Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Nano-SiO2/DBN: an efficacious and reusable catalyst for one-pot synthesis of tetrahydrobenzo[b]pyran derivatives

Nano-SiO2/DBN: an efficacious and reusable catalyst for one-pot synthesis of... Background: The nano-sized particles enhance the exposed surface area of the active part of the catalyst, thereby increasing the contact between precursors and catalyst considerably. In this study, nano-SiO /1,5-diazabicy- clo[4.3.0]non-5-en was synthesized, characterized and used as a heterogeneous nanocatalyst for the synthesis of tetrahydrobenzo[b]pyran derivatives. Fourier Transform Infrared Spectroscopy, Field Emission Scanning Electron Microscopy, Brunauer–Emmett–Teller plot, Energy Dispersive X-ray Spectroscopy and Thermo Gravimetric Analysis were used to discern nano-SiO /1,5-diazabicyclo[4.3.0]non-5-en. Results: Tetrahydrobenzo[b]pyrans were synthesized by using nano-SiO /1,5-diazabicyclo[4.3.0]non-5-en via one-pot three-component condensation of malononitrile, aldehydes and dimedone in H O/EtOH at 60 °C. The results indicate that tetrahydrobenzo[b]pyrans were synthesized in good to high yields and short reaction times. Conclusions: The fundamental privileges of this method are short reaction time, plain procedure, recyclability of catalyst and high yields of products. Keywords: Nano-SiO /DBN, Benzopyrans, Heterogeneous catalyst, Multicomponent reaction, Nano-silica Introduction and hypotensive antiviral [11]. Some pharmacologically Multi-component reactions (MCRs) have significant role and biologically active benzopyrans are shown in Fig. 1. in organic chemistry, because of some merits like selec- A suitable method for synthesis of benzopyrans is tivity, synthetic convergence, high atom economy, sim- three-component condensation of malononitrile and plicity, short reaction time, facility of workup, synthetic dimedone with various aldehydes. This reaction has been efficiency and high yield of products [1, 2]. An efficient investigated in the presence of various catalysts such a way for the synthesis of heterocyclic compounds is using Fe O @SiO @NiSB [12], oxyammonium-based ionic 3 4 2 multi-component reactions, which have great value in liquid [13], WEMFSA [14], [Bmim]Sac [15], MNPs– design of biologically new active compounds [1, 3–5]. PhSO H [16], NH @SiO @Fe O MNPs [17], choline 3 2 2 3 4 Tetrahydrobenzo[b]pyrans as one of the significant chloride-oxalic acid [18], SCMNPs@PC/VB1-Zn [19], group of oxygen-containing heterocycle compounds are MMWCNTs-D-(CH )4-SO H [20] and Chlorophyll 2 3 highly considered due to their medicinal and biological [21]. In this research a practical, simple and inexpensive properties such as spasmolytic [6], antitumor [7], anti- procedure for the synthesis of tetrahydrobenzo[b]pyran bacterial [8], anti HIV [9], insulin-sensitizing activity [10] derivatives is reported by the reaction of aldehydes, malononitrile and dimedone in the presence of catalytic amount of nano-silica supported 1,5-diazabicyclo[4.3.0] *Correspondence: fmirjalili@yazd.ac.ir non-5-en (Nano-SiO /DBN). Moreover, the amount of Department of Chemistry, College of Science, Yazd University, Yazd, Iran Full list of author information is available at the end of the article catalyst used in the reaction and its effect on the product © The Author(s) 2021. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/. The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Mehravar et al. BMC Chemistry (2021) 15:34 Page 2 of 10 Fig. 1 Selected examples of pharmacologically and biologically active benzopyrans yields, as well as the ability to recovery have been studied. the 2θ range from 10° to 80°. Thermo gravimetric analy - Inexpensive and readily available catalyst, easy work-up sis (TGA) was accomplished using a STA 505 instrument and high yield of the products, usage of environmen- under argon atomosphere. The BET surface area, pore tally benign solvents, short reaction times and simplicity size and pore volume were measured by using Tristar II of experimental procedure are some advantages of this 3020 analyzer. Melting points were recorded on a Buchi procedure. B-540 B. V. CHI apparatus. Energy Dispersive X-ray Spectroscopy (EDS) was measured by Phenom pro X. Experimental Materials and methods Chemistry General General procedure for  synthesis of  tetrahydrobenzo[b] Whole reagents and solvent were procured from Merck, pyran derivatives Nano-SiO /DBN (0.03  g) as a nano- Aldrich and fluka chemical companies. Fourier transform catalyst was combined with a mixture of dimedone infrared spectroscopy (FT-IR) (ATR or KBr pellets) was (1  mmol), aromatic and aliphatic aldehyde (1  mmol), run on a Bruker, Eqinox 55 spectrometer. The nanopar - malononitrile (1 mmol) in a round bottom flask and then ticles size and catalyst morphology were ascertained at the mixture was stirred magnetically in H O/EtOH (1:1) Field emission scanning electron microscope (FE-SEM) at 60 °C. The advancement of the reaction was controlled using a Mira 3-XMU. Proton nuclear magnetic resonance by TLC (n-hexane–ethyl acetate, 3:1). When the reaction 1 13 ( H NMR) and carbon nuclear magnetic resonance ( C was over, the catalyst was separated and recovered for the NMR) spectra were record at Bruker (DRX-400 Avance) next run. Then, the crude products were recrystallized in in DMSO-d as the solvent. The crystallographic char - EtOH. acteristics of the sample were obtained by X-ray diffrac - tometer (XRD, Philips Xpert) using Ni-filtered CuKα Procedure for  synthesis of  silica chloride Thionyl chlo - (kCuK = 0.1542  nm, radiation at 40  kV and 30  Ma) in ride (40 mL) (toxic and should be used under ventilator) M ehravar et al. BMC Chemistry (2021) 15:34 Page 3 of 10 and nano-silicagel (10 g) were added to a round bottomed which is dried, reacted with DBN in n‑hexane  under flask (250  mL) provided with a condenser under reflux reflux condition. The chlorine atoms in nano-silica condition for 48 h. Then it was cooled to room tempera - chloride were replaced with N-nucleophiles in DBN ture, the mixture of reaction was filtrated via a Buchner (Scheme1). funnel, then the remainder was rinsed several times with Figure  2a–c shows the FT-IR spectra of the synthe- dichloromethane. Finally, obtained sillica chloride was sized materials. Figure  2d shows absorption band at −1 dried at ambient temperature.3397  cm which is due to the SiO–H stretching vibra- −1 tion, 1652  cm for the C=N stretching vibration and −1 −1 Procedure for  synthesis of  nano‑SiO /DBN Silica chlo-1056  cm for Si–O stretching vibration and 796  cm ride (1 g), DBN (1.5 mL) and n-hexane (10 mL) were added due to the Si–O–Si bending vibrational mode. to a round bottomed flask (100 mL) furnished with a con - Energy-dispersive X-ray spectroscopy (EDS) was used denser, under reflux conditions for 15  h. When reaction to determine the percentage of elements in