Hantzsch Reaction using Copper Nitrate Hydroxide- Containing Mesoporous Silica Nanoparticle with C 3 N 4 Framework as A Novel Powerful and Reusable Catalyst

Hantzsch Reaction using Copper Nitrate Hydroxide- Containing Mesoporous Silica Nanoparticle with C 3 N 4 Framework as A Novel Powerful and Reusable Catalyst | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Hantzsch Reaction using Copper Nitrate Hydroxide- Containing Mesoporous Silica Nanoparticle with C 3 N 4 Framework as A Novel Powerful and Reusable Catalyst Ensiyeh Rahmati, Zahra Rafiee This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-2064047/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 12 Jun, 2023 Read the published version in Scientific Reports → Version 1 posted 12 You are reading this latest preprint version Abstract Copper nitrate hydroxide (CNH)-containing mesoporous silica nanoparticle (MSN) with g-C 3 N 4 framework (MSN/C 3 N 4 /CNH) was fabricated via a four-step hydrothermal synthesis method. Functionalized MSN-based C 3 N 4 was prepared, decorated with CNH, and identified by different physicochemical techniques such as FT-IR, XRD, SEM, EDX, and STA analyses. Then, MSN/C 3 N 4 /CNH composite was utilized as a robust catalyst for the fast fabrication of biologically active polyhydroquinoline derivatives with high yields between 88 and 97% via Hantzsch reaction under mild reaction conditions and short reaction time (within 15 min) owing to synergistic influence of Lewis acid and base sites. Moreover, MSN/C 3 N 4 /CNH can be straightforwardly recovered and used up to six reaction cycles without a conspicuous decrease in efficiency. Mesoporous silica Copper nitrate hydroxide C3N4 Nanocomposite Hantzsch reaction Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction Multicomponent reactions (MCRs) are defined as attractive and powerful synthetic protocols for producing highly complex molecules and biological significance molecules owing to the formation of C-C and C-heteroatom bonds in a one-pot manner through an easy tandem synthetic method with step-efficiency and atom-economy ( 1 – 10 ). Polyhydroquinoline (PHQ) derivatives as a significant class of nitrogen heterocycle compounds can be converted into biological compounds, displaying promising pharmaceutical and biological properties, including antitumor, antidiabetic, platelet anti-aggregation, bronchodilator, antibacterial, and neurotropic ( 11 – 14 ). Thus, the production of PHQ derivatives is of great importance. The new techniques have been developed to improve the reaction efficiency in the preparation of PHQ derivatives in the presence of catalysts including [CholineCl][ZnCl 2 ] 3 ( 15 ), SBA-15@Glycine-Cu ( 16 ), Fe 3 O 4 @SiO 2 /ZnCl 2 ( 17 ), ascorbic acid ( 18 ), NiAlTi LDH ( 19 ), and CNNs-Bu-SO 3 H ( 20 ). However, some of these synthetic methods suffer from the usage of toxic organic solvents, long reaction time, harsh reaction conditions, a great amount of catalyst, and low yields. Consequently, there is further improvement toward more sustainable protocol for the fabrication of PHQ derivatives. Lately, remarkable attention has been developed to designing eco-friendly catalysts and synthetic procedures for the Hantzsch reaction. The environmentally benign processes comprise the use of effective, biodegradable, and economical catalysts and non-toxic systems such as solvent-free conditions, water, and supercritical fluids ( 21 – 25 ). The substantial advance in nanotechnology during the last decades has led to the development of a large variety of nanomaterials with outstanding catalysis applications. It is possible to design and construct numerous nanomaterials suitable as heterogeneous catalysts ( 26 – 37 ). The support material selection possesses a key role in the overall efficiency of the catalyst because these materials impact the catalytic properties of nano-scale catalysts ( 38 , 39 ). The materials for catalyst supports indicate the high surface area, capability to disperse the supported metal, and chemical stability. Amongst the various support materials, mesoporous silica materials (MSMs) are promising materials owing to their thermally and chemically stability, large surface area, easy surface functionalization, good biocompatibility, and can be produced with tunable micro/meso porosity ( 40 , 41 ). MSMs are amorphous inorganic materials composed of silicon and oxygen elements in their framework with pore diameters ranging from 2 to 50 nm. The well-defined pore structure of porous silica can function as a molecular sieve at small sizes and may ultimately be utilized to control substrate access to the catalyst which is very important in improving/tuning the selectivity ( 42 , 43 ). These materials have proved their versatility in separation ( 44 ), sensor ( 45 ), drug delivery ( 46 ), and catalysis ( 47 ). Carbon nanostructures are especially of attention owing to their promising properties including high specific surface area, excellent mechanical strength, high conductivity, and fascinating physicochemical features. Among these, graphitic carbon nitride (g-C 3 N 4 ) as a free metals material is especially of attention, owing to its unique crystal structure, nontoxic, cost-effectiveness, high thermal and chemical stability, and resistance to acidic and basic conditions ( 48 ). C 3 N 4 has a stacked two-dimensional structure and can be synthesized easily from low-cost precursors such as urea, thiourea, melamine, and cyanamide via pyrolysis. Owing to its promising features, g-C 3 N 4 and its composites are applied in a variety of photocatalytic applications ( 49 ). So far, g-C 3 N 4 has been utilized as a catalyst or catalyst support in various organic reactions ( 50 – 55 ). However, the practical application of g-C 3 N 4 is limited by its low surface area, insufficient light absorption, reduction potential, inappropriate rapid recombination, and large diffusion resistance of charges. The g-C 3 N 4 can enhance the surface area, promote charge transfer and mass diffusion through nanostructure materials design. Copper hydroxide nitrate, [Cu 2 (OH) 3 NO 3 ], is a basic copper(II) salt with a layered structure, that have applications in vehicle airbags, catalyst, and ion exchangers ( 56 – 60 ). [Cu 2 (OH) 3 NO 3 ] exists as two structurally related dimorphs, a synthetic metastable monoclinic phase and a natural orthorhombic phase occurring in the mineral gerhardtite. The structure can be observed as layers of copper octahedra stacked with each other. The Cu octahedral form layers of stoichiometry [Cu 2 (OH) 3 ] + , and NO 3 - ions stand in between the positive layers for charge balance, which are linked to the hydroxyl groups via hydrogen bonding belonging to the copper octahedra layers. In this study, g-C 3 N 4 /MSN was fabricated and utilized as support to load copper nitrate hydroxide (CNH) (Cu 2 (OH) 3 NO 3 ) and emerged as a competent heterogeneous nanocatalyst for the Hantzsch reaction. 2. Experimental 2.1. Preparation of MSN 0.2 g of glucose was dissolved in 90 mL of ethanol. Then, 4 mL of TEOS (as the silica source) and 6 mL of distilled water were added to the above solution and subsequently stirred at room temperature for 12 h. The solid was separated by centrifuge and washed with distilled water and ethanol, respectively. The obtained white solid calcined at 550°C for 6 to the production of porous silica hollow sphere. 2.2. Synthesis of MSN/C 3 N 4 1.0 g of MSN, 5.0 g of urea, and 3 wt% of KBr were placed in a porcelain dish and the mixture was ground completely. Subsequently, the reaction was performed at 550°C for 2 h in a crucible for calcination. 2.3. Synthesis of MSN/C 3 N 4 /CNH 0.25 g of MSN/C 3 N 4 and 0.15 g of Cu(NO 3 ) 2 .3H 2 O were mixed in 40 mL of ethanol and heated under reflux conditions and argon atmosphere for 24 h. The resultant precipitate was washed (ethanol) and dried at 80 ᵒC under vacuum for 10 h. 2.4. The Hantzsch reaction using MSN/C 3 N 4 /CNH catalyst General procedure : A mixture of MSN/C 3 N 4 /CNH (15 mg), ammonium acetate (1.4 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol), and aldehyde (1 mmol) was stirred at 50°C, as monitored via TLC (ethyl acetate/n-hexane 50:50) for a complete reaction. Then, 10 mL of solvent (warm ethanol) was added to the mixture and MSN/C 3 N 4 /CNH was separated via filtration. The underlying solution was heated to boiling temperature and then a piece of ice was added to precipitate the desired crystalline product. The solvent was vaporized and ethanol was utilized to crystallize the resultant product. Then, the recovered MSN/C 3 N 4 /CNH was reused in six runs under similar conditions as the first run to represent the recyclability and stability of the prepared catalyst. 3. Results And Discussion 3.1. Synthesis of MSN/C 3 N 4 /CNH An adequate amount of TEOS as silica precursor was added to a mixture of glucose as sacrificial template and ethanol, the shell of silica, and glucose as the core were formed. After calcination at elevated temperature, glucose core was removed and the space vacant was performed. MSN/C 3 N 4 was fabricated via calcination technique onto MSN surface using melamine as a precursor. MSN/C 3 N 4 was applied as support material to anchor CNH to afford MSN/C 3 N 4 /CNH (Fig. 1 ). 3.2. Characterization of synthesized compounds FTIR spectra of MSN (a), MSN/C 3 N 4 (b), and MSN/C 3 N 4 /CNH (c) are revealed in Fig. 2 . In the spectrum of MSN, the peak appeared at 3429 cm − 1 belonged to the stretching vibration of O-H; the absorption bands at 1082 and 810 cm − 1 assigned the asymmetric and symmetric stretching vibrations of Si-O-Si, respectively. In the spectrum of MSN/C 3 N 4 , the broad band in the range of 3500 − 3000 cm − 1 indicates the presence of N-H stretching vibration of the terminal amino group was observed in g-C 3 N 4 . The peak around 1640 cm − 1 contributed to the stretching mode of C = N bonds. The intense bands observed at 1560, 1427, 1320, and 1243 cm − 1 were due to the presence of C-N stretching of tri-s-triazine. The band around 800 cm − 1 reveals out-of-plane bending vibration of triazinecycle. In the spectrum of MSN/C 3 N 4 /CNH, the peak at 3427 cm − 1 corresponds to the stretching vibration of the O-H and O-H groups of molecular water, and the band at 1662 cm − 1 is owing to the bending mode of H 2 O molecules. The presence of NO 3 − in MSN/C 3 N 4 /CNH is evidenced by the vibration bands that appeared from middle to lower wavenumbers, confirming the presence of mono- or polydentate nitrate ligands. The sharp absorption bands at 1052 and 1393 cm − 1 revealing for copper nitrate hydroxide. The bands at 1384 cm − 1 (strong) and 872 cm − 1 are related to NO 3 groups. The absorption band at 1052 cm − 1 was assigned to the bending vibration of Cu-O-H. Besides, the peaks in the range of 700 − 500 cm − 1 were attributed to the presence of metal-oxygen bonds. The XRD pattern of MSN (a) and simulated CNH, and MSN/C 3 N 4 /CNH (b) was described in Fig. 3 . The XRD pattern of MSN exhibits a broad diffraction peak at approximately 22° which is characteristic of amorphous silica. In the XRD pattern of MSN/C 3 N 4 /CNH, all diffraction peaks can be well indexed to a pure phase of CNH with a monoclinic structure (JCPDS No. 74-1749). The intensive and clear peaks confirmed that MSN/C 3 N 4 /CNH nanocomposite is well crystallized. No peaks could be appeared for the impurities including Cu, CuO, Cu 2 O, Cu(OH) 2 , or Cu(NO 3 ) 2 , demonstrating the high purity of MSN/C 3 N 4 /CNH nanocomposite. Furthermore, the peak at 27.5°, which corresponded to the (002) plane, was designated graphitic interlayer stacking structure of g-C 3 N 4 . In FE-SEM image of MSN/C 3 N 4 /CNH composite, spherical nanoparticles were visible, distributed uniformly over the support material with some agglomeration (Fig. 4 ). The average particle size was found to be around 22–38 nm. The energy dispersive X-ray analysis proves the existence of Cu along with Si, N, C, and O elements in MSN/C 3 N 4 /CNH composite (Fig. 5 ). The thermal stability of MSN/C 3 N 4 /CNH nanocomposite was examined by the simultaneous thermal analysis (STA) under a nitrogen atmosphere (Fig. 6 ). The initial mass loss at 125°C is due to the evaporation of adsorbed H 2 O molecules. Between 220 and 280°C, a mass loss is attributed to Cu 2 (OH) 3 NO 3 decomposing into CuO and the removal of H 2 O, NO 2 , and O 2 . There is a weight loss between 390 and 520°C, which is assigned to the combustion of g-C 3 N 4 . 