All the commercia (...truncated)