nano-SiO / was completed, it was cooled, filtrated and rinsed three DBN (Fig.  3). The percentage of C, N, O, Si and Cl in times with n-hexane. Finally, the nano-SiO /DBN catalyst nano-SiO /DBN was 10.75, 4.88, 47.38, 36.48 and 0.25 2 2 was dehydrated at ambient temperature in open air. respectively. The EDX-map of elements in the structure of nano- Results and discussion SiO /DBN (Fig.  4) displays homogenous distribution of A new catalyst was prepared as nano-SiO /DBN in two elements in catalyst. steps. At first, a mixture of thionyl chloride and com - The particle size of nano-SiO /DBN was studied using mercial nano-silica gel was stirred for 48  h under reflux field emission scanning electron microscopy (FESEM) condition to carry out nano-silica chloride. In this reac- and found to be less than 50 nm (Fig. 5). tion, OH functional groups of silica gel were replaced by TGA analysis is shown in Fig.  6A, which exhibits the Cl atoms of thionyl chloride. Then, nano-silica chloride, stability of the nano-SiO /DBN as nano-catalyst which can be used up to 120  °C. The weight loss (4.2%) below 100 °C is likely due to the loss of catalyst moisture. How- ever, the main decomposition occurs at 165–450  °C (20.7%). Nano-SiO /DBN has noticeably high thermal stability with char yield 68.72% at 800 °C. Figure  6B display the XRD Patterns of nano-SiO , nano-SiO /DBN in the range of 10–80°. A broad peak (Fig.  6B (a)) is observed at 2θ = 23°, showing the SiO is Scheme 1 The preparation protocol for nano-SiO /DBN 2 2 Fig. 2 FT-IR spectra of a Nano-SiO , b nano-silica chloride, c DBN, d nano-SiO /DBN 2 2 Mehravar et al. BMC Chemistry (2021) 15:34 Page 4 of 10 Fig. 3 The EDX spectra of nano-SiO /DBN Fig. 4 EDX-map of elements in the structure of nano-SiO /DBN 2 M ehravar et al. BMC Chemistry (2021) 15:34 Page 5 of 10 Figure  7 shows (a) BJH plot, (b) BET (Brunauer– Emmett–Teller) plot, (c) t-plot, (d) Langmuir plot and (e) Adsorption/desorption isotherm of nano-SiO /DBN. The obtained data of BET, Langmuir, t and BJH plots were summarized in Table 1. To optimize the reaction conditions in the synthesis of tetrahydrobenzo[b]pyran, the one-pot three-compo- nent condensation reaction of 4-chlorobenzaldehyde, dimedone and malononitrile was investigated, as model reaction, for various factors such as the amount of nano- SiO /DBN, time, temperature and solvent (Table  2). Therefore, the best reaction condition was performed Fig. 5 FESEM images of nano-SiO /DBN using 0.03  g of catalyst in various solvents such as H O, 2 2 CHCl , MeOH, EtOH and H O/EtOH (Table  2, entries 3 2 1‒5). The use of H O/EtOH (1:1) as solvent at 60  °C is amorphous. While, the diffraction pattern of the nano- the most efficient condition for the model reaction with SiO /DBN (Fig.  6B (b)) indicated peak at 2θ = 23.525° high yield and short time (Table 2, entry 10). The reaction with FWHM = 2.3616. According to Scherrer equation, performed under solvent free conditions, gave a lower the particle size of catalyst is 3.4 nm. 120 0 -2 -4 -6 -8 T[ºC] -10 0200 400600 8001000 Fig. 6 (A) TGA patterns of nano-SiO /DBN and (B) XDR patterns of a) nano-SiO and b) nano-SiO /DBN 2 2 2 Langmuir-Plot BJH H-Plot B BET-Plot t-Plot 0.6 0.15 0.012 ADS 0.4 0.1 0.008 0.05 0.2 0.004 100 r /nm m p/p t/nm p/kPa p 0 0 0 0 0 1 10 100 0 0 1 2 0 45 90 0 0.250.5 ADS DES 45 50 30 00 15 50 p//p 0 0 0.5 1 Fig. 7 a BJH plot, b BET (Brunauer–Emmett–Teller) plot, c t-plot, d Langmuir plot and e adsorption/desorption isotherm of nano-SiO /DBN dV /dr p p rel.Quantity [%] 3 -1 V /cm (STP)g p/V (p -p) a 0 -1 V /cm (STP)g p p//V V a a Mehravar et al. BMC Chemistry (2021) 15:34 Page 6 of 10 Table 1 The summerized data of BET, Langmuir, t and BJH plots Table 2 The reaction of malononitrile, 4-chlorobenzaldehyde and dimedone in the presence of nano-SiO /DBN under various BET plot conditions 3 −1 V 49.439 [cm(STP) g ] 2 −1 a 215.18 [m g ] s,BET C 48.241 3 −1 Total pore volume (p/p = 0.990) 0.4823 [cm g ] Mean pore diameter 8.966 [nm] Langmuir plot 3 −1 Vm 47.372 [cm(STP) g ] 2 −1 a 206.18 [m g ] a s,Lang Entry Time (min) Yield (%) Conditions B 1.1678 Solvent/temp (°C)/catalyst (g) t plot 1 H O/EtOH (1:1)/60/‒ 180 28 Plot data Adsorption 2 H O/60/0.03 30 70 branch 3 EtOH/60/0.03 30 58 2 −1 a 362.85 [m g ] 4 CHCl /60/0.03 60 50 3 −1 V 0 [cm g ] 5 MeOH/60/0.03 60 70 2 −1 a 19.303 [m g ] 6 ‒/60/0.03 120 42 3 −1 V 0.3824 [cm g ] 7 ‒/80/0.03 90 58 2t 2.2126 [nm] 8 H O/EtOH (1:1)/r.t/0.03 15 10 BJH plot 9 H O/EtOH (1:1)/40/0.03 15 58 10 H O/EtOH (1:1)/60/0.03 15 92 Plot data Adsorption branch 11 H O/EtOH (1:1)/60/0.01 50 76 3 −1 12 H O/EtOH (1:1)/60/0.02 30 80 V 0.504 [cm g ] 13 H O/EtOH (1:1)/60/0.04 20 92 r (Area) 3.1 [nm] p,peak 2 −1 14 H O/EtOH (1:1)/60/0.05 35 70 a 290.06 [m g ] Reaction conditions: malononitrile (1 mmol), 4-chlorobenzaldehyde (1 mmol), dimedone (1 mmol) and nano-SiO /DBN as catalyst Isolated yield The modified condition yield in comparison with those performed in the solvent (Table 2, entries 6, 7). After determining the optimized condition, the reac- tion between different aldehydes with dimedone and malononitrile was investigated (Table  3). In result, A suggested mechanism for synthesis of tetrahydrobenzo[b]pyrans were synthesized in good to tetrahydrobenzo[b]pyran derivatives by using nano-SiO / high yields and short reaction times. The progress of DBN is illustrated in Scheme  2. Initially, the nano-SiO / reaction was monitored by TLC continuously. Mean- DBN catalyst activates both the methylene group 5 and while, the aldehydes with electron withdrawing group in the carbonyl group 1. After, the Knoevenagal condensa- 4-position have reacted in lower time with higher yields tion reaction between the malononitrile and aldehyde (Table 3, entries 2, 5, 8, 9, 10). The aldehydes with a sub - in existence of basic catalyst forms the intermediate 6. stitution group in 2-position, have steric hindrance which Then, the Michael addition of enol 4 and intermediate 6 caused longer reaction time (Table  3, entries 3, 4, 5) is performed to produce the intermediate 7. Finally, the (Additional file 1). product is formed by cyclization and tautomerization of As shown in Table  4, performance of synthesized the intermediate 8. catalyst compared to nano-SiO , DBN and previously The reusability of the nano-SiO /DBN was investigated. reported catalysts. Nano-SiO /DBN can be presented After completion of the reaction, the nanocatalyst was as an efficacious one, among others, catalyst in terms of separated and washed with some EtOH, then dried at reaction time and yields. There are many privileges in this 70 °C. The catalyst was regained in good yields and cata - regard simple procedure, nontoxic solvent and mild reac- lyst was used in the synthesis of tetrahydrobenzo[b]pyran tion conditions. DBN is a good catalyst for this reaction, for five times (Fig. 8). but is not a heterogeneous recoverable catalyst. M ehravar