3.3. Catalytic activity test The catalytic application of MSN/C 3 N 4 /CNH is tested in the Hantzsch reaction under diverse conditions (Table 1 ). The results illustrated that the reaction progress is highly affected by the amount of catalyst, temperature, and solvent. The amount of MSN/C 3 N 4 /CNH suitable to catalyze the reaction was examined by varying the amount of MSN/C 3 N 4 /CNH (5, 10, 15, and 20 mg) in the model reaction (ammonium acetate, dimedone, ethyl acetoacetate, and benzaldehyde). It was observed that the yield of the product enhanced with increasing the amount of MSN/C 3 N 4 /CNH from 5 to 10 mg (Table 1 , entries 1 and 2). The best result in an appropriate time was obtained using 10 mg of catalyst (Table 1 , entry 2). It is important to note that in the presence of 15 and 20 mg of MSN/C 3 N 4 /CNH the same result as 10 mg was observed (Table 1 , entries 3 and 4). The efficiency of MSN/C 3 N 4 /CNH catalyst was also considerably affected by solvent (Table 1 ). Among the applied solvents including toluene, acetonitrile, ethanol, water, and under solvent-free conditions, the best result was obtained after 15 min under solvent-free conditions in excellent yield (Table 1 , entries 5–9). Toluene delivered a low yield (25%) of the corresponding product (entry 5). Water proved to be a much better solvent in terms of yield (entry 8) than the others tested solvents including acetonitrile (entry 6), and ethanol (entry 7), which afforded the desired product in moderate yields (25–55%). With increasing temperature from room temperature to 50°C, a dominant increase in the yield was observed (Table 1 , entries 9–12). With the increasing temperature up to 70°C, no change in product yield was observed (Table 1 , entries 13 and 14). Table 1 The effect of catalyst loading, temperature and solvent in the Hantzsch reaction. Entry Catalyst (mg) Time (min) T (ᵒC) Solvent Yield (%) 1 5 15 50 - 47 2 10 15 50 - 94 3 15 15 50 - 94 4 20 15 50 - 94 5 10 15 50 Toluene 25 6 10 15 50 Acetonitrile 45 7 10 15 50 Ethanol 55 8 10 15 50 H 2 O 70 9 10 15 r.t. - 45 10 10 15 30 - 65 11 10 15 40 - 84 12 13 10 10 15 15 50 60 - - 94 94 14 10 15 70 - 94 Reaction conditions: benzaldehyde (1 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol), ammonium acetate (1.4 mmol). The reactions of various aldehydes possessing either electron-donating or electron-withdrawing substituents with ethyl acetoacetate, dimedone, and ammonium acetate in the presence of a catalytic amount (10 mg) of MSN/C 3 N 4 /CNH afforded high yields of the corresponding polyhydroquinoline derivatives (88–97%) in a short time under the optimized model reaction conditions (Table 2 ). The results demonstrate that the type and position of the substituent possess no substantial influence on the activity of MSN/C 3 N 4 /CNH catalyst. The results confirm the outstanding efficiency of MSN/C 3 N 4 /CNH for the conversion of an extensive range of aldehydes. Table 2 Synthesis of polyhydroquinoline derivatives by using MSN/C3N4/CNH catalyst under solvent free conditions. Entry R R' Yield (%) 1 C 6 H 5 Et 94 2 C 6 H 5 Me 94 3 4-NO 2 C 6 H 5 Et 96 4 4-NO 2 C 6 H 5 Me 95 5 4-ClC 6 H 5 Et 96 6 2-BrC 6 H 5 Et 97 7 4-MeC 6 H 5 Et 90 8 4-OHC 6 H 5 Et 92 9 3-EtO-4-OHC 6 H 5 Et 88 Reaction conditions: aldehyde (1 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol), ammonium acetate (1.4 mmol), catalyst (10 mg) and reaction time (15 min). The proposed mechanism for the synthesis of polyhydroquinoline compounds via the Hantzsch reaction is depicted in Scheme 1 . As CNH was comprised of copper hydroxide, Cu-OH bonds would exist, and Cu-OH cluster has been considered an active site for the construction of polyhydroquinoline. MSN/C 3 N 4 /CNH catalyst has both Lewis acidic sites (Cu) and basic sites (OH and C 3 N 4 ), hence it is an efficient heterogeneous catalyst for the Hantzsch reaction. According to literature, Cu-OH would firstly activate the carbonyl group of aldehyde by interacting oxygen with Cu metal. The role of MSN/C 3 N 4 /CNH comes in steps 1 and 4, in which catalyzes the Knoevenagel type coupling of aldehydes with 1,3-dicarbonyl compounds and in steps 3 and 6 where it catalyzes the Michael addition of intermediates A, B and C, D to provide the corresponding product. A second important intermediate is enamine B, formed via the condensation of ammonia with ethyl acetoacetate. 3.4. Reusability of MSN/C 3 N 4 /CNH After demonstrating the activity of MSN/C 3 N 4 /CNH catalyst for the various reactions, its reusability was examined in the model reaction. In each cycle, MSN/C 3 N 4 /CNH was straightforwardly recovered, washed with ethanol, and dried at 60°C. The reaction was repeated and the results exhibited that MSN/C 3 N 4 /CNH could be reused up to six times with a slight reduction in the catalytic activity (Fig. 7 ). This observation confirms the high recycling efficiency of MSN/C 3 N 4 /CNH, which is a noteworthy property from economic and environmental points of view. 3.5. Comparison of MSN/C 3 N 4 /CNH with previously reported catalysts for the Hantzsch reaction The performance of the MSN/C 3 N 4 /CNH catalyst was compared with that of catalysts reported in literature for the unsymmetrical Hantzsch reaction (Table 3 ). It is found that MSN/C 3 N 4 /CNH catalyst is superior to the majority of the reported catalysts in terms of cost-effectiveness, simplicity, short reaction time, amount of catalyst, type of solvent, and mild conditions. Table 3 Comparison of the proposed catalyst with reported catalysts for the unsymmetrical Hantzsch reaction. Catalyst Amount Time (min) Solvent Temp. (°C) Yield (%) Ref. SBA-15@Glycine-Cu 80 mg 90 Ethanol 60 96 (16) Fe 3 O 4 @SiO 2− /ZnCl 2 50 mg 25 - 110 90 (17) MCM-41@PDCA-C 10 mg 10 - 100 94 (22) IRMOF-3 4 mol% 180 - 60 91 (61) MoO 3 promotedCeO 2 -ZrO 2 200 mg 45 Ethanol reflux 93 (62) Fe 3 O 4 @MCM-41@Cu-P2C 20 mg 200 PEG 80 92 (63) MSN/C 3 N 4 /CNH 10 mg 15 - 50 94 Our work 4. Conclusions CNH grown on MSN/C 3 N 4 surface was fabricated and utilized as a recoverable and powerful nanocatalyst for the one-pot construction of polyhydroquinolines in 15 min with a quantity of catalyst 10 mg at 50°C under solvent-free conditions. The exceptional performance of MSN/C 3 N 4 /CNH catalyst can be attributed to the acid-base sites synergistic catalysis present in the catalyst. MSN/C 3 N 4 /CNH was straightforwardly recovered and reused six times with a slight reduction in the catalytic activity. The benefits of using MSN/C 3 N 4 /CNH catalyst include the low amount of catalyst, short reaction time, and solvent-free media. References H. Yazdani, S. E. Hooshmand, M. H. Stenzel, Fusion of Cellulose and multicomponent reactions: benign by design, ACS Sustain. Chem. Eng . 2022, 10, 4359-4373. M. Wang, C. Lv, C. Hu, Z. Su, Origin of enantioselectivity and product-distribution control in isocyanide-based multicomponent reaction catalysed by chiral N,N'-dioxide-Mg(II) complex, Mol. Catal . 2022, 524, 112277. P.-L. Wang, S.-Y. Ding, Z.-C. Zhang, Z.-P. Wang, W. Wang, Constructing robust covalent organic frameworks via multicomponent reactions, J. Am. Chem. Soc . 2019, 141, 18004-18008. N. Lohmann, V. Milovanovic, D. G. Piekarski, O. G. Mancheno, Metal-free oxoammonium salt-mediated C(sp 3 )-H oxidative Ugi-azide multicomponent reaction, Org. Biomol. Chem . 2022, 20, 2896-2908. G. A. Coppola, S. Pillitteri, E. V. Van der Eycken, S.-L. You, U. K. Sharma, Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency, Chem. Soc. Rev . 2022, 51, 2313-2382. A. R. Liandi, A. H. Cahyana, R. T. Yunarti, T. P. Wendari, Facile synthesis of magnetic Fe 3 O 4 @Chitosan nanocomposite as environmentally green catalyst in multicomponent Knoevenagel-Michael domino reaction, Ceram. Int . 2022, 48, 20266-20274. P. S. G. Nunes, H. D. A. Vidal, A. G. Correa, Recent advances in catalytic enantioselective multicomponent reactions, Org. Biomol. Chem . 2020, 18, 7751-7773. S. Yu, J. Wu, H. Lan, L. Gao, H. Qian, K. Fan, Z. Yin, Palladium and brønsted acid co-catalyzed biginelli-like multicomponent reactions via in situ-generated cyclic enol ether: access to spirofuran-hydropyrimidinones, Org. Lett . 2020, 22, 102-105. J. Wang, S. Zhu, Y. Liu, X. Zhu, K. Shi, X. Li, S. Zhu, Microwave-assisted multicomponent reaction: An efficient synthesis of indolyl substituted and spiroxindole pyrido[2,3-d]pyrimidine derivatives, Synth. Commun . 2022, In Press. Preeti, K. N. Singh, Metal-free multicomponent reactions: a benign access to monocyclic six-membered N-heterocycles, Org. Biomol. Chem . 2021, 19, 2622-2657. N. H. Sapariya, B. K. Vaghasiya, R. P. Thummar, R. D. Kamani, K. H. Patel, P. Thakor, S. S. Thakkar, A. Ray, D. K. Raval, Synthesis, characterization, in silico molecular docking study and biological evaluation of a 5-(phenylthio) pyrazole based polyhydroquinoline core moiety, New J. Chem . 2017, 41, 10686-10694. D. da Costa Cabrera, S. B. Rosa, F. Saes de Oliveira, M. A. G. Marinho, C. R. Montes DOca, D. Russowsky, A. P. Horn, M. G. Montes DOca, Synthesis and antiproliferative activity of novel hybrid 3-substituted polyhydroquinoline-fatty acids, Med. Chem. Commun . 2016, 7, 2167-2176. R. R. Raslan, S. A. Hessein, S. A. Fouad, N. A. M. Shmiess, Synthesis and antitumor evaluation of some new thiazolopyridine, nicotinonitrile, pyrazolopyridine, and polyhydroquinoline derivatives using ceric ammonium nitrate as a green catalyst, J Heterocyclic Chem . 2022, 59, 832-846. K. Venkatapathy, C. J. Magesh, G. Lavanya, P. T. Perumal, S. Prema, Design, synthesis, molecular docking, and spectral studies of new class of carbazolyl polyhydroquinoline derivatives as promising antibacterial agents with noncytotoxicity towards human mononuclear cells from peripheral blood, J Heterocyclic Chem . 2020, 57, 1936-1955. V. T. Nguyen, H. T. Nguyen, P. H. Tran, One-pot three-component synthesis of 1-amidoalkyl naphthols and polyhydroquinolines using a deep eutectic solvent: a green method and mechanistic insight, New J. Chem . 