The Utilization of Fe3O4 Nanocatalyst in Modifying Cinnamaldehyde Compound to Synthesis 2-Amino-4H-Chromene Derivative

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Materials Today: Proceedings 22 (2020) 193–198

2018 2nd International Conference on Nanomaterials and Biomaterials, ICNB 2018, 10–12 December 2018, Barcelona, Spain

The Utilization of Fe3O4 Nanocatalyst in Modifying Cinnamaldehyde Compound to Synthesis 2-Amino-4H-Chromene Derivative Agus Rimus Liandia, Rika Tri Yunartib, Muhammad Fajri Nurmawanc, and Antonius Herry Cahyanaa* a

b

Organic Synthesis Research Laboratory, Department of Chemistry, Faculty of Mathematics and Natural Sciences Research Laboratory, Universitas Indonesia, Kampus UI Baru, 16424 Depok, Jawa Barat, Indonesia.

Inorganic Chemistry Research Laboratory, Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Kampus UI Baru, 16424 Depok, Jawa Barat, Indonesia. c

Padang Industrial Research and Standardization Center, Padang City 25164, West Sumatera, Indonesia.

Abstract Fe3O4 nanoparticles have got more attention in their application as catalyst. This research aims to utilize Fe3O4 as nanocatalyst in modifying of cinnamaldehyde compound. In this study, Fe3O4 nanoparticles were synthesized by co-precipitation method using Fe2+ and Fe3+ ions and characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results of the characterization supports that Fe3O4 nanoparticles were successfully synthesized. Afterward, Fe3O4 would be applied in modifying of cinnamaldehyde compound. The results of the reaction were analyzed its absorbance, functional group, and molecular weight using UV/Vis Spectrophotometry, FT-IR and GC-MS. From the results of the synthesis and characterization, one cinnamaldehyde modified compounds was obtained, namely 2-amino-4-styryl-4Hbenzo[h]chromene-3-carbonitrile (Compound 1). From the yield of the reaction, a significant difference was found between the reaction with and without catalyst. © 2019 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of the 2018 2nd International Conference on Nanomaterials and Biomaterials. Keywords: Fe3O4; Nanocatalyst; Magnetite; Cinnamaldehyde; Chromene

1876-6102 © 2019 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of the 2018 2nd International Conference on Nanomaterials and Biomaterials.

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1. Introduction Nanoparticles have high surface area that increases the number of the active sites of the catalyst which allows for an increased reaction rate [1] because it can improve the interaction between reactants and catalyst [2]. Recently, Fe3O4 nanoparticles have got more attention in their application as catalyst [3]. It is due to their paramagnetic and insoluble characteristic that can make the catalyst to be separated from the reaction mixture using external magnet easily, which eliminates the requirements of catalyst filtration, reduces energy consumption, decreases losing catalyst and conserves time in getting catalyst recovery [4]. Beside that their environmentally friendly, economic viability and non-toxic properties become some considerations which support the utilization of Fe3O4 nanoparticles as catalyst [5]. Cinnamaldehyde or 3-Phenylprop-2-enal is one of the active chemical elements of cinnamon essential oil which is strong scented which is commonly used as spices in Indonesia and several other countries. It found in the cinnamon garden (Cinnamomum verum). For a long time, Cinnamaldehyde has been used as a flavoring agent in chewing gum, ice cream, drinks and candy. In addition, it has been widely used to give cinnamon flavor to medical products, cosmetics, and perfumes. Cinnamaldehyde is an active inhibitor of the growth of bacteria, yeast and filament fungi. Cinnamaldehyde has an inhibitory effect by inhibiting ATPase activity, cell wall biosynthesis, and changes in their structure and integrity [6] Several studies have reported that cinnamaldehyde as one of the active chemical elements of cinnamon essential oil and can contribute to various biological activities. Cinnamon or cinnamon has been reported to have bioactivity in the form of antifungal, antibacterial, antiviral, antioxidant, antidiabetic, anti-inflammatory, and anticancer properties. In addition, cinnamon has shown nematicide, activity of mosquito larvae, insecticides, and cinnamon is effective for the treatment of various cardiovascular diseases [7,8]. To enrich the cinnamaldehyde modification compound, it was carried out by doing a Michael addition reaction with malononitrile and phenol and naphthol. To increase the chance of this reaction, Fe3O4 nanoparticles are used as catalyst. 2. Experimental 2.1 Material All Chemical and reagents in this research were obtained from Merck Chemical Company and used of analytical grade. 2.2 Synthesis of Fe3O4 nanoparticles Fe3O4 nanoparticles were synthesized by a simple co-precipitation method. FeCl2. 4H2O and FeCl3. 6H2O with molar proportion of 1:2 were dissolved in 100 mL deionized water in three-neck rounded flask. Afterward, 10 mL NH4OH was dropped slowly to reaction under constant magnetic stirring and N2 condition. While dropping, the solution was stirred for 2 hours until pH=10. The black magnetite Fe3O4 nanoparticle was formed. Then, the magnetite was decanted with a magnet from the outside and washed with destilled water. The result was dried at 60 °C in oven and characterized with FTIR, XRD and SEM. 2.3 General procedure for the modification of cinnamaldehyde A mixture of cinnamaldehyde (1 mmol), malononitrile (1 mmol), β-naphthol (1 mmol) were diluted with water: ethanol (4:1) in the presence of Fe3O4 nanocatalyst under constant magnetic stirring condition. The result of reaction was monitored by TLC and the catalyst was separated by magnetic decantation. After that, the solvent was evaporated and the mixture was washed and purified by hot ethanol. Then, the products were characterized its absorbance, functional group, and molecular weight using UV/Vis Spectrophotometry by FTIR, and GC-MS.