et al. BMC Chemistry (2021) 15:34 Page 7 of 10 Table 3 Synthesis of tetrahydrobenzo[b]pyran in the presence of nano-SiO /DBN at 60 ºC in H O/EtOH (1:1) 2 2 a b Entry R Product Time (min) Yield (%) M.P (°C) found M.P (°C) reported (refs.) 1 C H - 4a 20 85 232‒234 234‒235 [22] 6 5 2 4-Cl-C H - 4b 15 92 214‒216 215‒216 [22] 6 4 3 2-Cl–C H - 4c 35 81 217‒218 218‒219 [23] 6 4 4 2,6-Cl -C H - 4d 50 79 245‒247 250‒252 [23] 2 6 3 5 4-NO -C H - 4e 15 89 181‒183 181‒182 [27] 2 6 4 6 3-NO -C H - 4f 20 91 215‒217 217‒218 [27] 2 6 4 7 2-NO -C H - 4 g 35 80 232‒234 233‒234 [22] 2 6 4 8 4-Br-C H - 4 h 30 89 199‒201 197‒201 [13] 6 4 9 4-F-C H - 4i 40 91 192‒194 191‒193 [15] 6 4 10 4-CN-C H - 4j 25 85 231‒233 226‒228 [24] 6 4 11 4-OCH -C H - 4 k 25 70 208‒210 208‒212 [23] 3 6 4 12 3,4-(OCH ) -C H - 4 l 50 82 175‒176 206‒208 [25] 3 2 6 3 13 4-OH-C H - 4 m 40 78 217‒219 214‒216 [23] 6 4 14 4-(CH ) CH-C H - 4n 30 90 197‒199 203‒207 [13] 3 2 6 4 15 4-CO CH -C H - 4o 15 78 257‒259 259‒260 [27] 2 3 6 4 16 1,4-Phenylene 4p 50 91 285 (d) 270 (d) [26] 17 2-Furyl- 4q 25 84 216‒218 217‒219 [23] 18 Pentyl- 4r 20 83 162‒164 164‒165 [27] 19 Styryl- 4 s 30 90 217‒219 218‒218 [23] 4a-s are the synthesized tetrahydrobenzo[b]pyrans with different R Reaction conditions: malononitrile (1 mmol), aldehyde (1 mmol), dimedone (1 mmol) and nano-SiO /DBN (0.03 g) Isolated yield Decomposed Conclusion Table 4 Comparison of nano-SiO /DBN catalyst with some other catalyst for the synthesis of 4b We have reported one-pot three component condensa- tion reaction of various aldehydes, malononitrile and Entry Conditions Time (min) Yield (%) (refs.) dimedone at 60  °C under mild conditions. The novel Solvent/temp (ºC)/catalyst synthesis has been explored of tetrahydrobenzo[b] 1 CH Cl /60/SiO /NH OAc 360 90 [28] 2 2 2 2 pyran derivatives in the presence nano-SiO /DBN as a 2 H O/80/Fe O @SiO /DABCO 25 90 [29] 2 3 4 2 heterogeneous nanocatalyst. The synthesized nanocata - 3 EtOH /reflux/ l -Proline 360 87 [30] lyst was characterized by FT-IR, XRD, FESEM, TGA, 2− 4 EtOH /reflux/SO /MCM-41 60 80 [31] EDS and BET analysers. The advantages of this method 5 H O/reflux/DABCO 150 68 [32] are summarized in the following orders, inexpensive, 6 H O/120/SDS 120 85 [33] recyclability and reusability of the catalyst, easy work- 7 H O/60/Thiourea dioxide 13 93 [34] up and good yield of the products, the use of relatively a c 8 H O/EtOH/60/catalyst 15 92 (this work) environmentally benign solvents, short reaction times 9 H O/EtOH/60/nano-SiO 15 40 (this work) 2 2 and simplicity experimental of the procedure. 10 H O/EtOH/DBN 15 93 (this work) Nano-SiO /DBN Isolated yield The modified condition Mehravar et al. BMC Chemistry (2021) 15:34 Page 8 of 10 Scheme 2 The plausible mechanism for the synthesis of tetrahydrobenzo[b]pyran derivatives M ehravar et al. BMC Chemistry (2021) 15:34 Page 9 of 10 Received: 13 February 2021 Accepted: 4 May 2021 References 1. Domling A, Wang W, Wang K (2012) Chemistry and biology of multicom- ponent reactions. Chem Rev 112(6):3083–3135 2. Shaabani A, Maleki A, Rezayan AH, Sarvary A (2011) Recent progress of isocyanide-based multicomponent reactions in Iran. Mol Divers 12 3 45 15(1):41–68 3. Shaabani A, Amini MM, Ghasemi S, Ghadari R, Rezayan AH, Fazaeli Y, Feizi Reaction runs S (2010) Pyridine-functionalized MCM-41 as an efficient and recoverable Fig. 8 Reusability of the nano-SiO /DBN catalyst. catalyst for the synthesis of pyran annulated heterocyclic systems. Chem Pharm Bull 58(2):270–272 4. Banerjee S, Horn A, Khatri H, Sereda G (2011) A green one-pot multicom- ponent synthesis of 4H-pyrans and polysubstituted aniline derivatives Abbreviations of biological, pharmacological, and optical applications using silica DBN: 1,5-Diazabicyclo[4.3.0]non-5-en; MCRs: Multi-component reactions; nanoparticles as reusable catalyst. Tetrahedron lett 52(16):1878–1881 EtOH: Ethanol; MeOH: Methanol; CH Cl: Chloroform; DMSO: Dimethyl 5. Banerjee S, Sereda G (2009) One-step, three-component synthesis of sulfoxide; FESEM: Field emission scanning electron microscope; FT-IR: Fourier highly substituted pyridines using silica nanoparticle as reusable catalyst. transform infrared; XRD: X-ray diffraction; EDX: Energy-dispersive X-ray; TGA Tetrahedron Lett 50(50):6959–6962 : Thermo gravimetric analysis; NMR: Nuclear magnetic resonance; TLC: Thin 6. Kumar D, Sharma P, Singh H, Nepali K, Gupta GK, Jain SK, Ntie-Kang F layer chromatography; EDS: Dispersive X-ray spectroscopy. (2017) The value of pyrans as anticancer scaffolds in medicinal chemistry. RSC Adv 7(59):36977–36999 7. Latif N, Mishriky N, Assad FM (1982) Carbonyl and thiocarbonyl com- Supplementary Information pounds. XIX. Intramolecular cyclization of (2-nitroetheny1)arylN-arylcar- The online version contains supplementary material available at https:// doi. bamates: synthesis of newer series of 3,4-dihydro-2H-1, 3-oxazin-2-ones org/ 10. 1186/ s13065- 021- 00760-3. and their antimicrobial activities. Aust J Chem 35(5):1037–1043 8. Chylińska JB, Urbański T, Mordarski M (1963) Dihydro-1,3-oxazine deriva- tives and their antitumor activity. J Med Chem 6(5):484–487 Additional file 1. Spectroscopic data for the synthesized 9. Patil AD, Freyer AJ, Eggleston DS, Haltiwanger RC, Bean MF, Taylor PB, tetrahydrobenzo[b]pyran derivatives. Bartus HR (1993) The inophyllums, novel inhibitors of HIV-1 reverse tran- scriptase isolated from the Malaysian tree Calophyllum inophyllum Linn. J Med Chem 36(26):4131–4138 Acknowledgements 10. Bisht SS, Jaiswal N, Sharma A, Fatima S, Sharma R, Rahuja N, Tripathi RP The Research Council of Yazd University gratefully acknowledged for the finan- (2011) A convenient synthesis of novel pyranosyl homo-C-nucleosides cial support for this work. and their antidiabetic activities. Carbohydr Res 346(10):1191–1201 11. Schiller R, Tichotová L, Pavlík J, Buchta V, Melichar B, Votruba I, Pour M Authors’ contributions (2010) 3,5-Disubstituted pyranone analogues of highly antifungally active MM and BFM designed and performed the research, analyzed the data, furanones: conversion of biological effect from antifungal to cytostatic. interpreted the results and prepared the manuscript. MM performed the assay, Bioorg Med Chem Lett 20(24):7358–7360 conducted the optimization, purification of compounds. EB and AB revised 12. Maleki H, Rakhtshah J, Shaabani B (2020) Eec ff tive one-pot synthesis of the manuscript. All authors read and approved the final manuscript. tetrahydrobenzo[b]pyran derivatives using nickel Schiff-base complex immobilized on iron oxide nanoparticles. Appl Organomet Chem Funding 34(8):e5683 This study was financially supported by Yazd University. The funding bodies 13. Zarei A, Yarie M, Zolfigol MA, Niknam K (2020) Synthesis of a novel bifunc- played no role in the design of the study and collection, analysis, and interpre- tional oxyammonium-based ionic liquid: application for the synthesis tation of data and in writing the manuscript. of pyrano[4,3-b]pyrans and tetrahydrobenzo[b]pyrans. J Chin Chem Soc 67(6):1120–1131 Availability of data and materials 14. Hiremath PB, Kantharaju K (2020) An efficient and facile synthesis of All data generated or analyzed during this study are included in this published 2-amino-4H-pyrans & tetrahydrobenzo[b]pyrans catalysed by WEMFSA at article. room temperature. ChemistrySelect 5(6):1896–1906 15. Sharma H, Srivastava S (2018) Anion–cation co-operative catalysis Declarations by artificial sweetener saccharine-based ionic liquid for sustainable synthesis of 3,4-dihydropyrano[c]chromenes, 4,5-dihydropyrano[4,3-b] Ethics approval and consent to participate pyran and tetrahydrobenzo[b]pyrans in aqueous medium. RSC Adv Not applicable. 