2021, 45, 2053-2059. T. Tamoradi, A. Ghorbani-Choghamarani, M. Ghadermazi, H. Veisi, SBA-15@Glycine-M (M= Ni and Cu): Two green, novel and efficient catalysts for the one-pot synthesis of 5-substituted tetrazole and polyhydroquinoline derivatives, Solid State Sci . 2019, 91, 96-107. B. Maleki, H. Alinezhad, H. Atharifar, R. Tayebee, A. Vedad Mofrad, One-Pot Synthesis of Polyhydroquinolines Catalyzed by ZnCl 2 Supported on Nano Fe 3 O 4 @SiO 2 , Org. Prep. Proced. Int . 2019, 51, 301-309. I. Sehout, R. Boulcina, B. Boumoud, T. Boumoud, A. Debache, Solvent-free synthesis of polyhydroquinoline and 1,8-dioxodecahydroacridine derivatives through the Hantzsch reaction catalyzed by a natural organic acid: A green method, Synth. Commun . 2017, 47, 1185-1191. G. Rathee, S. Kohli, S. Panchal, N. Singh, A. Awasthi, S. Singh, A. Singh, S. Hooda, R. Chandra, Fabrication of a gold-supported NiAlTi-layered double hydroxide nanocatalyst for organic transformations, ACS Omega 2020, 5, 23967-23974. M. Rahmati, H. Ghafuri, N. Ghanbari, Z. Tajik, 1,4 Butanesultone functionalized graphitic carbon nitride: efficient catalysts for the one-pot synthesis of 1,4-dihydropyridine and polyhydroquinoline derivative through hantzsch reaction, Polycycl. Aromat. Comp . 2022, In Press. E. Zare, Z. Rafiee, Magnetic chitosan supported covalent organic framework/copper nanocomposite as an efficient and recoverable catalyst for the unsymmetrical hantzsch reaction, J. Taiwan. Inst. Chem. Eng . 2020, 116, 205-214. S. Sharma, U. P. Singh, A. P. Singh, Synthesis of MCM-41 supported cobalt (II) complex for the formation of polyhydroquinoline derivatives, Polyhedron , 2021, 199, 115102. S. Rathod, V. Dhage, M. Lande, An eco-friendly synthesis of polyhydroquinoline derivatives using MoO 3 promoted CeO 2 -ZrO 2 solid heterogeneous catalyst, Mater. Today: Proc. 2021, 47, 1736-1740. M. Roozifar, N. Hazeri, H. Faroughi Niya, Application of salicylic acid as an eco-friendly and efficient catalyst for the synthesis of 2,4,6-triaryl pyridine, 2-amino-3-cyanopyridine, and polyhydroquinoline derivatives, J. Heterocyclic Chem . 2021, 58, 1117-1129. H. Aghahosseini, M. R. Ranjbar, A. Ramazani, Simple and efficient synthesis of guanidine-based magnetic nanocatalyst for the one-pot, four-component synthesis of polyhydroquinolines in water, ChemistrySelect 2020, 5, 8415-8420. Q. Zhang, X. Yang, J. Guan, Applications of magnetic nanomaterials in heterogeneous catalysis, ACS Appl. Nano Mater . 2019, 2, 4681-4697. P. Bhanja, A. Modak, A. Bhaumik, Supported porous nanomaterials as efficient heterogeneous catalysts for CO 2 fixation reactions, Chem. Eur. J . 2018, 24, 7278-7297. K. Shen, X. Chen, J. Chen, Y. Li, Development of MOF-derived carbon-based nanomaterials for efficient catalysis, ACS Catal . 2016, 6, 9, 5887-5903. J. G. Croissant, X. Cattoen, J.-O. Durand, M. W. C. Man, N. M. Khashab, Organosilica hybrid nanomaterials with a high organic content: syntheses and applications of silsesquioxanes, Nanoscale 2016, 8, 19945-19972 Y. Chen, Z. Fan, Z. Zhang, W. Niu, C. Li, N. Yang, B. Chen, H. Zhang, Two-dimensional metal nanomaterials: synthesis, properties, and applications, Chem. Rev . 2018, 118, 6409-6455. J. Huang, X. Tan, C. Li, R. Wu, Shuqin Ran, Yuxin Tao, and Tong Mou, Green synthesis of Au-NPs on g-C 3 N 4 hybrid nanomaterials based on supramolecular pillar[6]arene and its applications for catalysis, ACS Omega 2022, 7, 18085-18093. F. Hassanzadeh-Afruzi, H. Dogari, F. Esmailzadeh, A. Maleki, Magnetized melamine-modified polyacrylonitrile (PAN@melamine/Fe 3 O 4 ) organometallic nanomaterial: Preparation, characterization, and application as a multifunctional catalyst in the synthesis of bioactive dihydropyrano [2,3-c]pyrazole and 2-amino-3-cyano 4H-pyran derivatives, Appl. Organomet. Chem. 2021, 35, e6363. M. Khalil, G. T.M. Kadj, M. Muallifu lIlmi, Advanced nanomaterials for catalysis: Current progress in fine chemical synthesis, hydrocarbon processing, and renewable energy, J. Ind. Eng. Chem . 2021, 93, 78-100. Z. Rafiee, Fabrication of efficient Zn-MOF/COF catalyst for the Knoevenagel condensation reaction, J. Iran. Chem. Soc . 2021, 18, 2657-2664. A. Arabmarkadeh, R. Javahershenas, M. Kazemi, Nanomaterials: Catalysis in synthesis of highly substituted heterocycles, Synth. Commun . 2021, 51, 880-903. A. D. Kute, R. P. Gaikwad, I. R. Warkad, M. B. Gawand, A review on the synthesis and applications of sustainable copper-based nanomaterials, Green Chem . 2022, 24, 3502-3573. Recent advances in the synthesis of various analogues of MOF-based nanomaterials: A mini-review, K. O. Otun, S. O. Amusat, I. T. Bello, J. Abdulsalam, A. T. Ajiboye, A. A. Adeleke, S. O. Azeez, Inorg. Chim. Acta 2022, 120890. A. Villa, M. Schiavoni, L. Prati, Material science for the support design: a powerful challenge for catalysis, Catal. Sci. Technol . 2012, 2, 673-682. X. Sui, L. Zhang, J. Li, K. Doyle-Davis, R. Li, Z. Wang, X. Sun, Advanced support materials and interactions for atomically dispersed noble-metal catalysts: from support effects to design strategies, Adv. Energy Mater . 2022, 12, 2102556. J. C. S. Terra, A. Moores, F C. C. Moura, Amine-functionalized mesoporous silica as a support for on-demand release of copper in the A 3 -coupling reaction: Ultralow concentration catalysis and confinement effect, ACS Sustain. Chem. Eng . 2019, 7, 9, 8696-8705. A . Saad, C . Vard, M . Abderrabba, M . M. Chehimi, Triazole/triazine-functionalized mesoporous silica as a hybrid material support for palladium nanocatalyst, Langmuir 2017, 33, 28, 7137-7146. S. Thomas, T. A. Nguyen, M. Ahmadi, G. Yasin, N. Joshi, Silicon-based hybrid nanoparticles fundamentals, properties, and applications, Elsevier, 2022. N. Pal, J.-H. Lee, E.-B. Cho, Recent trends in morphology-controlled synthesis and application of mesoporous silica nanoparticles, Nanomaterials 2020, 10, 2122. W. Gao, Y. Wang, F. Zhang, S. Zhang, H.-Z. Lian, Tetrasulfonate calix[4]arene modified large pore mesoporous silica microspheres: Synthesis, characterization, and application in protein separation, Talanta 2021, 226, 122171. J. Huang, H.-B. Liu, J. Wang, Functionalized mesoporous silica as a fluorescence sensor for selective detection of Hg 2+ in aqueous medium, Spectrochim. Acta A Mol. Biomol. Spectrosc . 2021, 246, 118974. J. O. Otalvaro, T. R. Alvarez, M. S. V. Gurovic, V. Lassalle, M. Agotegaray, M. Avena, M. Brigante, Magnetic mesoporous silica nanoparticles for drug delivery systems: Synthesis, characterization and application as norfloxacin carrier, J. Pharm. Sci . 2022, In Press. A. A. Sosa, V. Palermo, P. Langer, R. Luque, G. P. Romanelli, L. R. Pizzio, Tungstophosphoric acid/mesoporous silicas as suitable catalysts in quinoxaline synthesis, Mol. Catal . 2022, 517, 112046. J. Zhu, P. Xiao, H. Li, S. A. C. Carabineiro, Graphitic carbon nitride: Synthesis, properties, and applications in catalysis, ACS Appl. Mater. Interfaces 2014, 6, 16449-16465. M. Ismael, A review on graphitic carbon nitride (g-C 3 N 4 ) based nanocomposites: Synthesis, categories, and their application in photocatalysis, J. Alloys Compd . 2020, 846, 15644. V V. Phatake, B. M. Bhanage, Cu@U-g-C 3 N 4 catalyzed cyclization of o-phenylenediamines for the synthesis of benzimidazoles by using CO 2 and dimethylamine borane as a hydrogen source, Catal. Lett . 2019, 149, 347-359 . H. Veisi, P. Mohammadi, T. Ozturk, Design, synthesis, characterization, and catalytic properties of g-C 3 N 4 -SO 3 H as an efficient nanosheet ionic liquid for one-pot synthesis of pyrazolo[3,4-b]pyridines and bis(indolyl)methanes, J. Mol. Liq . 2020, 303, 112625. N. Kong, X. Fan, F. Liu, L. Wang, H. Lin, Y. Li, S.-T. Lee, Single vanadium atoms anchored on graphitic carbon nitride as a high-performance catalyst for non-oxidative propane dehydrogenation, ACS Nano 2020, 14, 5772-5779 . I. Camussi, B. Mannucci, A. Speltini, A. Profumo, C. Milanese, L. Malavasi, P. Quadrelli, g-C 3 N 4 - Singlet oxygen made easy for organic synthesis: scope and limitations, ACS Sustainable Chem. Eng . 2019, 7, 8176-8182. M. L. Ur Rehman, Q. Hou, X. Bai, Y. Nie, H. Qian, T. Xia, R. Lai, G. Yu, M. Ju, Regulating the alkalinity of carbon nitride by magnesium doping to boost the selective isomerization of glucose to fructose, ACS Sustainable Chem. Eng . 2022, 10, 1986-1993. Y. Gong, M. Li, H. Li, Y. Wang, Graphitic carbon nitride polymers: promising catalysts or catalyst supports for heterogeneous oxidation and hydrogenation, Green Chem . 2015, 17, 715-736. Bing-Cheng Li, Jechan Lee, Eilhann Kwon, Bui Xuan Thanh, Jia-Yin Lin, Siming You, Chia-Hua Lin, Kun-Yi Andrew Lin, 2-Dimensional nanoleaf-like porous copper nitrate hydroxide as an effective heterogeneous catalyst for selective oxidation of hydroxymethylfurfural to diformylfuran, J. Taiwan. Inst. Chem. Eng . 2021, 126, 189-196. B. Liu, One-dimensional copper hydroxide nitrate nanorods and nanobelts for radiochemical applications, Nanoscale , 2012, 4, 7194-7198. B.-C.Li, N. N. Huy, J.-Y. Lin, S. Phattarapattamawong, G. Lisak, H. Wang, K.-Y. Andrew Lin, Nanopetal-like copper hydroxide nitrate as a highly selective heterogeneous catalyst for valorization of vanillic alcohol via oxidation, J. Environ. Chem. Eng . 2021, 9, 106092. H. Niu, Q. Yang, K. Tang, A new route to copper nitrate hydroxide microcrystals, Mater. Sci. Eng. B 2006, 135, 172-175. E. K. Guner, A. Ozer, Synthesis and characterization of copper hydroxynitrate and copper oxide by hydrothermal method, J. Turkish chem. Soc. 2017, 1, 183-192. S. Rostamnia, H. Xin Basic isoreticular metal-organic framework (IRMOF-3) porous nanomaterial as a suitable and green catalyst for selective unsymmetrical Hantzsch coupling reaction, Appl. Organomet. Chem . 2014, 28, 359-363. S. Rathod, V. Dhage, M. Lande, An eco-friendly synthesis of polyhydroquinoline derivatives using MoO 3 promoted CeO 2 -ZrO 2 solid heterogeneous catalyst, Mater. Today: Proc. 2021, 47, 1736-1740. M. Nikoorazm, Z. Erfani, Core-shell nanostructure (Fe 3 O 4 @MCM-41@Cu-P2C) as a highly efficient and recoverable nanocatalyst for the synthesis of polyhydroquinoline, 5-substituted 1H-tetrazoles and sulfides, Chem. Phys. Lett . 