Modification Structure of Cinnamaldehyde with Primary Amines by Reflux and Sonication Methods in the Presence of Sulfuric Acid as a Catalyst
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Abstract
Cinnamon is one of the most valuable natural resources that sustains life and exists freely in nature. Cinnamaldehyde is the primary compound in cinnamon oil. It has a unique structure that contains a benzene ring, an aldehyde group, and an unsaturated double bond. Cinnamaldehyde has been structurally modified to improve biological activity. In this research, cinnamaldehyde and nitrophenyl amines were reacted with sulfuric acid as a catalyst by refluxing and sonication. UV-Vis Spectroscopy, FT-IR, 1H-NMR, and 13C-NMR were used to validate the chemical structures. Thin-layer chromatography (TLC) revealed a new single spot formed by the reaction of cinnamaldehyde and 4-amino-2-nitrophenol. By refluxing for 2 hours or sonicating for 30 minutes, a novel imine chemical, 4-nitro-2-((3-phenylallylidene)amino)phenol, was effectively synthesized with a yield of 75.21% or 83.71%, respectively. This imine was obtained as a dark red powder with a melting point of 237 °C. Meanwhile, only sonication produced a novel product from the reaction of cinnamaldehyde and 4-nitroaniline. However, the structural elucidation has not yet been performed because the yield was so low. Surprisingly, there was no reaction between cinnamaldehyde and 2,4-dinitroaniline. It was most likely owing to the amine’s bulky structure and the presence of two nitro groups in the amine as electron-withdrawing groups that reduced the nucleophilicity of the amine. We demonstrated that sonication is a suitable approach for imine synthesis, as it is commonly utilized in organic compound synthesis protocols.
References
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Yaseen, O. K. and M. T. Mohammed (2020). Effects of Cinnamon and Their Beneficial Content on Treatment of Oxidative Stress. Systematic Reviews in Pharmacy, 11(9); 847–850
Ahmed, Y. M., M. M. Omar, and G. G. Mohamed (2022). Synthesis, Spectroscopic Characterization, and Thermal Studies of Novel Schiff Base Complexes: Theoretical Simulation Studies on Coronavirus (COVID-19) Using Molecular Docking. Journal of the Iranian Chemical Society, 19(3); 901–919
Akbarzadeh, Z. and J. Safaei-Ghomi (2020). UltrasoundAssisted Eco-friendly Synthesis of 3-Cinnamoyl Coumarins Using N,N-(1,2-Phenylene)bis(2-Aminobenzamide) Dichloro Cobalt Immobilized on Mesoporous Al-SBA-15 as a New and Recyclable Catalyst. Green Chemistry Letters and Reviews, 13(2); 141–154
Al Zoubi, W., A. A. S. Al-Hamdani, S. Duraid Ahmed, H. M. Basheer, R. S. A. Al-Luhaibi, A. Dib, and Y. G. Ko (2019). Synthesis, Characterization, and Antioxidant Activities of Imine Compounds. Journal of Physical Organic Chemistry, 32(3); 1–9
Altamimi, M. A., A. Hussain, S. Alshehri, S. S. Imam, A. Alnami, and A. Bari (2020). Novel Hemocompatible Imine Compounds as Alternatives for Antimicrobial Therapy in Pharmaceutical Application. Processes, 8(11); 1–19