8(68):38974–38979 16. Niya HF, Hazeri N, Kahkhaie MR, Maghsoodlou MT (2020) Preparation Consent for publication and characterization of MNPs–PhSO H as a heterogeneous catalyst for Not applicable. the synthesis of benzo[b]pyran and pyrano[3,2-c]chromenes. Res Chem Intermed 46(3):1685–1704 Competing interests 17. Singh P, Yadav P, Mishra A, Awasthi SK (2020) Green and mechano- The authors declare no competing interests. chemical One-Pot multicomponent synthesis of bioactive 2-amino-4H- benzo[b]pyrans via highly efficient amine-functionalized SiO @Fe O 2 3 4 Author details nanoparticles. ACS Omega 5(8):4223–4232 Department of Chemistry, College of Science, Yazd University, Yazd, Iran. 18. Sayahi MH, Gorjizadeh M, Meheiseni M, Sayyahi S (2020) One-pot Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, multi-component process for the synthesis of 4-azaphenanthrene- Kashan, Iran. 3,10-dione,1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives catalyzed by the deep eutectic solvent choline chloride-oxalic acid. Z Naturforsch B 75(3):269–279 Yields (%) Mehravar et al. BMC Chemistry (2021) 15:34 Page 10 of 10 19. Hou F, Zheng W, Yousefi N (2020) Design, characterization and applica- synthesis of tetrahydrobenzo[b]pyrans using Ca Mg (PO ) (SiO ) F 9.5 0.5 4 5.5 4 0.5 1.5 tion of the SCMNPs@PC/VB1-Zn as a green and recyclable biocatalyst for as a new bio-and nanocatalyst with Brønsted base and Lewis acid prop- synthesis of pyrano[2,3-c]pyrazole and 4H-benzo-[b]-pyran derivatives. erties. Res Chem Intermed 44(1):93–115 Bull Chem React Eng Catal 15:199–212 28. Gupta R, Gupta M, Paul S, Gupta R (2009) Silica supported ammonium 20. Adibian F, Pourali AR, Maleki B, Baghayeri M, Amiri A (2020) One-pot acetate: an efficient and recyclable heterogeneous catalyst for Knoeve - synthesis of dihydro-1H-indeno [1,2-b] pyridines and tetrahydrobenzo[b] nagel condensation between adehydes or ketones and active methylene pyran derivatives using a new and efficient nanocomposite catalyst group in liquid phase. Bull Korean Chem Soc 30(10):2419–2421 based on N-butylsulfonate-functionalized MMWCNTs-D-NH2. Polyhedron 29. Kiasat AR, Davarpanah J (2013) Fe O @silica sulfuric acid nanoparticles: 3 4 175:114179 an efficient reusable nanomagnetic catalyst as potent solid acid for 21. Shirzaei M, Mollashahi E, Maghsoodlou MT, Lashkari M (2020) Application one-pot solvent-free synthesis of indazolo[2,1-b]phthalazine-triones and of chlorophyll extracted from spinach as a green and affordable catalyst pyrazolo[1,2-b]phthalazine-diones. J Mol Catal A Chem 373:46–54 for the synthesis of tetrahydrobenzo[b]pyran and pyrano[c]chromene. 30. Karade NN, Budhewar VH, Shinde SV, Jadhav WN (2007) l -Proline as an Org Chem Res 6(2):179–187 efficient organo-catalyst for the synthesis of polyhydroquinoline via 22. Gao S, Tsai CH, Tseng C, Yao CF (2008) Fluoride ion catalyzed multicompo- multicomponent Hantzsch reaction. Lett Org Chem 4(1):16–19 nent reactions for efficient synthesis of 4H-chromene and N-arylquinoline 31. Abdollahi-Alibeik M, Nezampour F (2013) Synthesis of 4H-benzo[b]pyrans derivatives in aqueous media. Tetrahedron 64(38):9143–9149 in the presence of sulfated MCM-41 nanoparticles as efficient and reus- 23. Khazaei A, Gholami F, Khakyzadeh V, Moosavi-Zare AR, Afsar J (2015) Mag- able solid acid catalyst. React Kinet Mech Catal 108(1):213–229 netic core–shell titanium dioxide nanoparticles as an efficient catalyst for 32. Lohar T, Kumbhar A, Barge M, Salunkhe R (2016) DABCO functionalized domino Knoevenagel–Michael-cyclocondensation reaction of malononi- dicationic ionic liquid (DDIL): a novel green benchmark in multicom- trile, various aldehydes and dimedone. RSC Adv 5(19):14305–14310 ponent synthesis of heterocyclic scaffolds under sustainable reaction 24. Maleki B, Nasiri N, Tayebee R, Khojastehnezhad A, Akhlaghi HA (2016) conditions. J Mol Liq 224:1102–1108 Green synthesis of tetrahydrobenzo[b]pyrans, pyrano[2,3-c]pyrazoles and 33. Mansoor SS, Logaiya K, Aswin K, Sudhan PN (2015) An appropriate one- spiro[indoline-3,4′-pyrano[2,3-c]pyrazoles catalyzed by nano-structured pot synthesis of 3,4-dihydropyrano[c]chromenes and 6-amino-5-cyano- diphosphate in water. RSC Adv 6(82):79128–79134 4-aryl-2-methyl-4H-pyrans with thiourea dioxide as an efficient, reusable 25. Ren Y, Zhang W, Lu J, Gao K, Liao X, Chen X (2015) One-pot synthesis of organic catalyst in aqueous medium. J Taibah Univ Sci 9(2):213–226 tetrahydro-4 H-chromenes by supramolecular catalysis in water. RSC adv 34. Mehrabi H, Abusaidi H (2010) Synthesis of biscoumarin and 5(97):79405–79412 3,4-dihydropyrano[c]chromene derivatives catalysed by sodium dodecyl 26. Hasaninejad A, Golzar N, Beyrati M, Zare A, Doroodmand MM (2013) sulfate (SDS) in neat water. J Iran Chem Soc 7(4):890–894 Silica-bonded 5-n-propyl-octahydro-pyrimido[1,2-a]azepinium chloride (SB-DBU) Cl as a highly efficient, heterogeneous and recyclable silica- Publisher’s Note supported ionic liquid catalyst for the synthesis of benzo[b]pyran, Springer Nature remains neutral with regard to jurisdictional claims in pub- bis(benzo[b]pyran) and spiro-pyran derivatives. J Mol Catal A Chem lished maps and institutional affiliations. 372:137–150 27. Khazdooz L, Zarei A, Ahmadi T, Aghaei H, Golestanifar L, Sheikhan N (2018) Highly efficient and environmentally benign method for the Re Read ady y to to submit y submit your our re researc search h ? Choose BMC and benefit fr ? Choose BMC and benefit from om: : fast, convenient online submission thorough peer review by experienced researchers in your field rapid publication on acceptance support for research data, including large and complex data types • gold Open Access which fosters wider collaboration and increased citations maximum visibility for your research: over 100M website views per year At BMC, research is always in progress. Learn more biomedcentral.com/submissions http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemistry Central Journal Springer Journals

Nano-SiO2/DBN: an efficacious and reusable catalyst for one-pot synthesis of tetrahydrobenzo[b]pyran derivatives

Download PDF
10 pages

Loading next page...