2019, 737, 136784. Scheme 1 Scheme 1 is available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files Scheme1.png Scheme 1. Proposed mechanism of catalytic synthesis of polyhydroquinolines using MSN/C3N4/CNH. Cite Share Download PDF Status: Published Journal Publication published 12 Jun, 2023 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Major revision 08 Dec, 2022 Reviews received at journal 31 Oct, 2022 Reviewers agreed at journal 20 Oct, 2022 Reviews received at journal 11 Oct, 2022 Reviews received at journal 06 Oct, 2022 Reviewers agreed at journal 21 Sep, 2022 Reviewers agreed at journal 20 Sep, 2022 Reviewers invited by journal 19 Sep, 2022 Editor assigned by journal 19 Sep, 2022 Editor invited by journal 19 Sep, 2022 Submission checks completed at journal 19 Sep, 2022 First submitted to journal 14 Sep, 2022 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-2064047","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":137818316,"identity":"81a8699f-3ff7-4d5e-9386-ceebd12cbfa0","order_by":0,"name":"Ensiyeh Rahmati","email":"","orcid":"","institution":"Yasouj University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Ensiyeh","middleName":"","lastName":"Rahmati","suffix":""},{"id":137818317,"identity":"1a713d42-4fc6-4383-8080-634ae4f1c0c3","order_by":1,"name":"Zahra Rafiee","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAzElEQVRIiWNgGAWjYLCCCgMGBn4om4c4LWeAWiQbSNMCxAYHiHWTfAPvww8HCmzkjG/kGDD8qGGQMW8goIWxgd1Y4oBBmrEZUAtjzzEGHhlC1jEzsDFIfzA4nLgNZAtvAwOPBCGHsTGwMf84YPC/fvMMoC1/idHCw8DGBnTYgQQDiRwDZqJskWBmY7M4YJBsOOPMs4LDMsckCGuRb29jvnHgj508f3vyxodvamzsCWoB+h8KBBIYDgBtJagBCfAfIEX1KBgFo2AUjCQAANjfM64P1d3OAAAAAElFTkSuQmCC","orcid":"","institution":"Yasouj University","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Zahra","middleName":"","lastName":"Rafiee","suffix":""}],"badges":[],"createdAt":"2022-09-14 08:59:22","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-2064047/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-2064047/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-023-36059-7","type":"published","date":"2023-06-12T21:12:18+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":26789599,"identity":"f16df76b-bb4e-48e1-8bf8-086642ce19a4","added_by":"auto","created_at":"2022-09-21 22:06:14","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":135040,"visible":true,"origin":"","legend":"\u003cp\u003ePreparation of MSN/C3N4/CNH nanocomposite.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/7c1aaed7f58e99d02b208999.png"},{"id":26788792,"identity":"3f187b71-606a-461a-8760-4d59389f115c","added_by":"auto","created_at":"2022-09-21 22:01:14","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":42423,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of MSN (a), MSN/C3N4 (b), and MSN/C3N4/CNH (c).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/fc810748956c1d5f18808160.png"},{"id":26788794,"identity":"87357368-4b71-42c2-8616-d2bbce466f70","added_by":"auto","created_at":"2022-09-21 22:01:14","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":52409,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of MSN (a) and simulated CNH, and MSN/C3N4/CNH (b).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/d5f9ab23b8f6806d1fe82c85.png"},{"id":26788790,"identity":"a0647645-b63c-41e4-8925-e85f65905522","added_by":"auto","created_at":"2022-09-21 22:01:14","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":304521,"visible":true,"origin":"","legend":"\u003cp\u003eSEM image of MSN/C3N4/CNH.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/5dbbe09cb04427b52381fdb5.png"},{"id":26788791,"identity":"b174347f-e664-4a0a-87dd-46ea82d6afcb","added_by":"auto","created_at":"2022-09-21 22:01:14","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":32645,"visible":true,"origin":"","legend":"\u003cp\u003eEDS of MSN/C3N4/CNH\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/dbd17fd8629dd09238e8c392.png"},{"id":26789600,"identity":"b0d1696c-5281-492d-bfa5-1bf6c07c30b9","added_by":"auto","created_at":"2022-09-21 22:06:14","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":82512,"visible":true,"origin":"","legend":"\u003cp\u003eSTA thermogram of MSN/C3N4/CNH.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/5f777f6ebc81a0137facdc7c.png"},{"id":26788795,"identity":"e9745e12-69b2-4925-a145-24781981c98a","added_by":"auto","created_at":"2022-09-21 22:01:14","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":36101,"visible":true,"origin":"","legend":"\u003cp\u003eReusability of the MSN/C3N4/CNH.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/f2154ae21901b145812b9b15.png"},{"id":44731812,"identity":"b57b758e-3614-4e96-8bcb-926530e0063f","added_by":"auto","created_at":"2023-10-16 21:48:01","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":923086,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/d9e08994-39c2-4eca-a492-23bde5cfffd5.pdf"},{"id":26788788,"identity":"3d749443-2e2b-4b6f-833a-c8bfaec52dc8","added_by":"auto","created_at":"2022-09-21 22:01:14","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":29190,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1.\u003c/strong\u003e Proposed mechanism of catalytic synthesis of polyhydroquinolines using MSN/C3N4/CNH.\u003c/p\u003e","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-2064047/v1/c5cf3bf696ac0cc2fe6b1284.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Hantzsch Reaction using Copper Nitrate Hydroxide- Containing Mesoporous Silica Nanoparticle with C 3 N 4 Framework as A Novel Powerful and Reusable Catalyst","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eMulticomponent reactions (MCRs) are defined as attractive and powerful synthetic protocols for producing highly complex molecules and biological significance molecules owing to the formation of C-C and C-heteroatom bonds in a one-pot manner through an easy tandem synthetic method with step-efficiency and atom-economy (\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6 CR7 CR8 CR9\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e). Polyhydroquinoline (PHQ) derivatives as a significant class of nitrogen heterocycle compounds can be converted into biological compounds, displaying promising pharmaceutical and biological properties, including antitumor, antidiabetic, platelet anti-aggregation, bronchodilator, antibacterial, and neurotropic (\u003cspan additionalcitationids=\"CR12 CR13\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e). Thus, the production of PHQ derivatives is of great importance. The new techniques have been developed to improve the reaction efficiency in the preparation of PHQ derivatives in the presence of catalysts including [CholineCl][ZnCl\u003csub\u003e2\u003c/sub\u003e]\u003csub\u003e3\u003c/sub\u003e (\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e), SBA-15@Glycine-Cu (\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e), Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@SiO\u003csub\u003e2\u003c/sub\u003e/ZnCl\u003csub\u003e2\u003c/sub\u003e (\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e), ascorbic acid (\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e), NiAlTi LDH (\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e), and CNNs-Bu-SO\u003csub\u003e3\u003c/sub\u003eH (\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e). However, some of these synthetic methods suffer from the usage of toxic organic solvents, long reaction time, harsh reaction conditions, a great amount of catalyst, and low yields. Consequently, there is further improvement toward more sustainable protocol for the fabrication of PHQ derivatives. Lately, remarkable attention has been developed to designing eco-friendly catalysts and synthetic procedures for the Hantzsch reaction. The environmentally benign processes comprise the use of effective, biodegradable, and economical catalysts and non-toxic systems such as solvent-free conditions, water, and supercritical fluids (\u003cspan additionalcitationids=\"CR22 CR23 CR24\" citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe substantial advance in nanotechnology during the last decades has led to the development of a large variety of nanomaterials with outstanding catalysis applications. It is possible to design and construct numerous nanomaterials suitable as heterogeneous catalysts (\u003cspan additionalcitationids=\"CR27 CR28 CR29 CR30 CR31 CR32 CR33 CR34 CR35 CR36\" citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e). The support material selection possesses a key role in the overall efficiency of the catalyst because these materials impact the catalytic properties of nano-scale catalysts (\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e). The materials for catalyst supports indicate the high surface area, capability to disperse the supported metal, and chemical stability. Amongst the various support materials, mesoporous silica materials (MSMs) are promising materials owing to their thermally and chemically stability, large surface area, easy surface functionalization, good biocompatibility, and can be produced with tunable micro/meso porosity (\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e). MSMs are amorphous inorganic materials composed of silicon and oxygen elements in their framework with pore diameters ranging from 2 to 50 nm. The well-defined pore structure of porous silica can function as a molecular sieve at small sizes and may ultimately be utilized to control substrate access to the catalyst which is very important in improving/tuning the selectivity (\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e). These materials have proved their versatility in separation (\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e), sensor (\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e), drug delivery (\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e), and catalysis (\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e). Carbon nanostructures are especially of attention owing to their promising properties including high specific surface area, excellent mechanical strength, high conductivity, and fascinating physicochemical features. Among these, graphitic carbon nitride (g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e) as a free metals material is especially of attention, owing to its unique crystal structure, nontoxic, cost-effectiveness, high thermal and chemical stability, and resistance to acidic and basic conditions (\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e). C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e has a stacked two-dimensional structure and can be synthesized easily from low-cost precursors such as urea, thiourea, melamine, and cyanamide via pyrolysis. Owing to its promising features, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e and its composites are applied in a variety of photocatalytic applications (\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e). So far, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e has been utilized as a catalyst or catalyst support in various organic reactions (\u003cspan additionalcitationids=\"CR51 CR52 CR53 CR54\" citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e). However, the practical application of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e is limited by its low surface area, insufficient light absorption, reduction potential, inappropriate rapid recombination, and large diffusion resistance of charges. The g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e can enhance the surface area, promote charge transfer and mass diffusion through nanostructure materials design.\u003c/p\u003e \u003cp\u003eCopper hydroxide nitrate, [Cu\u003csub\u003e2\u003c/sub\u003e(OH)\u003csub\u003e3\u003c/sub\u003eNO\u003csub\u003e3\u003c/sub\u003e], is a basic copper(II) salt with a layered structure, that have applications in vehicle airbags, catalyst, and ion exchangers (\u003cspan additionalcitationids=\"CR57 CR58 CR59\" citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e). [Cu\u003csub\u003e2\u003c/sub\u003e(OH)\u003csub\u003e3\u003c/sub\u003eNO\u003csub\u003e3\u003c/sub\u003e] exists as two structurally related dimorphs, a synthetic metastable monoclinic phase and a natural orthorhombic phase occurring in the mineral gerhardtite. The structure can be observed as layers of copper octahedra stacked with each other. The Cu octahedral form layers of stoichiometry [Cu\u003csub\u003e2\u003c/sub\u003e(OH)\u003csub\u003e3\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e, and NO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e ions stand in between the positive layers for charge balance, which are linked to the hydroxyl groups via hydrogen bonding belonging to the copper octahedra layers.