Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

doi:10.1016/j.cjche.2024.03.026

Abstract

Abstract: Daidzein has been widely used in pharmaceuticals, nutraceuticals, cosmetics, feed additives, etc. Its preparation process and related reaction mechanism need to be further investigated. A cost-effective process for synthesizing daidzein was developed in this work. In this article, a two-step synthesis of daidzein (Friedel–Crafts acylation and [5+1] cyclization) was developed via the employment of trifluoromethanesulfonic acid (TfOH) as an effective promoting reagent. The effect of reaction conditions such as solvent, the amount of TfOH, reaction temperature, and reactant ratio on the conversion rate and the yield of the reaction, respectively, was systematically investigated, and daidzein was obtained in 74.0% isolated yield under optimal conditions. Due to the facilitating effect of TfOH, the Friedel–Crafts acylation was completed within 10 min at 90 °C and the [5+1] cyclization was completed within 180 min at 25 °C. In addition, a possible reaction mechanism for this process was proposed. The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Key words: Synthesis, Optimal design, Chemical processes, Reaction mechanism

摘要： Daidzein has been widely used in pharmaceuticals, nutraceuticals, cosmetics, feed additives, etc. Its preparation process and related reaction mechanism need to be further investigated. A cost-effective process for synthesizing daidzein was developed in this work. In this article, a two-step synthesis of daidzein (Friedel–Crafts acylation and [5+1] cyclization) was developed via the employment of trifluoromethanesulfonic acid (TfOH) as an effective promoting reagent. The effect of reaction conditions such as solvent, the amount of TfOH, reaction temperature, and reactant ratio on the conversion rate and the yield of the reaction, respectively, was systematically investigated, and daidzein was obtained in 74.0% isolated yield under optimal conditions. Due to the facilitating effect of TfOH, the Friedel–Crafts acylation was completed within 10 min at 90 °C and the [5+1] cyclization was completed within 180 min at 25 °C. In addition, a possible reaction mechanism for this process was proposed. The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

关键词: Synthesis, Optimal design, Chemical processes, Reaction mechanism

Hai Cao, Haibin Yang, Yanxiong Fang, Yuandi Zeng, Xiaolan Cai, Jingjing Ma. Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism[J]. Chinese Journal of Chemical Engineering, 2024, 71(7): 132-139.