 
/lp/springer-journals/nano-sio2-dbn-an-efficacious-and-reusable-catalyst-for-one-pot-xR8SXr05RA

References (42)

Publisher
Springer Journals
Copyright
Copyright © The Author(s) 2021
eISSN
2661-801X
DOI
10.1186/s13065-021-00760-3
Publisher site
See Article on Publisher Site

Abstract

Background: The nano-sized particles enhance the exposed surface area of the active part of the catalyst, thereby increasing the contact between precursors and catalyst considerably. In this study, nano-SiO /1,5-diazabicy- clo[4.3.0]non-5-en was synthesized, characterized and used as a heterogeneous nanocatalyst for the synthesis of tetrahydrobenzo[b]pyran derivatives. Fourier Transform Infrared Spectroscopy, Field Emission Scanning Electron Microscopy, Brunauer–Emmett–Teller plot, Energy Dispersive X-ray Spectroscopy and Thermo Gravimetric Analysis were used to discern nano-SiO /1,5-diazabicyclo[4.3.0]non-5-en. Results: Tetrahydrobenzo[b]pyrans were synthesized by using nano-SiO /1,5-diazabicyclo[4.3.0]non-5-en via one-pot three-component condensation of malononitrile, aldehydes and dimedone in H O/EtOH at 60 °C. The results indicate that tetrahydrobenzo[b]pyrans were synthesized in good to high yields and short reaction times. Conclusions: The fundamental privileges of this method are short reaction time, plain procedure, recyclability of catalyst and high yields of products. Keywords: Nano-SiO /DBN, Benzopyrans, Heterogeneous catalyst, Multicomponent reaction, Nano-silica Introduction and hypotensive antiviral [11]. Some pharmacologically Multi-component reactions (MCRs) have significant role and biologically active benzopyrans are shown in Fig. 1. in organic chemistry, because of some merits like selec- A suitable method for synthesis of benzopyrans is tivity, synthetic convergence, high atom economy, sim- three-component condensation of malononitrile and plicity, short reaction time, facility of workup, synthetic dimedone with various aldehydes. This reaction has been efficiency and high yield of products [1, 2]. An efficient investigated in the presence of various catalysts such a way for the synthesis of heterocyclic compounds is using Fe O @SiO @NiSB [12], oxyammonium-based ionic 3 4 2 multi-component reactions, which have great value in liquid [13], WEMFSA [14], [Bmim]Sac [15], MNPs– design of biologically new active compounds [1, 3–5]. PhSO H [16], NH @SiO @Fe O MNPs [17], choline 3 2 2 3 4 Tetrahydrobenzo[b]pyrans as one of the significant chloride-oxalic acid [18], SCMNPs@PC/VB1-Zn [19], group of oxygen-containing heterocycle compounds are MMWCNTs-D-(CH )4-SO H [20] and Chlorophyll 2 3 highly considered due to their medicinal and biological [21]. In this research a practical, simple and inexpensive properties such as spasmolytic [6], antitumor [7], anti- procedure for the synthesis of tetrahydrobenzo[b]pyran bacterial [8], anti HIV [9], insulin-sensitizing activity [10] derivatives is reported by the reaction of aldehydes, malononitrile and dimedone in the presence of catalytic amount of nano-silica supported 1,5-diazabicyclo[4.3.0] *Correspondence: fmirjalili@yazd.ac.ir non-5-en (Nano-SiO /DBN). Moreover, the amount of Department of Chemistry, College of Science, Yazd University, Yazd, Iran Full list of author information is available at the end of the article catalyst used in the reaction and its effect on the product © The Author(s) 2021. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/. The Creative Commons Public Domain Dedication waiver (http:// creat iveco mmons. org/ publi cdoma in/ zero/1. 0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. Mehravar et al. BMC Chemistry (2021) 15:34 Page 2 of 10 Fig. 1 Selected examples of pharmacologically and biologically active benzopyrans yields, as well as the ability to recovery have been studied. the 2θ range from 10° to 80°. Thermo gravimetric analy - Inexpensive and readily available catalyst, easy work-up sis (TGA) was accomplished using a STA 505 instrument and high yield of the products, usage of environmen- under argon atomosphere. The BET surface area, pore tally benign solvents, short reaction times and simplicity size and pore volume were measured by using Tristar II of experimental procedure are some advantages of this 3020 analyzer. Melting points were recorded on a Buchi procedure. B-540 B. V. CHI apparatus. Energy Dispersive X-ray Spectroscopy (EDS) was measured by Phenom pro X. Experimental Materials and methods Chemistry General General procedure for  synthesis of  tetrahydrobenzo[b] Whole reagents and solvent were procured from Merck, pyran derivatives Nano-SiO /DBN (0.03  g) as a nano- Aldrich and fluka chemical companies. Fourier transform catalyst was combined with a mixture of dimedone infrared spectroscopy (FT-IR) (ATR or KBr pellets) was (1  mmol), aromatic and aliphatic aldehyde (1  mmol), run on a Bruker, Eqinox 55 spectrometer. The nanopar - malononitrile (1 mmol) in a round bottom flask and then ticles size and catalyst morphology were ascertained at the mixture was stirred magnetically in H O/EtOH (1:1) Field emission scanning electron microscope (FE-SEM) at 60 °C. The advancement of the reaction was controlled using a Mira 3-XMU. Proton nuclear magnetic resonance by TLC (n-hexane–ethyl acetate, 3:1). When the reaction 1 13 ( H NMR) and carbon nuclear magnetic resonance ( C was over, the catalyst was separated and recovered for the NMR) spectra were record at Bruker (DRX-400 Avance) next run. Then, the crude products were recrystallized in in DMSO-d as the solvent. The crystallographic char - EtOH. acteristics of the sample were obtained by X-ray diffrac - tometer (XRD, Philips Xpert) using Ni-filtered CuKα Procedure for  synthesis of  silica chloride Thionyl chlo - (kCuK = 0.1542  nm, radiation at 40  kV and 30  Ma) in ride (40 mL) (toxic and should be used under ventilator) M ehravar et al. BMC Chemistry (2021) 15:34 Page 3 of 10 and nano-silicagel (10 g) were added to a round bottomed which is dried, reacted with DBN in n‑hexane  under flask (250  mL) provided with a condenser under reflux reflux condition. The chlorine atoms in nano-silica condition for 48 h. Then it was cooled to room tempera - chloride were replaced with N-nucleophiles in DBN ture, the mixture of reaction was filtrated via a Buchner (Scheme1). funnel, then the remainder was rinsed several times with Figure  2a–c shows the FT-IR spectra of the synthe- dichloromethane. Finally, obtained sillica chloride was sized materials. Figure  2d shows absorption band at −1 dried at ambient temperature.3397  cm which is due to the SiO–H stretching vibra- −1 tion, 1652  cm for the C=N stretching vibration and −1 −1 Procedure for  synthesis of  nano‑SiO /DBN Silica chlo-1056  cm for Si–O stretching vibration and 796  cm ride (1 g), DBN (1.5 mL) and n-hexane (10 mL) were added due to the Si–O–Si bending vibrational mode. to a round bottomed flask (100 mL) furnished with a con - Energy-dispersive