\u003c/p\u003e \u003cp\u003eIn this study, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/MSN was fabricated and utilized as support to load copper nitrate hydroxide (CNH) (Cu\u003csub\u003e2\u003c/sub\u003e(OH)\u003csub\u003e3\u003c/sub\u003eNO\u003csub\u003e3\u003c/sub\u003e) and emerged as a competent heterogeneous nanocatalyst for the Hantzsch reaction.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Preparation of MSN\u003c/h2\u003e \u003cp\u003e0.2 g of glucose was dissolved in 90 mL of ethanol. Then, 4 mL of TEOS (as the silica source) and 6 mL of distilled water were added to the above solution and subsequently stirred at room temperature for 12 h. The solid was separated by centrifuge and washed with distilled water and ethanol, respectively. The obtained white solid calcined at 550\u0026deg;C for 6 to the production of porous silica hollow sphere.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Synthesis of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003e1.0 g of MSN, 5.0 g of urea, and 3 wt% of KBr were placed in a porcelain dish and the mixture was ground completely. Subsequently, the reaction was performed at 550\u0026deg;C for 2 h in a crucible for calcination.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Synthesis of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH\u003c/h2\u003e \u003cp\u003e0.25 g of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e and 0.15 g of Cu(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e.3H\u003csub\u003e2\u003c/sub\u003eO were mixed in 40 mL of ethanol and heated under reflux conditions and argon atmosphere for 24 h. The resultant precipitate was washed (ethanol) and dried at 80 ᵒC under vacuum for 10 h.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. The Hantzsch reaction using MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst\u003c/h2\u003e \u003cp\u003e \u003cem\u003eGeneral procedure\u003c/em\u003e: A mixture of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH (15 mg), ammonium acetate (1.4 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol), and aldehyde (1 mmol) was stirred at 50\u0026deg;C, as monitored via TLC (ethyl acetate/n-hexane 50:50) for a complete reaction. Then, 10 mL of solvent (warm ethanol) was added to the mixture and MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH was separated via filtration. The underlying solution was heated to boiling temperature and then a piece of ice was added to precipitate the desired crystalline product. The solvent was vaporized and ethanol was utilized to crystallize the resultant product. Then, the recovered MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH was reused in six runs under similar conditions as the first run to represent the recyclability and stability of the prepared catalyst.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results And Discussion","content":"\u003cdiv class=\"Section2\" id=\"Sec8\"\u003e\n \u003ch2\u003e3.1. Synthesis of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH\u003c/h2\u003e\n \u003cp\u003eAn adequate amount of TEOS as silica precursor was added to a mixture of glucose as sacrificial template and ethanol, the shell of silica, and glucose as the core were formed. After calcination at elevated temperature, glucose core was removed and the space vacant was performed. MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e was fabricated via calcination technique onto MSN surface using melamine as a precursor. MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e was applied as support material to anchor CNH to afford MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec9\"\u003e\n \u003ch2\u003e3.2. Characterization of synthesized compounds\u003c/h2\u003e\n \u003cp\u003eFTIR spectra of MSN (a), MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e (b), and MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH (c) are revealed in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. In the spectrum of MSN, the peak appeared at 3429 cm\u003csup\u003e− 1\u003c/sup\u003e belonged to the stretching vibration of O-H; the absorption bands at 1082 and 810 cm\u003csup\u003e− 1\u003c/sup\u003e assigned the asymmetric and symmetric stretching vibrations of Si-O-Si, respectively. In the spectrum of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, the broad band in the range of 3500 − 3000 cm\u003csup\u003e− 1\u003c/sup\u003e indicates the presence of N-H stretching vibration of the terminal amino group was observed in g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e. The peak around 1640 cm\u003csup\u003e− 1\u003c/sup\u003e contributed to the stretching mode of C = N bonds. The intense bands observed at 1560, 1427, 1320, and 1243 cm\u003csup\u003e− 1\u003c/sup\u003e were due to the presence of C-N stretching of tri-s-triazine. The band around 800 cm\u003csup\u003e− 1\u003c/sup\u003e reveals out-of-plane bending vibration of triazinecycle. In the spectrum of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH, the peak at 3427 cm\u003csup\u003e− 1\u003c/sup\u003e corresponds to the stretching vibration of the O-H and O-H groups of molecular water, and the band at 1662 cm\u003csup\u003e− 1\u003c/sup\u003e is owing to the bending mode of H\u003csub\u003e2\u003c/sub\u003eO molecules. The presence of NO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e−\u003c/sup\u003e in MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH is evidenced by the vibration bands that appeared from middle to lower wavenumbers, confirming the presence of mono- or polydentate nitrate ligands. The sharp absorption bands at 1052 and 1393 cm\u003csup\u003e− 1\u003c/sup\u003e revealing for copper nitrate hydroxide. The bands at 1384 cm\u003csup\u003e− 1\u003c/sup\u003e (strong) and 872 cm\u003csup\u003e− 1\u003c/sup\u003e are related to NO\u003csub\u003e3\u003c/sub\u003e groups. The absorption band at 1052 cm\u003csup\u003e− 1\u003c/sup\u003e was assigned to the bending vibration of Cu-O-H. Besides, the peaks in the range of 700 − 500 cm\u003csup\u003e− 1\u003c/sup\u003e were attributed to the presence of metal-oxygen bonds.\u003c/p\u003e\n \u003cp\u003eThe XRD pattern of MSN (a) and simulated CNH, and MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH (b) was described in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. The XRD pattern of MSN exhibits a broad diffraction peak at approximately 22° which is characteristic of amorphous silica. In the XRD pattern of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH, all diffraction peaks can be well indexed to a pure phase of CNH with a monoclinic structure (JCPDS No. 74-1749). The intensive and clear peaks confirmed that MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH nanocomposite is well crystallized. No peaks could be appeared for the impurities including Cu, CuO, Cu\u003csub\u003e2\u003c/sub\u003eO, Cu(OH)\u003csub\u003e2\u003c/sub\u003e, or Cu(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e, demonstrating the high purity of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH nanocomposite. Furthermore, the peak at 27.5°, which corresponded to the (002) plane, was designated graphitic interlayer stacking structure of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e.\u003c/p\u003e\n \u003cp\u003eIn FE-SEM image of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH composite, spherical nanoparticles were visible, distributed uniformly over the support material with some agglomeration (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e). The average particle size was found to be around 22–38 nm. The energy dispersive X-ray analysis proves the existence of Cu along with Si, N, C, and O elements in MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH composite (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eThe thermal stability of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH nanocomposite was examined by the simultaneous thermal analysis (STA) under a nitrogen atmosphere (Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e). The initial mass loss at 125°C is due to the evaporation of adsorbed H\u003csub\u003e2\u003c/sub\u003eO molecules. Between 220 and 280°C, a mass loss is attributed to Cu\u003csub\u003e2\u003c/sub\u003e(OH)\u003csub\u003e3\u003c/sub\u003eNO\u003csub\u003e3\u003c/sub\u003e decomposing into CuO and the removal of H\u003csub\u003e2\u003c/sub\u003eO, NO\u003csub\u003e2\u003c/sub\u003e, and O\u003csub\u003e2\u003c/sub\u003e. There is a weight loss between 390 and 520°C, which is assigned to the combustion of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec10\"\u003e\n \u003ch2\u003e3.3. Catalytic activity test\u003c/h2\u003e\n \u003cp\u003eThe catalytic application of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH is tested in the Hantzsch reaction under diverse conditions (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). The results illustrated that the reaction progress is highly affected by the amount of catalyst, temperature, and solvent. The amount of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH suitable to catalyze the reaction was examined by varying the amount of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH (5, 10, 15, and 20 mg) in the model reaction (ammonium acetate, dimedone, ethyl acetoacetate, and benzaldehyde). It was observed that the yield of the product enhanced with increasing the amount of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH from 5 to 10 mg (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 1 and 2). The best result in an appropriate time was obtained using 10 mg of catalyst (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, entry 2). It is important to note that in the presence of 15 and 20 mg of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH the same result as 10 mg was observed (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 3 and 4). The efficiency of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst was also considerably affected by solvent (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). Among the applied solvents including toluene, acetonitrile, ethanol, water, and under solvent-free conditions, the best result was obtained after 15 min under solvent-free conditions in excellent yield (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 5–9). Toluene delivered a low yield (25%) of the corresponding product (entry 5). Water proved to be a much better solvent in terms of yield (entry 8) than the others tested solvents including acetonitrile (entry 6), and ethanol (entry 7), which afforded the desired product in moderate yields (25–55%). With increasing temperature from room temperature to 50°C, a dominant increase in the yield was observed (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 9–12). With the increasing temperature up to 70°C, no change in product yield was observed (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e, entries 13 and 14).