References

[1] Y. He, W.J. Niu, C.Q. Xia, B.H. Cao, Daidzein reduces the proliferation and adiposeness of 3T3-L1 preadipocytes via regulating adipogenic gene expression, J. Funct. Foods 22 (2016) 446-453.
[2] S.H. Nile, A. Nile, J.W. Oh, G.Y. Kai, Soybean processing waste: Potential antioxidant, cytotoxic and enzyme inhibitory activities, Food Biosci. 38 (2020) 100778.
[3] A.P. Laddha, Y.A. Kulkarni, Pharmacokinetics, pharmacodynamics, toxicity, and formulations of daidzein: An important isoflavone, Phytother. Res. 37 (6) (2023) 2578-2604.
[4] J.C. Shu, L.Z. Hu, Y.C. Wu, L. Chen, K. Huang, Z.H. Wang, M.L. Liang, Daidzein suppresses TGF-β1-induced cardiac fibroblast activation via the TGF-β1/SMAD2/3 signaling pathway, Eur. J. Pharmacol. 919 (2022) 174805.
[5] X.H. Zhao, Z.D. Chen, S. Zhou, X.Z. Song, K.H. Ouyang, K. Pan, L.J. Xu, C.J. Liu, M.R. Qu, Effects of daidzein on performance, serum metabolites, nutrient digestibility, and fecal bacterial community in bull calves, Anim. Feed. Sci. Technol. 225 (2017) 87-96.
[6] H.M. Xie, E. Yu, H.M. Wen, B.Y. Jiang, G.H. Fu, H.T. Sun, J. He, Maternal daidzein supplementation during lactation promotes growth performance, immunity, and intestinal health in neonatal rabbits, Agriculture 13 (9) (2023) 1654.
[7] F.C. Stintzing, M. Hoffmann, R. Carle, Thermal degradation kinetics of isoflavone aglycones from soy and red clover, Mol. Nutr. Food Res. 50 (4-5) (2006) 373-377.
[8] J. Liggins, A. Mulligan, S. Runswick, S.A. Bingham, Daidzein and genistein content of cereals, Eur. J. Clin. Nutr. 56 (10) (2002) 961-966.
[9] J. Liggins, L.J.C. Bluck, S. Runswick, C. Atkinson, W.A. Coward, S.A. Bingham, Daidzein and genistein content of fruits and nuts, J. Nutr. Biochem. 11 (6) (2000) 326-331.
[10] S.H. Nile, B. Venkidasamy, R. Samynathan, A. Nile, K. Shao, T. Chen, M. Sun, M.U. Khan, N. Dutta, M. Thiruvengadam, M.A. Shariati, M. Rebezov, G. Kai, Soybean processing wastes: Novel insights on their production, extraction of isoflavones, and their therapeutic properties, J. Agric. Food Chem. 70 (23) (2022) 6849-6863.
[11] W.D. Ollis, K.L. Ormand, I.O. Sutherland, The oxidative rearrangement of chalcones by thallic acetate: A chemical analogy for isoflavone biosynthesis, Chem. Commun. (London) (20) (1968) 1237.
[12] L. Farkas, A. Gottsegen, M. Noagradi, S. Antus, Synthesis of sophorol, violanone, lonchocarpan, claussequinone, philenopteran, leiocalycin, and some other natural isoflavonoids by the oxidative rearrangement of chalcones with thallium(III) nitrate, J. Chem. Soc., Perkin Trans. 1 (1974) 305-312.
[13] N. Al-Maharik, N.P. Botting, A versatile synthesis of[2, 3, 4-¹³C₃]isoflavones, J. Label. Compd. Radiopharm. 53 (3) (2010) 95-103.
[14] F.X. Felpin, Practical and efficient Suzuki-Miyaura cross-coupling of 2-iodocycloenones with arylboronic acids catalyzed by recyclable Pd(0)/C, J. Org. Chem. 70 (21) (2005) 8575-8578.
[15] K.F. Biegasiewicz, J.D.S. Denis, V.M. Carroll, R. Priefer, An efficient synthesis of daidzein, dimethyldaidzein, and isoformononetin, Tetrahedron Lett. 51 (33) (2010) 4408-4410.
[16] K.F. Biegasiewicz, J.S. Gordon, D.A. Rodriguez, R. Priefer, Development of a general approach to the synthesis of a library of isoflavonoid derivatives, Tetrahedron Lett. 55 (37) (2014) 5210-5212.
[17] J.P. Wan, Z. Tu, Y.Y. Wang, Transient and recyclable halogenation coupling (TRHC) for isoflavonoid synthesis with site-selective arylation, Chemistry 25 (28) (2019) 6907-6910.