X-ray spectroscopy (EDS) was used denser, under reflux conditions for 15  h. When reaction to determine the percentage of elements in nano-SiO / was completed, it was cooled, filtrated and rinsed three DBN (Fig.  3). The percentage of C, N, O, Si and Cl in times with n-hexane. Finally, the nano-SiO /DBN catalyst nano-SiO /DBN was 10.75, 4.88, 47.38, 36.48 and 0.25 2 2 was dehydrated at ambient temperature in open air. respectively. The EDX-map of elements in the structure of nano- Results and discussion SiO /DBN (Fig.  4) displays homogenous distribution of A new catalyst was prepared as nano-SiO /DBN in two elements in catalyst. steps. At first, a mixture of thionyl chloride and com - The particle size of nano-SiO /DBN was studied using mercial nano-silica gel was stirred for 48  h under reflux field emission scanning electron microscopy (FESEM) condition to carry out nano-silica chloride. In this reac- and found to be less than 50 nm (Fig. 5). tion, OH functional groups of silica gel were replaced by TGA analysis is shown in Fig.  6A, which exhibits the Cl atoms of thionyl chloride. Then, nano-silica chloride, stability of the nano-SiO /DBN as nano-catalyst which can be used up to 120  °C. The weight loss (4.2%) below 100 °C is likely due to the loss of catalyst moisture. How- ever, the main decomposition occurs at 165–450  °C (20.7%). Nano-SiO /DBN has noticeably high thermal stability with char yield 68.72% at 800 °C. Figure  6B display the XRD Patterns of nano-SiO , nano-SiO /DBN in the range of 10–80°. A broad peak (Fig.  6B (a)) is observed at 2θ = 23°, showing the SiO is Scheme 1 The preparation protocol for nano-SiO /DBN 2 2 Fig. 2 FT-IR spectra of a Nano-SiO , b nano-silica chloride, c DBN, d nano-SiO /DBN 2 2 Mehravar et al. BMC Chemistry (2021) 15:34 Page 4 of 10 Fig. 3 The EDX spectra of nano-SiO /DBN Fig. 4 EDX-map of elements in the structure of nano-SiO /DBN 2 M ehravar et al. BMC Chemistry (2021) 15:34 Page 5 of 10 Figure  7 shows (a) BJH plot, (b) BET (Brunauer– Emmett–Teller) plot, (c) t-plot, (d) Langmuir plot and (e) Adsorption/desorption isotherm of nano-SiO /DBN. The obtained data of BET, Langmuir, t and BJH plots were summarized in Table 1. To optimize the reaction conditions in the synthesis of tetrahydrobenzo[b]pyran, the one-pot three-compo- nent condensation reaction of 4-chlorobenzaldehyde, dimedone and malononitrile was investigated, as model reaction, for various factors such as the amount of nano- SiO /DBN, time, temperature and solvent (Table  2). Therefore, the best reaction condition was performed Fig. 5 FESEM images of nano-SiO /DBN using 0.03  g of catalyst in various solvents such as H O, 2 2 CHCl , MeOH, EtOH and H O/EtOH (Table  2, entries 3 2 1‒5). The use of H O/EtOH (1:1) as solvent at 60  °C is amorphous. While, the diffraction pattern of the nano- the most efficient condition for the model reaction with SiO /DBN (Fig.  6B (b)) indicated peak at 2θ = 23.525° high yield and short time (Table 2, entry 10). The reaction with FWHM = 2.3616. According to Scherrer equation, performed under solvent free conditions, gave a lower the particle size of catalyst is 3.4 nm. 120 0 -2 -4 -6 -8 T[ºC] -10 0200 400600 8001000 Fig. 6 (A) TGA patterns of nano-SiO /DBN and (B) XDR patterns of a) nano-SiO and b) nano-SiO /DBN 2 2 2 Langmuir-Plot BJH H-Plot B BET-Plot t-Plot 0.6 0.15 0.012 ADS 0.4 0.1 0.008 0.05 0.2 0.004 100 r /nm m p/p t/nm p/kPa p 0 0 0 0 0 1 10 100 0 0 1 2 0 45 90 0 0.250.5 ADS DES 45 50 30 00 15 50 p//p 0 0 0.5 1 Fig. 7 a BJH plot, b BET (Brunauer–Emmett–Teller) plot, c t-plot, d Langmuir plot and e adsorption/desorption isotherm of nano-SiO /DBN dV /dr p p rel.Quantity [%] 3 -1 V /cm (STP)g p/V (p -p) a 0 -1 V /cm (STP)g p p//V V a a Mehravar et al. BMC Chemistry (2021) 15:34 Page 6 of 10 Table 1 The summerized data of BET, Langmuir, t and BJH plots Table 2 The reaction of malononitrile, 4-chlorobenzaldehyde and dimedone in the presence of nano-SiO /DBN under various BET plot conditions 3 −1 V 49.439 [cm(STP) g ] 2 −1 a 215.18 [m g ] s,BET C 48.241 3 −1 Total pore volume (p/p = 0.990) 0.4823 [cm g ] Mean pore diameter 8.966 [nm] Langmuir plot 3 −1 Vm 47.372 [cm(STP) g ] 2 −1 a 206.18 [m g ] a s,Lang Entry Time (min) Yield (%) Conditions B 1.1678 Solvent/temp (°C)/catalyst (g) t plot 1 H O/EtOH (1:1)/60/‒ 180 28 Plot data Adsorption 2 H O/60/0.03 30 70 branch 3 EtOH/60/0.03 30 58 2 −1 a 362.85 [m g ] 4 CHCl /60/0.03 60 50 3 −1 V 0 [cm g ] 5 MeOH/60/0.03 60 70 2 −1 a 19.303 [m g ] 6 ‒/60/0.03 120 42 3 −1 V 0.3824 [cm g ] 7 ‒/80/0.03 90 58 2t 2.2126 [nm] 8 H O/EtOH (1:1)/r.t/0.03 15 10 BJH plot 9 H O/EtOH (1:1)/40/0.03 15 58 10 H O/EtOH (1:1)/60/0.03 15 92 Plot data Adsorption branch 11 H O/EtOH (1:1)/60/0.01 50 76 3 −1 12 H O/EtOH (1:1)/60/0.02 30 80 V 0.504 [cm g ] 13 H O/EtOH (1:1)/60/0.04 20 92 r (Area) 3.1 [nm] p,peak 2 −1 14 H O/EtOH (1:1)/60/0.05 35 70 a 290.06 [m g ] Reaction conditions: malononitrile (1 mmol), 4-chlorobenzaldehyde (1 mmol), dimedone (1 mmol) and nano-SiO /DBN as catalyst Isolated yield The modified condition yield in comparison with those performed in the solvent (Table 2, entries 6, 7). After determining the optimized condition, the reac- tion between different aldehydes with dimedone and malononitrile was investigated (Table  3). In result, A suggested mechanism for synthesis of tetrahydrobenzo[b]pyrans were synthesized in good to tetrahydrobenzo[b]pyran derivatives by using nano-SiO / high yields and short reaction times. The progress of DBN is illustrated in Scheme  2. Initially, the nano-SiO / reaction was monitored by TLC continuously. Mean- DBN catalyst activates both the methylene group 5 and while, the aldehydes with electron withdrawing group in the carbonyl group 1. After, the Knoevenagal condensa- 4-position have reacted in lower time with higher yields tion reaction between the malononitrile and aldehyde (Table 3, entries 2, 5, 8, 9, 10). The aldehydes with a sub - in existence of basic catalyst forms the intermediate 6. stitution group in 2-position, have steric hindrance which Then, the Michael addition of enol 4 and intermediate 6 caused longer reaction time (Table  3, entries 3, 4, 5) is performed to produce the intermediate 7. Finally, the (Additional file 1). product is formed by cyclization and tautomerization of As shown in Table  4, performance of synthesized the intermediate 8. catalyst compared to nano-SiO , DBN and previously The reusability of the nano-SiO /DBN was investigated. reported catalysts. Nano-SiO /DBN can be presented After completion of the reaction, the nanocatalyst was as an efficacious one, among others, catalyst in terms of separated and washed with some EtOH, then dried at reaction time and yields. There are many privileges in this 70 °C. The catalyst was regained in good yields and cata - regard simple procedure, nontoxic solvent and mild reac- lyst was used in the synthesis of tetrahydrobenzo[b]pyran