\u003c/p\u003e\u0026nbsp;\u003ctable border=\"1\" id=\"Tab1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eThe effect of catalyst loading, temperature and solvent in the Hantzsch reaction.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"6\"\u003e\u003cimg 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\"\u003e\u003cbr\u003e\u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCatalyst (mg)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eTime\u003c/p\u003e\n \u003cp\u003e(min)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eT (ᵒC)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eSolvent\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eYield\u003c/p\u003e\n \u003cp\u003e(%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e47\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e10\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e15\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e50\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cstrong\u003e94\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eToluene\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eAcetonitrile\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e45\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEthanol\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e55\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e70\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003er.t.\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e45\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e30\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e65\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e40\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e84\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e12\u003c/p\u003e\n \u003cp\u003e13\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003cp\u003e60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e70\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"6\"\u003eReaction conditions: benzaldehyde (1 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol), ammonium acetate (1.4 mmol).\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n \u003cp\u003eThe reactions of various aldehydes possessing either electron-donating or electron-withdrawing substituents with ethyl acetoacetate, dimedone, and ammonium acetate in the presence of a catalytic amount (10 mg) of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH afforded high yields of the corresponding polyhydroquinoline derivatives (88–97%) in a short time under the optimized model reaction conditions (Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e). The results demonstrate that the type and position of the substituent possess no substantial influence on the activity of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst. The results confirm the outstanding efficiency of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH for the conversion of an extensive range of aldehydes.\u003c/p\u003e\u0026nbsp;\u003ctable border=\"1\" id=\"Tab2\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eSynthesis of polyhydroquinoline derivatives by using MSN/C3N4/CNH catalyst under solvent free conditions.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"4\"\u003e\u003cimg 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\"\u003e\u003cbr\u003e\u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEntry\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eR\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eR'\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eYield\u003c/p\u003e\n \u003cp\u003e(%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eMe\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4-NO\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e96\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4-NO\u003csub\u003e2\u003c/sub\u003eC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eMe\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e95\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4-ClC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e96\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2-BrC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e97\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4-MeC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4-OHC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e92\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3-EtO-4-OHC\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEt\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e88\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"4\"\u003eReaction conditions: aldehyde (1 mmol), dimedone (1 mmol), ethyl acetoacetate (1 mmol), ammonium acetate (1.4 mmol), catalyst (10 mg) and reaction time (15 min).\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n \u003cp\u003eThe proposed mechanism for the synthesis of polyhydroquinoline compounds via the Hantzsch reaction is depicted in Scheme \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e. As CNH was comprised of copper hydroxide, Cu-OH bonds would exist, and Cu-OH cluster has been considered an active site for the construction of polyhydroquinoline. MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst has both Lewis acidic sites (Cu) and basic sites (OH and C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e), hence it is an efficient heterogeneous catalyst for the Hantzsch reaction. According to literature, Cu-OH would firstly activate the carbonyl group of aldehyde by interacting oxygen with Cu metal. The role of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH comes in steps 1 and 4, in which catalyzes the Knoevenagel type coupling of aldehydes with 1,3-dicarbonyl compounds and in steps 3 and 6 where it catalyzes the Michael addition of intermediates A, B and C, D to provide the corresponding product. A second important intermediate is enamine B, formed via the condensation of ammonia with ethyl acetoacetate.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec11\"\u003e\n \u003ch2\u003e3.4. Reusability of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH\u003c/h2\u003e\n \u003cp\u003eAfter demonstrating the activity of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst for the various reactions, its reusability was examined in the model reaction. In each cycle, MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH was straightforwardly recovered, washed with ethanol, and dried at 60°C. The reaction was repeated and the results exhibited that MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH could be reused up to six times with a slight reduction in the catalytic activity (Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e). This observation confirms the high recycling efficiency of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH, which is a noteworthy property from economic and environmental points of view.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec12\"\u003e\n \u003ch2\u003e\u003cem\u003e3.5. Comparison of\u003c/em\u003e MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH \u003cem\u003ewith previously reported catalysts for the Hantzsch reaction\u003c/em\u003e\u003c/h2\u003e\n \u003cp\u003eThe performance of the MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst was compared with that of catalysts reported in literature for the unsymmetrical Hantzsch reaction (Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e). It is found that MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst is superior to the majority of the reported catalysts in terms of cost-effectiveness, simplicity, short reaction time, amount of catalyst, type of solvent, and mild conditions.\u003c/p\u003e\u0026nbsp;\u003ctable border=\"1\" id=\"Tab3\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eComparison of the proposed catalyst with reported catalysts for the unsymmetrical Hantzsch reaction.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCatalyst\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eAmount\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eTime (min)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSolvent\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eTemp.\u003c/p\u003e\n \u003cp\u003e(°C)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eYield (%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eRef.\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eSBA-15@Glycine-Cu\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e80 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEthanol\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e96\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e(16)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@SiO\u003csub\u003e2−\u003c/sub\u003e/ZnCl\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e110\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e90\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e(17)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eMCM-41@PDCA-C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e100\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e(22)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eIRMOF-3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e4 mol%\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e91\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e(61)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eMoO\u003csub\u003e3\u003c/sub\u003e promotedCeO\u003csub\u003e2\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e200 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e45\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eEthanol\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ereflux\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e93\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e(62)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eFe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@MCM-41@Cu-P2C\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e20 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e200\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003ePEG\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e80\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e92\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e(63)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eMSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e10 mg\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e94\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eOur work\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eCNH grown on MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e surface was fabricated and utilized as a recoverable and powerful nanocatalyst for the one-pot construction of polyhydroquinolines in 15 min with a quantity of catalyst 10 mg at 50\u0026deg;C under solvent-free conditions. The exceptional performance of MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst can be attributed to the acid-base sites synergistic catalysis present in the catalyst. MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH was straightforwardly recovered and reused six times with a slight reduction in the catalytic activity. The benefits of using MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH catalyst include the low amount of catalyst, short reaction time, and solvent-free media.