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3. Result and discussion Fe3O4 nanoparticles have been prepared by co-precipitation method using Fe2+ and Fe3+ ions from FeCl2 and FeCl3 with a comparison of mol 1:2. In this study, NH4OH base was used as a precipitation agent. During the preparation, N2 gas is needed to prevent oxidation by free oxygen in the air. Fe3O4 which has been synthesized is shown in Fig. 1. From that picture, it can be seen that the synthesized Fe3O4 is black and has magnetic properties. When the magnet from the outside is brought closer, the Fe3O4 magnetite will stick. To find out its physical properties, Fe3O4 is characterized using FTIR, XRD and SEM. Based on the result of the characterization using FTIR (Fig. 2), shows the bond vibration of Fe3O4 nanoparticles. The broad peak at 3330 cm-1 is the O-H stretching bond vibration. Whereas, the peak at 1632 cm-1 is O-H bending bond vibration and peak at 574 cm-1 is the bond vibration of Fe-O stretching.

Fig. 1. Fe3O4 nanoparticles synthesis results

Determination of the crystal lattice parameters and particle size, Fe3O4 nanoparticles were analyzed by X-ray diffraction. The diffractogram of Fe3O4 nanoparticles shows in Fig. 3 and compared to the standard Fe3O4 which has been examined [9] and corresponds to the cubic phase of the Fe3O4 (magnetite, JCPDS card number 85-1436). There are six diffraction peaks which show that Fe3O4 has been successfully synthesized, videlicet (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1) and (4 4 0). Based on calculations using the Scherrer equation, the average size of the crystal is 8 nm. Fe3O4

% Transmittance

O-H1632

3330

O-H

Fe-O 574 4000

3500

3000

2500

2000

1500 -1

wavenumber (cm ) Fig. 2. IR spectra of Fe3O4 nanoparticles

1000

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(311)

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(440)

(511)

Intensity (a.u)

(422)

(400)

(220)

Fe3O4

Standar Fe3O4

20

30

40

50

60

70

o

2θ ( ) Fig. 3. XRD patterns of the Fe3O4 nanoparticles

Morphology and distribution of Fe3O4 nanoparticles further characterized by SEM as shown Fig. 4. From the results of SEM, it is clear that the form Fe3O4 is a round shape and occurs in aggregate. The aggregate that occurs may be due to the imperfection of the distribution of Fe3O4 nanoparticles in water. Besides, the magnetic nature of itself can also be the cause of this aggregate. In this SEM analysis, it was taken three points for the determination of Fe3O4 particle size, which is 89,40 nm ; 59,66 nm ; and 85,68 nm. The average value of the three points is 78,25 nm.

Fig. 4. Morphology of Fe3O4 nanoparticles by SEM

Evaluation the ability of Fe3O4 as a magnetic catalyst, modification of cinnamaldehyde was carried out into a 2amini-4-H-Chromene derivative, namely 2-amino-4-styryl-4H-benzo[h]chromene-3-carbonitrile (Compound 1) that showed in Fig. 5. This reaction was conducted using a one-pot three component method by mixing all the

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components in one flask added with a number of catalysts in water: ethanol solvent. Reaction mechanisms offered include Knoevenagel condensation, Michael additions, and cyclization. Fe3O4 as Lewis acid will improve the electrophilic properties of cinnamaldehyde and be able to activate carbonyl on the aldehyde so that it is susceptible to nucleophilic attack from malononitrile. Furthermore Michael's addition occurs to form an oxygen bond with nucleophilic carbon and is continued with cyclization.

O OH H

+

N

N

+

C

O

N

NH2

Fig. 5. Reaction of modification cinnamaldehyde for Compound 1

The oraganic compound synthesized was characterized by FTIR, UV/Vis Spectroscopy, and GC-MS. Fig. 6a and 6b show the Uv/Vis and FTIR spectra of compound 1. The measurement result shows a shift in the maximum wavelenght from reactants to product. Vλmax of compound 1 is at 350 nm (Fig. 6a). Fig. 6b shows the important bond vibration of compound 1 like C-N at 3380 cm-1, N-H stretching at 3185 cm-1, C≡N at 2250 cm-1, C-H sp2 at 2938 cm-1 and C-H sp3 stretching at 3035 cm-1, C-O at 1074 cm-1, and N-H bending at 689 cm-1 . The presence of all vibrations of these functional group bonds, supports the formation of compound 1.