tion conditions. DBN is a good catalyst for this reaction, for five times (Fig. 8). but is not a heterogeneous recoverable catalyst. M ehravar et al. BMC Chemistry (2021) 15:34 Page 7 of 10 Table 3 Synthesis of tetrahydrobenzo[b]pyran in the presence of nano-SiO /DBN at 60 ºC in H O/EtOH (1:1) 2 2 a b Entry R Product Time (min) Yield (%) M.P (°C) found M.P (°C) reported (refs.) 1 C H - 4a 20 85 232‒234 234‒235 [22] 6 5 2 4-Cl-C H - 4b 15 92 214‒216 215‒216 [22] 6 4 3 2-Cl–C H - 4c 35 81 217‒218 218‒219 [23] 6 4 4 2,6-Cl -C H - 4d 50 79 245‒247 250‒252 [23] 2 6 3 5 4-NO -C H - 4e 15 89 181‒183 181‒182 [27] 2 6 4 6 3-NO -C H - 4f 20 91 215‒217 217‒218 [27] 2 6 4 7 2-NO -C H - 4 g 35 80 232‒234 233‒234 [22] 2 6 4 8 4-Br-C H - 4 h 30 89 199‒201 197‒201 [13] 6 4 9 4-F-C H - 4i 40 91 192‒194 191‒193 [15] 6 4 10 4-CN-C H - 4j 25 85 231‒233 226‒228 [24] 6 4 11 4-OCH -C H - 4 k 25 70 208‒210 208‒212 [23] 3 6 4 12 3,4-(OCH ) -C H - 4 l 50 82 175‒176 206‒208 [25] 3 2 6 3 13 4-OH-C H - 4 m 40 78 217‒219 214‒216 [23] 6 4 14 4-(CH ) CH-C H - 4n 30 90 197‒199 203‒207 [13] 3 2 6 4 15 4-CO CH -C H - 4o 15 78 257‒259 259‒260 [27] 2 3 6 4 16 1,4-Phenylene 4p 50 91 285 (d) 270 (d) [26] 17 2-Furyl- 4q 25 84 216‒218 217‒219 [23] 18 Pentyl- 4r 20 83 162‒164 164‒165 [27] 19 Styryl- 4 s 30 90 217‒219 218‒218 [23] 4a-s are the synthesized tetrahydrobenzo[b]pyrans with different R Reaction conditions: malononitrile (1 mmol), aldehyde (1 mmol), dimedone (1 mmol) and nano-SiO /DBN (0.03 g) Isolated yield Decomposed Conclusion Table 4 Comparison of nano-SiO /DBN catalyst with some other catalyst for the synthesis of 4b We have reported one-pot three component condensa- tion reaction of various aldehydes, malononitrile and Entry Conditions Time (min) Yield (%) (refs.) dimedone at 60  °C under mild conditions. The novel Solvent/temp (ºC)/catalyst synthesis has been explored of tetrahydrobenzo[b] 1 CH Cl /60/SiO /NH OAc 360 90 [28] 2 2 2 2 pyran derivatives in the presence nano-SiO /DBN as a 2 H O/80/Fe O @SiO /DABCO 25 90 [29] 2 3 4 2 heterogeneous nanocatalyst. The synthesized nanocata - 3 EtOH /reflux/ l -Proline 360 87 [30] lyst was characterized by FT-IR, XRD, FESEM, TGA, 2− 4 EtOH /reflux/SO /MCM-41 60 80 [31] EDS and BET analysers. The advantages of this method 5 H O/reflux/DABCO 150 68 [32] are summarized in the following orders, inexpensive, 6 H O/120/SDS 120 85 [33] recyclability and reusability of the catalyst, easy work- 7 H O/60/Thiourea dioxide 13 93 [34] up and good yield of the products, the use of relatively a c 8 H O/EtOH/60/catalyst 15 92 (this work) environmentally benign solvents, short reaction times 9 H O/EtOH/60/nano-SiO 15 40 (this work) 2 2 and simplicity experimental of the procedure. 10 H O/EtOH/DBN 15 93 (this work) Nano-SiO /DBN Isolated yield The modified condition Mehravar et al. BMC Chemistry (2021) 15:34 Page 8 of 10 Scheme 2 The plausible mechanism for the synthesis of tetrahydrobenzo[b]pyran derivatives M ehravar et al. BMC Chemistry (2021) 15:34 Page 9 of 10 Received: 13 February 2021 Accepted: 4 May 2021 References 1. Domling A, Wang W, Wang K (2012) Chemistry and biology of multicom- ponent reactions. Chem Rev 112(6):3083–3135 2. Shaabani A, Maleki A, Rezayan AH, Sarvary A (2011) Recent progress of isocyanide-based multicomponent reactions in Iran. Mol Divers 12 3 45 15(1):41–68 3. Shaabani A, Amini MM, Ghasemi S, Ghadari R, Rezayan AH, Fazaeli Y, Feizi Reaction runs S (2010) Pyridine-functionalized MCM-41 as an efficient and recoverable Fig. 8 Reusability of the nano-SiO /DBN catalyst. catalyst for the synthesis of pyran annulated heterocyclic systems. Chem Pharm Bull 58(2):270–272 4. Banerjee S, Horn A, Khatri H, Sereda G (2011) A green one-pot multicom- ponent synthesis of 4H-pyrans and polysubstituted aniline derivatives Abbreviations of biological, pharmacological, and optical applications using silica DBN: 1,5-Diazabicyclo[4.3.0]non-5-en; MCRs: Multi-component reactions; nanoparticles as reusable catalyst. Tetrahedron lett 52(16):1878–1881 EtOH: Ethanol; MeOH: Methanol; CH Cl: Chloroform; DMSO: Dimethyl 5. Banerjee S, Sereda G (2009) One-step, three-component synthesis of sulfoxide; FESEM: Field emission scanning electron microscope; FT-IR: Fourier highly substituted pyridines using silica nanoparticle as reusable catalyst. transform infrared; XRD: X-ray diffraction; EDX: Energy-dispersive X-ray; TGA Tetrahedron Lett 50(50):6959–6962 : Thermo gravimetric analysis; NMR: Nuclear magnetic resonance; TLC: Thin 6. Kumar D, Sharma P, Singh H, Nepali K, Gupta GK, Jain SK, Ntie-Kang F layer chromatography; EDS: Dispersive X-ray spectroscopy. (2017) The value of pyrans as anticancer scaffolds in medicinal chemistry. RSC Adv 7(59):36977–36999 7. Latif N, Mishriky N, Assad FM (1982) Carbonyl and thiocarbonyl com- Supplementary Information pounds. XIX. Intramolecular cyclization of (2-nitroetheny1)arylN-arylcar- The online version contains supplementary material available at https:// doi. bamates: synthesis of newer series of 3,4-dihydro-2H-1, 3-oxazin-2-ones org/ 10. 1186/ s13065- 021- 00760-3. and their antimicrobial activities. Aust J Chem 35(5):1037–1043 8. Chylińska JB, Urbański T, Mordarski M (1963) Dihydro-1,3-oxazine deriva- tives and their antitumor activity. J Med Chem 6(5):484–487 Additional file 1. Spectroscopic data for the synthesized 9. Patil AD, Freyer AJ, Eggleston DS, Haltiwanger RC, Bean MF, Taylor PB, tetrahydrobenzo[b]pyran derivatives. Bartus HR (1993) The inophyllums, novel inhibitors of HIV-1 reverse tran- scriptase isolated from the Malaysian tree Calophyllum inophyllum Linn. J Med Chem 36(26):4131–4138 Acknowledgements 10. Bisht SS, Jaiswal N, Sharma A, Fatima S, Sharma R, Rahuja N, Tripathi RP The Research Council of Yazd University gratefully acknowledged for the finan- (2011) A convenient synthesis of novel pyranosyl homo-C-nucleosides cial support for this work. and their antidiabetic activities. Carbohydr Res 346(10):1191–1201 11. Schiller R, Tichotová L, Pavlík J, Buchta V, Melichar B, Votruba I, Pour M Authors’ contributions (2010) 3,5-Disubstituted pyranone analogues of highly antifungally active MM and BFM designed and performed the research, analyzed the data, furanones: conversion of biological effect from antifungal to cytostatic. interpreted the results and prepared the manuscript. MM performed the assay, Bioorg Med Chem Lett 20(24):7358–7360 conducted the optimization, purification of compounds. EB and AB revised 12. Maleki H, Rakhtshah J, Shaabani B (2020) Eec ff tive one-pot synthesis of the manuscript. All authors read and approved the final manuscript. tetrahydrobenzo[b]pyran derivatives using nickel Schiff-base complex immobilized on iron oxide nanoparticles. Appl Organomet Chem Funding 34(8):e5683 This study was financially supported by Yazd University. The funding bodies 13. Zarei A, Yarie M, Zolfigol MA, Niknam K (2020) Synthesis of a novel bifunc- played no role in the design of the study and collection, analysis, and interpre- tional oxyammonium-based ionic liquid: application for the synthesis tation of data and in writing the manuscript. of pyrano[4,3-b]pyrans and tetrahydrobenzo[b]pyrans. J Chin Chem Soc 67(6):1120–1131 Availability of data and materials 14. Hiremath PB, Kantharaju K (2020) An efficient and facile synthesis of All data generated or analyzed during this study are included in this published 2-amino-4H-pyrans & tetrahydrobenzo[b]pyrans catalysed by WEMFSA at article. room temperature. ChemistrySelect 5(6):1896–1906 15. Sharma H, Srivastava S (2018) Anion–cation co-operative catalysis Declarations by artificial sweetener saccharine-based ionic liquid for sustainable synthesis of 3,4-dihydropyrano[c]chromenes, 4,5-dihydropyrano[4,3-b] Ethics approval and consent to participate pyran and tetrahydrobenzo[b]pyrans in aqueous medium. RSC Adv Not applicable. 