Asadi, M., H. Sepehrpour, and K. Mohammadi (2011). Tetradentate Schiff Base Ligands of 3,4-Diaminobenzophenone: Synthesis, Characterization, and Thermodynamics of Complex Formation with Ni(II), Cu(II), and Zn(II) Metal Ions. Journal of the Serbian Chemical Society, 76(1); 63–74
Basha, M. H., C. Subramanyam, and K. P. Rao (2020). Ultrasound-Promoted Solvent-Free Synthesis of Some New α-Aminophosphonates as Potential Antioxidants. Main Group Metal Chemistry, 43(1); 147–153
Begum, N., S. Mustaq, S. Sameena Aziz, and M. Arifuddin (2021). Rapid and Spontaneous Synthesis of Schiff Bases Catalyzed by Sulfuric Acid under Environmentally Benign Condition. July; 218–225
Bekdemir, Y. and K. Efil (2014). Microwave-Assisted SolventFree Synthesis of Some Imine Derivatives. Organic Chemistry International, 2014; 1–5
Belghit, M. Y., A. Moussi, and D. Barkat (2017). In Vitro Antifungal Activity of Some Schiff Bases Derived from Ortho-Hydroxybenzaldehyde against Fusarium. Journal of Engineering Science and Technology, 12(6); 1709–1722
Celik, S., F. Ozkok, A. E. Ozel, E. Cakir, and S. Akyuz (2021). Synthesis, FT-IR and NMR Characterization, Antibacterial and Antioxidant Activities, and DNA Docking Analysis of a New Vanillin-Derived Imine Compound. Journal of Molecular Structure, 1236
Ddorovic, J., Z. Markovic, Z. D. Petrovic, D. Simijonovic, and V. P. Petrovic (2017). Theoretical Analysis of the Experimental UV-Vis Absorption Spectra of Some Phenolic Schiff Bases. Molecular Physics, 115(19); 2460–2468
Devidas, S. M. (2011). Organic Chemistry. Organic Chemistry, 7(3); 175–179
Doyle, A. A. and J. C. Stephens (2019). A Review of Cinnamaldehyde and Its Derivatives as Antibacterial Agents. Fitoterapia, 139; 104405
Gan, Z., J. Huang, J. Chen, M. F. Nisar, and W. Qi (2020). Synthesis and Antifungal Activities of Cinnamaldehyde Derivatives against Penicillium Digitatum Causing Citrus Green Mold. Journal of Food Quality, 2020; 1–7
Guzman, J. D. (2014). Natural Cinnamic Acids, Synthetic Derivatives and Hybrids with Antimicrobial Activity. Molecules, 19(12); 19292–19349
Hameed, A., M. al Rashida, M. Uroos, S. Abid Ali, and K. M. Khan (2017). Schiff Bases in Medicinal Chemistry: A Patent Review (2010-2015). Expert Opinion on Therapeutic Patents, 27(1); 63–79
Hussain, Z., E. Yousif, A. Ahmed, and A. Altaie (2014). Synthesis and Characterization of Schiff’s Bases of Sulfamethoxazole. Organic and Medicinal Chemistry Letters, 4(1); 2–5
Indriyanti, E. and M. S. Prahasiwi (2020). Synthesis of Cinnamic Acid Based on Perkin Reaction Using Sonochemical Method and Its Potential as a Photoprotective Agent. JKPK (Jurnal Kimia dan Pendidikan Kimia), 5(1); 54
Jezuita, A., H. Szatylowicz, and T. M. Krygowski (2020). How Amino and Nitro Substituents Affect the Aromaticity of Benzene Ring. Chemical Physics Letters, 753; 137567
Kajal, A., S. Bala, S. Kamboj, N. Sharma, and V. Saini (2013). Schiff Bases: A Versatile Pharmacophore. Journal of Catalysts, 2013; 1–14
Nazeruddin, G. M. and Y. I. Shaikh (2014). Tamarind Juice Catalyzed One-Pot Synthesis of Dihydropyrimidinone and Thione under Ultrasound Irradiation at Ambient Conditions: A Green Approach. Der Pharmacia Sinica, 5(6); 64–68
Nigam, M., D. Tuttle, B. Morra, A. P. Dicks, and J. Rodriguez (2023). Putting the Squeeze on Imine Synthesis: Citrus Juice as a Reaction Medium in the Introductory Organic Laboratory. Green Chemistry Letters and Reviews, 16(1); 2185107