B-naphthol Cinnamaldehyde Compound 1 Malononitrile

(b)

Intensity (a.u)

%Transmittance

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200

300

400

Wavelength (nm)

500

3500

3000

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Fig. 6. (a) UV/Vis and (b) FTIR spectrum of compound 1

Molecular wight and the fragment of compound 1 have been analyzed using gas chromatography-mass spectrometry. This fragment was obtained from GC-MS with a single peak in chromatogram of sample. Compound 1 had a retention time of 11.847 and the molecular weight (m/z) is 326 (Fig. 7). There are some important numbers in fragment of compound 1, including 180,1 ; 153,1 ; 115,1 ; 95,9 ; 76,1 ; and 51,1. The greatest abundance is in the fragment with m/z = 115,1.

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Fig. 7. Mass spectrometry fragments Compound 1

The optimum conditions for the use of Fe3O4 nanocatalyst were tested by varying the number of catalysts starting from 2.5%, 5%, 7.5%, and 10%. Then, the optimization of temperatures starting from room temperature, 50oC, 70oC, and 90oC. Afterward performed with the reaction time treatment starting from 45 minutes, 60 minutes, 90 minutes, and 120 minutes. The optimum conditions obtained for compound 1 are 5% catalyst, temperature 90oC with a time of 90 minutes with a yield of around 75%. 4. Conclusions Fe3O4 nanoparticles have been successfully synthesized with black characteristics and have magnetic properties, which is supported by data analysis using FTIR and XRD. When Fe3O4 nanoparticles were applied, the magnetic catalyst was tested by modifying the cinnamaldehyde and obtained 2-amino-4H-chromene derivative named 2amino-4-styryl-4H-benzo[h]chromene-3-carbonitrile (Compound 1). The optimum conditions obtained for both compounds are 5% catalyst, temperature 90oC with a time of 90 minutes with a yield of around 75%. Acknowledgements This research was financially funded by the Indonesia Endowment Fund for Education (LPDP RI). References [1] Chng, L. L., Erathodiyil, N., & Ying, J. Y. (2013). Nanostructured catalysts for organic transformations. Accounts of Chemical Research, 46(8), 18251837. https://doi.org/10.1021/ar300197s [2] Nasir Baig, R. B., Nadagouda, M. N., & Varma, R. S. (2015). Magnetically retrievable catalysts for asymmetric synthesis. Coordination Chemistry Reviews, 287, 137156. https://doi.org/10.1016/j.ccr.2014.12.017 [3] Lu, A. H., Salabas, E. L., & Schüth, F. (2007). Magnetic nanoparticles: Synthesis, protection, functionalization, and application. Angewandte Chemie - International Edition, 46(8), 12221244. https://doi.org/10.1002/anie.200602866 [4] Sharma, R. K., Dutta, S., Sharma, S., Zboril, R., Varma, R. S., & Gawande, M. B. (2016). Fe3O4 (iron oxide)-supported nanocatalysts: synthesis, characterization and applications in coupling reactions. Green Chemistry, 18, 31843209. https://doi.org/10.1039/c6gc00864j [5] Habibi, D., Kaamyabi, S., & Hazarkhani, H. (2015). Fe 3O 4 nanoparticles as an efficient and reusable catalyst for the solvent ‐ free synthesis of. Journal of Saudi Chemical Society, 36(3), 362–366. https://doi.org/10.1016/S1872 [6] Shreaz, S., Wani, W. A., Behbehani, J. M., Raja, V., Karched, M., Ali, I., … Ting, L. (2016). Fitoterapia Cinnamaldehyde and its derivatives , a novel class of antifungal agents, 112, 116–131. https://doi.org/10.1016/j.fitote.2016.05.016 [7] Satya, N. S., V, S. P. D., & Meena, V. (2012). Purification of Cinnamaldehyde from Cinnamon Species by Column Chromatography, 1(7), 49–51. [8] Zhu, R., Liu, H., Liu, C., Wang, L., Ma, R., Chen, B., … Gao, S. (2017). Cinnamaldehyde in diabetes : A review of pharmacology , pharmacokinetics and safety, 122, 78–89 https://doi.org/10.1016/j.phrs.2017.05.019 [9] Silva V.A.J., Andrade P.L., Silva M.P.C., Bustamante A.D., De Los Santos Valladares L., Albino Aguiar J. (2013) Journal of Magnetism and Magnetic Materials, 343 , pp. 138-143. https://doi.org/10.1016/j.jmmm.2013.04.062