8(68):38974–38979 16. Niya HF, Hazeri N, Kahkhaie MR, Maghsoodlou MT (2020) Preparation Consent for publication and characterization of MNPs–PhSO H as a heterogeneous catalyst for Not applicable. the synthesis of benzo[b]pyran and pyrano[3,2-c]chromenes. Res Chem Intermed 46(3):1685–1704 Competing interests 17. Singh P, Yadav P, Mishra A, Awasthi SK (2020) Green and mechano- The authors declare no competing interests. chemical One-Pot multicomponent synthesis of bioactive 2-amino-4H- benzo[b]pyrans via highly efficient amine-functionalized SiO @Fe O 2 3 4 Author details nanoparticles. ACS Omega 5(8):4223–4232 Department of Chemistry, College of Science, Yazd University, Yazd, Iran. 18. Sayahi MH, Gorjizadeh M, Meheiseni M, Sayyahi S (2020) One-pot Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, multi-component process for the synthesis of 4-azaphenanthrene- Kashan, Iran. 3,10-dione,1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives catalyzed by the deep eutectic solvent choline chloride-oxalic acid. Z Naturforsch B 75(3):269–279 Yields (%) Mehravar et al. BMC Chemistry (2021) 15:34 Page 10 of 10 19. Hou F, Zheng W, Yousefi N (2020) Design, characterization and applica- synthesis of tetrahydrobenzo[b]pyrans using Ca Mg (PO ) (SiO ) F 9.5 0.5 4 5.5 4 0.5 1.5 tion of the SCMNPs@PC/VB1-Zn as a green and recyclable biocatalyst for as a new bio-and nanocatalyst with Brønsted base and Lewis acid prop- synthesis of pyrano[2,3-c]pyrazole and 4H-benzo-[b]-pyran derivatives. erties. Res Chem Intermed 44(1):93–115 Bull Chem React Eng Catal 15:199–212 28. Gupta R, Gupta M, Paul S, Gupta R (2009) Silica supported ammonium 20. Adibian F, Pourali AR, Maleki B, Baghayeri M, Amiri A (2020) One-pot acetate: an efficient and recyclable heterogeneous catalyst for Knoeve - synthesis of dihydro-1H-indeno [1,2-b] pyridines and tetrahydrobenzo[b] nagel condensation between adehydes or ketones and active methylene pyran derivatives using a new and efficient nanocomposite catalyst group in liquid phase. Bull Korean Chem Soc 30(10):2419–2421 based on N-butylsulfonate-functionalized MMWCNTs-D-NH2. Polyhedron 29. Kiasat AR, Davarpanah J (2013) Fe O @silica sulfuric acid nanoparticles: 3 4 175:114179 an efficient reusable nanomagnetic catalyst as potent solid acid for 21. Shirzaei M, Mollashahi E, Maghsoodlou MT, Lashkari M (2020) Application one-pot solvent-free synthesis of indazolo[2,1-b]phthalazine-triones and of chlorophyll extracted from spinach as a green and affordable catalyst pyrazolo[1,2-b]phthalazine-diones. J Mol Catal A Chem 373:46–54 for the synthesis of tetrahydrobenzo[b]pyran and pyrano[c]chromene. 30. Karade NN, Budhewar VH, Shinde SV, Jadhav WN (2007) l -Proline as an Org Chem Res 6(2):179–187 efficient organo-catalyst for the synthesis of polyhydroquinoline via 22. Gao S, Tsai CH, Tseng C, Yao CF (2008) Fluoride ion catalyzed multicompo- multicomponent Hantzsch reaction. Lett Org Chem 4(1):16–19 nent reactions for efficient synthesis of 4H-chromene and N-arylquinoline 31. Abdollahi-Alibeik M, Nezampour F (2013) Synthesis of 4H-benzo[b]pyrans derivatives in aqueous media. Tetrahedron 64(38):9143–9149 in the presence of sulfated MCM-41 nanoparticles as efficient and reus- 23. Khazaei A, Gholami F, Khakyzadeh V, Moosavi-Zare AR, Afsar J (2015) Mag- able solid acid catalyst. React Kinet Mech Catal 108(1):213–229 netic core–shell titanium dioxide nanoparticles as an efficient catalyst for 32. Lohar T, Kumbhar A, Barge M, Salunkhe R (2016) DABCO functionalized domino Knoevenagel–Michael-cyclocondensation reaction of malononi- dicationic ionic liquid (DDIL): a novel green benchmark in multicom- trile, various aldehydes and dimedone. RSC Adv 5(19):14305–14310 ponent synthesis of heterocyclic scaffolds under sustainable reaction 24. Maleki B, Nasiri N, Tayebee R, Khojastehnezhad A, Akhlaghi HA (2016) conditions. J Mol Liq 224:1102–1108 Green synthesis of tetrahydrobenzo[b]pyrans, pyrano[2,3-c]pyrazoles and 33. Mansoor SS, Logaiya K, Aswin K, Sudhan PN (2015) An appropriate one- spiro[indoline-3,4′-pyrano[2,3-c]pyrazoles catalyzed by nano-structured pot synthesis of 3,4-dihydropyrano[c]chromenes and 6-amino-5-cyano- diphosphate in water. RSC Adv 6(82):79128–79134 4-aryl-2-methyl-4H-pyrans with thiourea dioxide as an efficient, reusable 25. Ren Y, Zhang W, Lu J, Gao K, Liao X, Chen X (2015) One-pot synthesis of organic catalyst in aqueous medium. J Taibah Univ Sci 9(2):213–226 tetrahydro-4 H-chromenes by supramolecular catalysis in water. RSC adv 34. Mehrabi H, Abusaidi H (2010) Synthesis of biscoumarin and 5(97):79405–79412 3,4-dihydropyrano[c]chromene derivatives catalysed by sodium dodecyl 26. Hasaninejad A, Golzar N, Beyrati M, Zare A, Doroodmand MM (2013) sulfate (SDS) in neat water. J Iran Chem Soc 7(4):890–894 Silica-bonded 5-n-propyl-octahydro-pyrimido[1,2-a]azepinium chloride (SB-DBU) Cl as a highly efficient, heterogeneous and recyclable silica- Publisher’s Note supported ionic liquid catalyst for the synthesis of benzo[b]pyran, Springer Nature remains neutral with regard to jurisdictional claims in pub- bis(benzo[b]pyran) and spiro-pyran derivatives. J Mol Catal A Chem lished maps and institutional affiliations. 372:137–150 27. Khazdooz L, Zarei A, Ahmadi T, Aghaei H, Golestanifar L, Sheikhan N (2018) Highly efficient and environmentally benign method for the Re Read ady y to to submit y submit your our re researc search h ? Choose BMC and benefit fr ? Choose BMC and benefit from om: : fast, convenient online submission thorough peer review by experienced researchers in your field rapid publication on acceptance support for research data, including large and complex data types • gold Open Access which fosters wider collaboration and increased citations maximum visibility for your research: over 100M website views per year At BMC, research is always in progress. Learn more biomedcentral.com/submissions

Journal

Chemistry Central Journal – Springer Journals

Published: May 21, 2021

There are no references for this article.