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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

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Front. Chem. Sci. Eng.    2021, Vol. 15 Issue (4) : 1008-1020    https://doi.org/10.1007/s11705-020-1996-8
RESEARCH ARTICLE
Trihydrazinotriazine-grafting Fe3O4/SiO2 core-shell nanoparticles with expanded porous structure for organic reactions
Jamal Rahimi, Seyedeh Shadi Mirmohammadi, Ali Maleki()
Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, Iran
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Abstract

This study focuses on the synthesis and characterization of a novel magnetic nanocomposite 2,4,6-trihydrazino-1,3,5-triazine (THDT)-functionalized with silica-coated iron oxide magnetic nanoparticles (MNPs). This nanocomposite has porous morphology decorated with the spherical MNPs. Through co-precipitation of iron salts, MNPs were obtained. The prepared THDT was placed on the chlorine surface-modified MNPs. The present environment-friendly nanocatalyst intensely accelerated the synthesis of highly functionalized tetrahydrobenzo[b]pyran derivatives as well as reduced the reaction times and increased yields of the products.
Keywords trihydrazino-triazine      porous      magnetic nanocatalyst      green chemistry      tetrahydrobenzo[b]pyrans     
Corresponding Author(s): Ali Maleki   
Just Accepted Date: 05 November 2020   Online First Date: 16 December 2020    Issue Date: 04 June 2021
 Cite this article:   
Jamal Rahimi,Seyedeh Shadi Mirmohammadi,Ali Maleki. Trihydrazinotriazine-grafting Fe3O4/SiO2 core-shell nanoparticles with expanded porous structure for organic reactions[J]. Front. Chem. Sci. Eng., 2021, 15(4): 1008-1020.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1996-8
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I4/1008
Fig.1  Scheme 1 Fe3O4@SiO2—THDT catalyst used in the synthesis of tetrahydrobenzo[b]pyrans 4a-4p.
Fig.2  Comparison of FTIR spectra for (a) Fe3O4, (b) Fe3O4@SiO2, (c) Fe3O4@SiO2-Cl, (d) Fe3O4@SiO2-THDT and (e) recycled-Fe3O4@SiO2-THDT.
Fig.3  EDX spectra of (a) Fe3O4@SiO2, (b) Fe3O4@SiO2-Cl, (c) Fe3O4@SiO2-THDT and (d)recycled-Fe3O4-SiO2@THDT; (e) elemental maps of Fe, O, Si, C, and N atoms (The scale bar is 1 mm. y-axis: number of counts (intensity), x-axis: energy (keV)).
Fig.4  SEM images of (a) Fe3O4@SiO2-Cl microsphere, (b, c) Fe3O4@SiO2—THDT.
Fig.5  VSM magnetization curves of (a) Fe3O4, (b) Fe3O4@SiO2-Cl, (c) Fe3O4@SiO2-THDT and (d) recycled-Fe3O4@SiO2-THDT.
Fig.6  TGA curve of Fe3O4@SiO2—THDT.
Fig.7  The XRD pattern for Fe3O4@SiO2—THDT.
Fig.8  Raman spectra of (a) Fe3O4, (b) Fe3O4@SiO2, (c) Fe3O4@SiO2-Cl, (d) Fe3O4@SiO2-THDT and (e) recycled-Fe3O4@SiO2—THDT.
Entry Solvent Catalyst Catalyst/g Time/min Yield/% a)
1 H2O ? ? 60 Trace
2 H2O Fe3O4@SiO2-THDT 0.04 60 21
3 EtOH THDT 0.04 60 36
4 EtOH Fe3O4 0.04 60 27
5 EtOH Fe3O4@SiO2 0.04 60 45
6 EtOH Fe3O4@SiO2-Cl 0.04 60 75
7 EtOH Fe3O4@SiO2-Cl 0.06 60 65
8 EtOH Fe3O4@SiO2-THDT 0.03 60 90
9 EtOH Fe3O4@SiO2-THDT 0.04 60 93
10 EtOH Fe3O4@SiO2-THDT 0.04 10 94b)
11 EtOH Fe3O4@SiO2-THDT 0.06 10 90
Tab.1  Reaction optimization of 4h catalyzed by the Fe3O4@SiO2-THDT
Fig.9  Scheme 2 Synthesis of tetrahydrobenzo[b]pyrans 4a?4p using as-prepared catalyst Fe3O4@SiO2-THDT at 75 °C.
Entry Ar 1,3- Dicarbonyl compound Product Time/min Yield/% a) Mp/°C
Found Reported
1 4-Chlorophenyl Dimedone 4a 10 94 218?220 217?219 [22]
2 2-Methoxyphenyl Dimedone 4b 16 84 203?205 200?201[22]
3 4-Hydroxyphenyl Dimedone 4c 15 87 206?210 205?206 [24]
4 3-Hydroxyphenyl Dimedone 4d 20 80 229-233 231?234 [22]
5 2-Methylphenyl Dimedone 4e 25 82 207?210 205?207 [25]
6 3-Flourophenyl Dimedone 4f 5 96 209?211 210?212 [23]
7 3-Nitrophenyl Dimedone 4g 9 95 212?214 213-216 [22]
8 Phenyl Dimedone 4h 10 93 231?233 229?231 [24]
9 2,4-Dichlorophenyl Dimedone 4i 10 84 180?184 183?186 [23]
10 4-Cyanophenyl Dimedone 4j 6 97 231?232 230?232 [22]
11 2-Nitrophenyl Ethyl acetoacetate 4k 15 91 181?183 177?180 [26]
12 3-Bromophenyl Ethyl acetoacetate 4l 12 86 169?171 166-167 [27]
13 2-Chlorophenyl Dimedone 4m 15 80 290?292 289?291 [24]
14 3-Bromophenyl Dimedone 4n 10 90 229?231 228?230 [23]
15 4-(Dimethylamino)phenyl Dimedone 4o 7 93 214?216 212?213 [22]
16 Phenyl Ethyl acetoacetate 4p 9 95 190?192 191?193 [25]
Tab.2  Reaction optimization of the synthesis of tetrahydrobenzo[b]pyrans 4a?4p using as-prepared catalyst Fe3O4@SiO2-THDT at 75 °C
Fig.10  Scheme 3 Proposed mechanism for the synthesis of 4a–4p using Fe3O4@SiO2-THDT.
Fig.11  Diagram of the recycled Fe3O4@SiO2-THDT nanocatalyst in the synthesis of 4h.
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