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eH. Yazdani, S. E. Hooshmand, M. H. Stenzel, Fusion of Cellulose and multicomponent reactions: benign by design, \u003cem\u003eACS Sustain. Chem. Eng\u003c/em\u003e. 2022, 10, 4359-4373.\u003c/li\u003e\n\u003cli\u003eM. Wang, C. Lv, C. Hu, Z. Su, Origin of enantioselectivity and product-distribution control in isocyanide-based multicomponent reaction catalysed by chiral N,N\u0026apos;-dioxide-Mg(II) complex, \u003cem\u003eMol. Catal\u003c/em\u003e. 2022, 524, 112277.\u003c/li\u003e\n\u003cli\u003eP.-L. Wang, S.-Y. Ding, Z.-C. Zhang, Z.-P. Wang, W. Wang, Constructing robust covalent organic frameworks via multicomponent reactions, \u003cem\u003eJ. Am. Chem. Soc\u003c/em\u003e. 2019, 141, 18004-18008.\u003c/li\u003e\n\u003cli\u003eN. Lohmann, V. Milovanovic, D. G. Piekarski, O. G. Mancheno, Metal-free oxoammonium salt-mediated C(sp\u003csup\u003e3\u003c/sup\u003e)-H oxidative Ugi-azide multicomponent reaction, \u003cem\u003eOrg. Biomol. Chem\u003c/em\u003e. 2022, 20, 2896-2908.\u003c/li\u003e\n\u003cli\u003eG. A. Coppola, S. Pillitteri, E. V. Van der Eycken, S.-L. You, U. K. Sharma, Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency, \u003cem\u003eChem. Soc. Rev\u003c/em\u003e. 2022, 51, 2313-2382.\u003c/li\u003e\n\u003cli\u003eA. R. Liandi, A. H. Cahyana, R. T. Yunarti, T. P. Wendari, Facile synthesis of magnetic Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@Chitosan nanocomposite as environmentally green catalyst in multicomponent Knoevenagel-Michael domino reaction, \u003cem\u003eCeram. Int\u003c/em\u003e. 2022, 48, 20266-20274.\u003c/li\u003e\n\u003cli\u003eP. S. G. Nunes, H. D. A. Vidal, A. G. Correa, Recent advances in catalytic enantioselective multicomponent reactions, \u003cem\u003eOrg. Biomol. Chem\u003c/em\u003e. 2020, 18, 7751-7773.\u003c/li\u003e\n\u003cli\u003eS. Yu, J. Wu, H. Lan, L. Gao, H. Qian, K. Fan, Z. Yin, Palladium and br\u0026oslash;nsted acid co-catalyzed biginelli-like multicomponent reactions via in situ-generated cyclic enol ether: access to spirofuran-hydropyrimidinones, \u003cem\u003eOrg. Lett\u003c/em\u003e. 2020, 22, 102-105.\u003c/li\u003e\n\u003cli\u003eJ. Wang, S. Zhu, Y. Liu, X. Zhu, K. Shi, X. Li, S. Zhu, Microwave-assisted multicomponent reaction: An efficient synthesis of indolyl substituted and spiroxindole pyrido[2,3-d]pyrimidine derivatives, \u003cem\u003eSynth. Commun\u003c/em\u003e. 2022, In Press.\u003c/li\u003e\n\u003cli\u003ePreeti, K. N. Singh, Metal-free multicomponent reactions: a benign access to monocyclic six-membered N-heterocycles, \u003cem\u003eOrg. Biomol. Chem\u003c/em\u003e. 2021, 19, 2622-2657.\u003c/li\u003e\n\u003cli\u003eN. H. Sapariya, B. K. Vaghasiya, R. P. Thummar, R. D. Kamani, K. H. Patel, P. Thakor, S. S. Thakkar, A. Ray, D. K. Raval, Synthesis, characterization, in silico molecular docking study and biological evaluation of a 5-(phenylthio) pyrazole based polyhydroquinoline core moiety, \u003cem\u003eNew J. Chem\u003c/em\u003e. 2017, 41, 10686-10694.\u003c/li\u003e\n\u003cli\u003eD. da Costa Cabrera, S. B. Rosa, F. Saes de Oliveira, M. A. G. Marinho, C. R. Montes DOca, D. Russowsky, A. P. Horn, M. G. Montes DOca, Synthesis and antiproliferative activity of novel hybrid 3-substituted polyhydroquinoline-fatty acids, \u003cem\u003eMed. Chem. Commun\u003c/em\u003e. 2016, 7, 2167-2176.\u003c/li\u003e\n\u003cli\u003eR. R. Raslan, S. A. Hessein, S. A. Fouad, N. A. M. Shmiess, Synthesis and antitumor evaluation of some new thiazolopyridine, nicotinonitrile, pyrazolopyridine, and polyhydroquinoline derivatives using ceric ammonium nitrate as a green catalyst, \u003cem\u003eJ Heterocyclic Chem\u003c/em\u003e. 2022, 59, 832-846.\u003c/li\u003e\n\u003cli\u003eK. Venkatapathy, C. J. Magesh, G. Lavanya, P. T. Perumal, S. Prema, Design, synthesis, molecular docking, and spectral studies of new class of carbazolyl polyhydroquinoline derivatives as promising antibacterial agents with noncytotoxicity towards human mononuclear cells from peripheral blood, \u003cem\u003eJ Heterocyclic Chem\u003c/em\u003e. 2020, 57, 1936-1955.\u003c/li\u003e\n\u003cli\u003eV. T. Nguyen, H. T. Nguyen, P. H. Tran, One-pot three-component synthesis of 1-amidoalkyl naphthols and polyhydroquinolines using a deep eutectic solvent: a green method and mechanistic insight, \u003cem\u003eNew J. Chem\u003c/em\u003e. 2021, 45, 2053-2059.\u003c/li\u003e\n\u003cli\u003eT. Tamoradi, A. Ghorbani-Choghamarani, M. Ghadermazi, H. Veisi, SBA-15@Glycine-M (M= Ni and Cu): Two green, novel and efficient catalysts for the one-pot synthesis of 5-substituted tetrazole and polyhydroquinoline derivatives, \u003cem\u003eSolid State Sci\u003c/em\u003e. 2019, 91, 96-107.\u003c/li\u003e\n\u003cli\u003eB. Maleki, H. Alinezhad, H. Atharifar, R. Tayebee, A. Vedad Mofrad, One-Pot Synthesis of Polyhydroquinolines Catalyzed by ZnCl\u003csub\u003e2\u003c/sub\u003e Supported on Nano Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@SiO\u003csub\u003e2\u003c/sub\u003e, \u003cem\u003eOrg. Prep. Proced. Int\u003c/em\u003e. 2019, 51, 301-309.\u003c/li\u003e\n\u003cli\u003eI. Sehout, R. Boulcina, B. Boumoud, T. Boumoud, A. Debache, Solvent-free synthesis of polyhydroquinoline and 1,8-dioxodecahydroacridine derivatives through the Hantzsch reaction catalyzed by a natural organic acid: A green method, \u003cem\u003eSynth. Commun\u003c/em\u003e. 2017, 47, 1185-1191.\u003c/li\u003e\n\u003cli\u003eG. Rathee, S. Kohli, S. Panchal, N. Singh, A. Awasthi, S. Singh, A. Singh, S. Hooda, R. Chandra, Fabrication of a gold-supported NiAlTi-layered double hydroxide nanocatalyst for organic transformations, \u003cem\u003eACS Omega\u003c/em\u003e 2020, 5, 23967-23974.\u003c/li\u003e\n\u003cli\u003eM. Rahmati, H. Ghafuri, N. Ghanbari, Z. Tajik, 1,4 Butanesultone functionalized graphitic carbon nitride: efficient catalysts for the one-pot synthesis of 1,4-dihydropyridine and polyhydroquinoline derivative through hantzsch reaction, \u003cem\u003ePolycycl. Aromat. Comp\u003c/em\u003e. 2022, In Press.\u003c/li\u003e\n\u003cli\u003eE. Zare, Z. Rafiee, Magnetic chitosan supported covalent organic framework/copper nanocomposite as an efficient and recoverable catalyst for the unsymmetrical hantzsch reaction, \u003cem\u003eJ. Taiwan. Inst. Chem. Eng\u003c/em\u003e. 2020, 116, 205-214.\u003c/li\u003e\n\u003cli\u003eS. Sharma, U. P. Singh, A. P. Singh, Synthesis of MCM-41 supported cobalt (II) complex for the formation of polyhydroquinoline derivatives, \u003cem\u003ePolyhedron\u003c/em\u003e, 2021, 199, 115102.\u003c/li\u003e\n\u003cli\u003eS. Rathod, V. Dhage, M. Lande, An eco-friendly synthesis of polyhydroquinoline derivatives using MoO\u003csub\u003e3\u003c/sub\u003e promoted CeO\u003csub\u003e2\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e solid heterogeneous catalyst, \u003cem\u003eMater. Today: Proc. \u003c/em\u003e2021, 47, 1736-1740.\u003c/li\u003e\n\u003cli\u003eM. Roozifar, N. Hazeri, H. Faroughi Niya, Application of salicylic acid as an eco-friendly and efficient catalyst for the synthesis of 2,4,6-triaryl pyridine, 2-amino-3-cyanopyridine, and polyhydroquinoline derivatives, \u003cem\u003eJ. Heterocyclic Chem\u003c/em\u003e. 2021, 58, 1117-1129.\u003c/li\u003e\n\u003cli\u003eH. Aghahosseini, M. R. Ranjbar, A. Ramazani, Simple and efficient synthesis of guanidine-based magnetic nanocatalyst for the one-pot, four-component synthesis of polyhydroquinolines in water, \u003cem\u003eChemistrySelect\u003c/em\u003e 2020, 5, 8415-8420.\u003c/li\u003e\n\u003cli\u003e\u003cspan dir=\"RTL\"\u003e \u003c/span\u003eQ. Zhang, X. Yang, J. Guan, Applications of magnetic nanomaterials in heterogeneous catalysis, \u003cem\u003eACS Appl. Nano Mater\u003c/em\u003e. 2019, 2, 4681-4697.\u003c/li\u003e\n\u003cli\u003eP. Bhanja, A. Modak, A. Bhaumik, Supported porous nanomaterials as efficient heterogeneous catalysts for CO\u003csub\u003e2\u003c/sub\u003e fixation reactions, \u003cem\u003eChem. Eur. J\u003c/em\u003e. 2018, 24, 7278-7297.\u003c/li\u003e\n\u003cli\u003eK. Shen, X. Chen, J. Chen, Y. Li, Development of MOF-derived carbon-based nanomaterials for efficient catalysis, \u003cem\u003eACS Catal\u003c/em\u003e. 2016, 6, 9, 5887-5903.\u003c/li\u003e\n\u003cli\u003eJ. G. Croissant, X. Cattoen, J.-O. Durand, M. W. C. Man, N. M. Khashab, Organosilica hybrid nanomaterials with a high organic content: syntheses and applications of silsesquioxanes, \u003cem\u003eNanoscale\u003c/em\u003e 2016, 8, 19945-19972\u003c/li\u003e\n\u003cli\u003eY. Chen, Z. Fan, Z. Zhang, W. Niu, C. Li, N. Yang, B. Chen, H. Zhang, Two-dimensional metal nanomaterials: synthesis, properties, and applications, \u003cem\u003eChem. Rev\u003c/em\u003e. 2018, 118, 6409-6455.\u003c/li\u003e\n\u003cli\u003e\u003cspan dir=\"RTL\"\u003e \u003c/span\u003eJ. Huang, X. Tan, C. Li, R. Wu, Shuqin Ran, Yuxin Tao, and Tong Mou, Green synthesis of Au-NPs on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e hybrid nanomaterials based on supramolecular pillar[6]arene and its applications for catalysis, \u003cem\u003eACS Omega\u003c/em\u003e 2022, 7, 18085-18093.\u003c/li\u003e\n\u003cli\u003eF. Hassanzadeh-Afruzi, H. Dogari, F. Esmailzadeh, A. Maleki, Magnetized melamine-modified polyacrylonitrile (PAN@melamine/Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e) organometallic nanomaterial: Preparation, characterization, and application as a multifunctional catalyst in the synthesis of bioactive dihydropyrano [2,3-c]pyrazole and 2-amino-3-cyano 4H-pyran derivatives, \u003cem\u003eAppl. Organomet. Chem.\u003c/em\u003e 2021, 35, e6363.\u003c/li\u003e\n\u003cli\u003eM. Khalil, G. T.M. Kadj, M. Muallifu lIlmi, Advanced nanomaterials for catalysis: Current progress in fine chemical synthesis, hydrocarbon processing, and renewable energy, \u003cem\u003eJ. Ind. Eng. Chem\u003c/em\u003e. 2021, 93, 78-100.\u003c/li\u003e\n\u003cli\u003eZ. Rafiee, Fabrication of efficient Zn-MOF/COF catalyst for the Knoevenagel condensation reaction, \u003cem\u003eJ. Iran. Chem. Soc\u003c/em\u003e. 2021, 18, 2657-2664.\u003c/li\u003e\n\u003cli\u003eA. Arabmarkadeh, R. Javahershenas, M. Kazemi, Nanomaterials: Catalysis in synthesis of highly substituted heterocycles, \u003cem\u003eSynth. Commun\u003c/em\u003e. 2021, 51, 880-903.\u003c/li\u003e\n\u003cli\u003eA. D. Kute, R. P. Gaikwad, I. R. Warkad, M. B. Gawand, A review on the synthesis and applications of sustainable copper-based nanomaterials, \u003cem\u003eGreen Chem\u003c/em\u003e. 2022, 24, 3502-3573.\u003c/li\u003e\n\u003cli\u003eRecent advances in the synthesis of various analogues of MOF-based nanomaterials: A mini-review, K. O. Otun, S. O. Amusat, I. T. Bello, J. Abdulsalam, A. T. Ajiboye, A. A. Adeleke, S. O. Azeez, \u003cem\u003eInorg. Chim. Acta\u003c/em\u003e 2022, 120890.