Omprakash, B. G., M. Pharm, O. G. Bhusnure, Y. BVibhute, P. S. Giram, and A. Y. Vibhute (2015). Innovative Green Synthesis of Schiff Bases and Their Antimicrobial Activity. Journal of Pharmacy Research, 9(12); 670–677
Patel, G., A. R. Patel, T. L. Lambat, and S. Banerjee (2021). Direct One-Pot Synthesis of Imines/Benzothiazoles/Benzoxazoles from Nitroarenes via Sequential Hydrogenation Condensation Using Nano-NiFe2O4 as Catalyst under Microwave Irradiation. Current Research in Green and Sustainable Chemistry, 4; 100149
Rashdan, H. R. M., S. M. Nasr, H. A. El-Refai, and M. S. Abdel-Aziz (2017). A Novel Approach of Potent Antioxidant and Antimicrobial Agents Containing Coumarin Moiety Accompanied with Cytotoxicity Studies on the Newly Synthesized Derivatives. Journal of Applied Pharmaceutical Science, 7(7); 186–196
Shaikh, S. K. J., R. R. Kamble, S. M. Somagond, A. A. Kamble, and M. N. Kumbar (2018). One-Pot Multicomponent Synthesis of Novel Thiazol-2-imines via Microwave Irradiation and Their Antifungal Evaluation. Synthetic Communications, 48(16); 2061–2073
Silva, W. A., C. K. Z. Andrade, H. B. Napolitano, I. Vencato, C. Lariucci, M. M. R. C. De Castro, and A. J. Camargo (2013). Biological and Structure-Activity Evaluation of Chalcone Derivatives against Bacteria and Fungi. Journal of the Brazilian Chemical Society, 24(1); 133–144
Supriana, T., T. C. Pane, and M. Khaliqi (2022). Export of Indonesian Cinnamon in International Market: Competitive and Performance. Journal of Central European Agriculture, 23(3); 704–713
Suryanti, V., F. R. Wibowo, and S. Handayani (2020a). Methyl-3-(2-Hydroxy-5-Nitrophenyl Amino)-3-Phenylpropanoate Based Colorimetric Sensor for Oxyanions. Indonesian Journal of Chemistry, 20(2); 257–263
Suryanti, V., F. R. Wibowo, S. Khotijah, and N. Andalucki (2018). Antioxidant Activities of Cinnamaldehyde Derivatives. IOP Conference Series: Materials Science and Engineering, 333(1); 012077
Suryanti, V., F. R. Wibowo, A. Marzuki, and M. R. K. Sari (2020b). Cation Sensing Capabilities of a Nitrophenyl Cinnamaldehyde Derivative. Molekul, 15(3); 191–198
Ubani, O. C., N. C. Oforka, R. I. Ngochindo, and L. O. Odokuma (2015). Synthesis, Characterization, and Antimicrobial Studies of Cinnamaldehydebenzylamine Schiff Base Metal Ion Complexes. Research Journal of Chemical Sciences, 5(6); 64–68
Wahab, A., S. S. Haider, and S. K. Sherwani (2017). A Facile and Environmentally Friendly Synthesis of Arylaldimines and Their Significant Antimicrobial, Antioxidant, and Enzyme Inhibition Activities. FUUAST Journal of Biology, 7(2); 207–225
Yaseen, O. K. and M. T. Mohammed (2020). Effects of Cinnamon and Their Beneficial Content on Treatment of Oxidative Stress. Systematic Reviews in Pharmacy, 11(9); 847–850
Authors
Setyono, H. A., Suryanti, V., Putri, A. U., & Koketsu, M. (2024). Modification Structure of Cinnamaldehyde with Primary Amines by Reflux and Sonication Methods in the Presence of Sulfuric Acid as a Catalyst. Science and Technology Indonesia, 9(3), 586–593. https://doi.org/10.26554/sti.2024.9.3.586-593
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