[18] K. Wahala, T.A. Hase, Expedient synthesis of polyhydroxyisoflavones, J. Chem. Soc., Perkin Trans. 1 (12) (1991) 3005-3008.
[19] S. Balasubramanian, M.G. Nair, An efficient “one pot” synthesis of isoflavones, Synth. Commun. 30 (3) (2000) 469-484.
[20] S. Sepulveda-Boza, G. H. Walizei, M. C. Rezende, Y. Vasquez, C. Mascayano, L. Mejias. The Preparation of New Isoflavones. Synth. Commun. 31 (12) (2001) 1933-1940.
[21] W.M. Li, F.M. Liu, P.F. Zhang, Synthesis of isoflavones via base catalysed condensation reaction of deoxybenzoin, J. Chem. Res. 2008 (12) (2008) 683-685.
[22] C. Hai, P. Zhou, J. Ma, Y. Fang, A synthesis method of daidzein. Chinese Pat. CN116332893A (2023).
[23] C. Jin, J. Li, W. Su, Ytterbium triflate catalysed Friedel-Crafts reaction using carboxylic acids as acylating reagents under solvent-free conditions, J. Chem. Res. 2009 (2009) 607-611.
[24] G.C. Liu, B. Xu, Hydrogen bond donor solvents enabled metal and halogen-free Friedel-Crafts acylations with virtually no waste stream, Tetrahedron Lett. 59 (10) (2018) 869-872.
[25] J.C. Onwuka, E.B. Agbaji, V.O. Ajibola, F.G. Okibe, Thermodynamic pathway of lignocellulosic acetylation process, BMC Chem. 13 (1) (2019) 79.
[26] M.O. Adebajo, R.L. Frost, Acetylation of raw cotton for oil spill cleanup application: An ftir and 13c mas nmr spectroscopic investigation, Spectrochim. Acta A Mol. Biomol. Spectrosc. 60 (10) (2004) 2315-2321.
[27] S.R. Koppolu, N. Naveen, R. Balamurugan, Triflic acid promoted direct α-alkylation of unactivated ketones using benzylic alcohols via in situ formed acetals, J. Org. Chem. 79 (13) (2014) 6069-6078.
[28] Q.M. Zhang, P. Mischnick, Borate-mediated stereo- and topo-selective methylation of 1, 4-β-glucomannan, Macromol. Chem. Phys. 219 (6) (2018) 1700502.
[29] A. Mahmood, T. Akram, M. Kiani, T. Akram, X.Q. Tian, Y.W. Sun, Mechanism and regioselectivity in methylation of nitronates[CH₂NO₂]^-: resonance vs. inductive effects, New J. Chem. 46 (34) (2022) 16593-16602.
[30] Y. Wang, Y. Yuan, C.H. Xing, L. Lu, Trifluoromethanesulfonic acid-catalyzed solvent-free bisindolylation of trifluoromethyl ketones, Tetrahedron Lett. 55 (5) (2014) 1045-1048.
[31] M. Guisnet, D.B. Lukyanov, F. Jayat, P. Magnoux, I. Neves, Kinetic modeling of phenol acylation with acetic acid on HZSM5, Ind. Eng. Chem. Res. 34 (5) (1995) 1624-1629.
[32] M.K. Montanez Valencia, C.L. Padro, M.E. Sad, Gas phase acylation of guaiacol with acetic acid on acid catalysts, Appl. Catal. B Environ. 278 (2020) 119317.
[33] I. Neves, F. Jayat, P. Magnoux, G. Perot, F.R. Ribeiro, M. Gubelmann, M. Guisnet, Acylation of phenol with acetic acid over a HZSM5 zeolite, reaction scheme, J. Mol. Catal. 93 (2) (1994) 169-179.
[34] A.J. Hoefnagel, H. van Bekkum, Direct fries reaction of resorcinol with benzoic acids catalyzed by zeolite H-beta, Appl. Catal. A Gen. 97 (2) (1993) 87-102.
[35] F. Jayat, M.J. Sabater Picot, M. Guisnet, Solvent effects in liquid phase Fries rearrangement of phenyl acetate over a HBEA zeolite, Catal. Lett. 41 (3) (1996) 181-187.
[36] S.F. Teloxa, S.C.D. Kennington, M. Camats, P. Romea, F. Urpi, G. Aullon, M. Font-Bardia, Direct, enantioselective, and nickel(II) catalyzed reactions of N-azidoacetyl thioimides with trimethyl orthoformate: A new combined methodology for the rapid synthesis of lacosamide and derivatives, Chem. 26 (50) (2020) 11540-11548.
[37] Y. Janin, C. Huel, G. Flad, S. Thirot, Methyl orthocarboxylates as methylating agents of heterocycles, Eur. J. Org. Chem. 2002 (11) (2002) 1763-1769.