\u003c/li\u003e\n\u003cli\u003eA. Villa, M. Schiavoni, L. Prati, Material science for the support design: a powerful challenge for catalysis, \u003cem\u003eCatal. Sci. Technol\u003c/em\u003e. 2012, 2, 673-682.\u003c/li\u003e\n\u003cli\u003eX. Sui, L. Zhang, J. Li, K. Doyle-Davis, R. Li, Z. Wang, X. Sun, Advanced support materials and interactions for atomically dispersed noble-metal catalysts: from support effects to design strategies, \u003cem\u003eAdv. Energy Mater\u003c/em\u003e. 2022, 12, 2102556.\u003c/li\u003e\n\u003cli\u003e\u003cspan dir=\"RTL\"\u003e \u003c/span\u003eJ. C. S. Terra, A. Moores, F C. C. Moura, Amine-functionalized mesoporous silica as a support for on-demand release of copper in the A\u003csup\u003e3\u003c/sup\u003e-coupling reaction: Ultralow concentration catalysis and confinement effect, \u003cem\u003eACS Sustain. Chem. Eng\u003c/em\u003e. 2019, 7, 9, 8696-8705.\u003c/li\u003e\n\u003cli\u003e\u003cspan dir=\"RTL\"\u003e \u003c/span\u003eA\u003cspan dir=\"RTL\"\u003e.\u003c/span\u003e Saad, C\u003cspan dir=\"RTL\"\u003e.\u003c/span\u003e Vard, M\u003cspan dir=\"RTL\"\u003e.\u003c/span\u003e Abderrabba, M\u003cspan dir=\"RTL\"\u003e.\u003c/span\u003e M. Chehimi, Triazole/triazine-functionalized mesoporous silica as a hybrid material support for palladium nanocatalyst, \u003cem\u003eLangmuir\u003c/em\u003e 2017, 33, 28, 7137-7146.\u003c/li\u003e\n\u003cli\u003eS. Thomas, T. A. Nguyen, M. Ahmadi, G. Yasin, N. Joshi, Silicon-based hybrid nanoparticles fundamentals, properties, and applications, Elsevier, 2022.\u003c/li\u003e\n\u003cli\u003eN. Pal, J.-H. Lee, E.-B. Cho, Recent trends in morphology-controlled synthesis and application of mesoporous silica nanoparticles, \u003cem\u003eNanomaterials \u003c/em\u003e2020, 10, 2122.\u003c/li\u003e\n\u003cli\u003eW. Gao, Y. Wang, F. Zhang, S. Zhang, H.-Z. Lian, Tetrasulfonate calix[4]arene modified large pore mesoporous silica microspheres: Synthesis, characterization, and application in protein separation, \u003cem\u003eTalanta\u003c/em\u003e 2021, 226, 122171.\u003c/li\u003e\n\u003cli\u003eJ. Huang, H.-B. Liu, J. Wang, Functionalized mesoporous silica as a fluorescence sensor for selective detection of Hg\u003csup\u003e2+\u003c/sup\u003e in aqueous medium, \u003cem\u003eSpectrochim. Acta A Mol. Biomol. Spectrosc\u003c/em\u003e. 2021, 246, 118974.\u003c/li\u003e\n\u003cli\u003eJ. O. Otalvaro, T. R. Alvarez, M. S. V. Gurovic, V. Lassalle, M. Agotegaray, M. Avena, M. Brigante, Magnetic mesoporous silica nanoparticles for drug delivery systems: Synthesis, characterization and application as norfloxacin carrier, \u003cem\u003eJ. Pharm. Sci\u003c/em\u003e. 2022, In Press.\u003c/li\u003e\n\u003cli\u003eA. A. Sosa, V. Palermo, P. Langer, R. Luque, G. P. Romanelli, L. R. Pizzio, Tungstophosphoric acid/mesoporous silicas as suitable catalysts in quinoxaline synthesis, \u003cem\u003eMol. Catal\u003c/em\u003e. 2022, 517, 112046.\u003c/li\u003e\n\u003cli\u003eJ. Zhu, P. Xiao, H. Li, S. A. C. Carabineiro, Graphitic carbon nitride: Synthesis, properties, and applications in catalysis, \u003cem\u003eACS Appl. Mater. Interfaces\u003c/em\u003e 2014, 6, 16449-16465.\u003c/li\u003e\n\u003cli\u003eM. Ismael, A review on graphitic carbon nitride (g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e) based nanocomposites: Synthesis, categories, and their application in photocatalysis, \u003cem\u003eJ. Alloys Compd\u003c/em\u003e. 2020, 846, 15644.\u003c/li\u003e\n\u003cli\u003eV V. Phatake, B. M. Bhanage, Cu@U-g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e catalyzed cyclization of o-phenylenediamines for the synthesis of benzimidazoles by using CO\u003csub\u003e2\u003c/sub\u003e and dimethylamine borane as a hydrogen source, \u003cem\u003eCatal. Lett\u003c/em\u003e. 2019, 149, 347-359\u003cspan dir=\"RTL\"\u003e.\u003c/span\u003e\u003c/li\u003e\n\u003cli\u003eH. Veisi, P. Mohammadi, T. Ozturk, Design, synthesis, characterization, and catalytic properties of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e-SO\u003csub\u003e3\u003c/sub\u003eH as an efficient nanosheet ionic liquid for one-pot synthesis of pyrazolo[3,4-b]pyridines and bis(indolyl)methanes, \u003cem\u003eJ. Mol. Liq\u003c/em\u003e. 2020, 303, 112625.\u003c/li\u003e\n\u003cli\u003eN. Kong, X. Fan, F. Liu, L. Wang, H. Lin, Y. Li, S.-T. Lee, Single vanadium atoms anchored on graphitic carbon nitride as a high-performance catalyst for non-oxidative propane dehydrogenation, \u003cem\u003eACS Nano\u003c/em\u003e 2020, 14, 5772-5779\u003cspan dir=\"RTL\"\u003e.\u003c/span\u003e\u003c/li\u003e\n\u003cli\u003eI. Camussi, B. Mannucci, A. Speltini, A. Profumo, C. Milanese, L. Malavasi, P. Quadrelli, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e- Singlet oxygen made easy for organic synthesis: scope and limitations, \u003cem\u003eACS Sustainable Chem. Eng\u003c/em\u003e. 2019, 7, 8176-8182.\u003c/li\u003e\n\u003cli\u003eM. L. Ur Rehman, Q. Hou, X. Bai, Y. Nie, H. Qian, T. Xia, R. Lai, G. Yu, M. Ju, Regulating the alkalinity of carbon nitride by magnesium doping to boost the selective isomerization of glucose to fructose, \u003cem\u003eACS Sustainable Chem. Eng\u003c/em\u003e. 2022, 10, 1986-1993.\u003c/li\u003e\n\u003cli\u003eY. Gong, M. Li, H. Li, Y. Wang, Graphitic carbon nitride polymers: promising catalysts or catalyst supports for heterogeneous oxidation and hydrogenation, \u003cem\u003eGreen Chem\u003c/em\u003e. 2015, 17, 715-736.\u003c/li\u003e\n\u003cli\u003eBing-Cheng Li, Jechan Lee, Eilhann Kwon, Bui Xuan Thanh, Jia-Yin Lin, Siming You, Chia-Hua Lin, Kun-Yi Andrew Lin, 2-Dimensional nanoleaf-like porous copper nitrate hydroxide as an effective heterogeneous catalyst for selective oxidation of hydroxymethylfurfural to diformylfuran, \u003cem\u003eJ. Taiwan. Inst. Chem. Eng\u003c/em\u003e. 2021, 126, 189-196.\u003c/li\u003e\n\u003cli\u003eB. Liu, One-dimensional copper hydroxide nitrate nanorods and nanobelts for radiochemical applications, \u003cem\u003eNanoscale\u003c/em\u003e, 2012, 4, 7194-7198.\u003c/li\u003e\n\u003cli\u003eB.-C.Li, N. N. Huy, J.-Y. Lin, S. Phattarapattamawong, G. Lisak, H. Wang, K.-Y. Andrew Lin, Nanopetal-like copper hydroxide nitrate as a highly selective heterogeneous catalyst for valorization of vanillic alcohol via oxidation, \u003cem\u003eJ. Environ. Chem. Eng\u003c/em\u003e. 2021, 9, 106092.\u003c/li\u003e\n\u003cli\u003eH. Niu, Q. Yang, K. Tang, A new route to copper nitrate hydroxide microcrystals, \u003cem\u003eMater. Sci. Eng. B\u003c/em\u003e 2006, 135, 172-175.\u003c/li\u003e\n\u003cli\u003eE. K. Guner, A. Ozer, Synthesis and characterization of copper hydroxynitrate and copper oxide by hydrothermal method, \u003cem\u003eJ. Turkish chem. Soc.\u003c/em\u003e 2017, 1, 183-192.\u003c/li\u003e\n\u003cli\u003eS. Rostamnia, H. Xin Basic isoreticular metal-organic framework (IRMOF-3) porous nanomaterial as a suitable and green catalyst for selective unsymmetrical Hantzsch coupling reaction, \u003cem\u003eAppl. Organomet. Chem\u003c/em\u003e. 2014, 28, 359-363.\u003c/li\u003e\n\u003cli\u003eS. Rathod, V. Dhage, M. Lande, An eco-friendly synthesis of polyhydroquinoline derivatives using MoO\u003csub\u003e3\u003c/sub\u003e promoted CeO\u003csub\u003e2\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e solid heterogeneous catalyst, \u003cem\u003eMater. Today: Proc. \u003c/em\u003e2021, 47, 1736-1740.\u003c/li\u003e\n\u003cli\u003eM. Nikoorazm, Z. Erfani, Core-shell nanostructure (Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@MCM-41@Cu-P2C) as a highly efficient and recoverable nanocatalyst for the synthesis of polyhydroquinoline, 5-substituted 1H-tetrazoles and sulfides, \u003cem\u003eChem. Phys. Lett\u003c/em\u003e. 2019, 737, 136784.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Scheme 1","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Mesoporous silica, Copper nitrate hydroxide, C3N4, Nanocomposite, Hantzsch reaction","lastPublishedDoi":"10.21203/rs.3.rs-2064047/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-2064047/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eCopper nitrate hydroxide (CNH)-containing mesoporous silica nanoparticle (MSN) with g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e framework (MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH) was fabricated via a four-step hydrothermal synthesis method. Functionalized MSN-based C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e was prepared, decorated with CNH, and identified by different physicochemical techniques such as FT-IR, XRD, SEM, EDX, and STA analyses. Then, MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH composite was utilized as a robust catalyst for the fast fabrication of biologically active polyhydroquinoline derivatives with high yields between 88 and 97% via Hantzsch reaction under mild reaction conditions and short reaction time (within 15 min) owing to synergistic influence of Lewis acid and base sites. Moreover, MSN/C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/CNH can be straightforwardly recovered and used up to six reaction cycles without a conspicuous decrease in efficiency.\u003c/p\u003e","manuscriptTitle":"Hantzsch Reaction using Copper Nitrate Hydroxide- Containing Mesoporous Silica Nanoparticle with C 3 N 4 Framework as A Novel Powerful and Reusable Catalyst","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2022-09-21 22:01:12","doi":"10.21203/rs.3.rs-2064047/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Major revision","date":"2022-12-09T03:47:44+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2022-10-31T13:02:46+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"38119560-164f-4558-84f2-fa63f82f1619","date":"2022-10-21T03:15:11+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2022-10-12T03:34:48+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2022-10-06T10:08:48+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"90075da3-c803-4377-811a-16202b70d526","date":"2022-09-21T08:58:37+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"7bd7b791-fc6b-4612-9e0f-04d10ecbdc30","date":"2022-09-20T06:19:18+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2022-09-19T12:58:20+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2022-09-19T12:53:15+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2022-09-19T12:32:39+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2022-09-19T12:18:15+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2022-09-14T08:48:39+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"e928dd38-72c8-4348-9004-e73168639c58","owner":[],"postedDate":"September 21st, 2022","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2023-10-16T21:31:09+00:00","versionOfRecord":{"articleIdentity":"rs-2064047","link":"https://doi.org/10.1038/s41598-023-36059-7","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2023-06-12 21:12:18","publishedOnDateReadable":"June 12th, 2023"},"versionCreatedAt":"2022-09-21 22:01:12","video":"","vorDoi":"10.1038/s41598-023-36059-7","vorDoiUrl":"https://doi.org/10.1038/s41598-023-36059-7","workflowStages":[]},"version":"v1","identity":"rs-2064047","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-2064047","identity":"rs-2064047","version":["v1"]},"buildId":"rHA-KDH7Qsr4HCuvH75dn","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}