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Assessments on the transition metal salt-catalyzed β-citronellal condensation reactions with alkyl alcohols

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Abstract

In this work, inexpensive and simple commercial transition metal salts were evaluated as catalysts in the acetalization of alkyl alcohols with β-citronellal, a renewable origin substrate. After an initial screening, FeCl3 was the most active and selective catalyst among the various transition metal salts evaluated toward the β-citronellal methyl acetal. The impacts of main reaction parameters such as time, temperature, catalyst load, and type of alcohol on conversion and selectivity of the reactions were investigated. Different iron salts were also investigated. It was demonstrated that both oxidation number and type of anion present in the salt play an essential role in this reaction. Notably, the dissolution of catalyst salts in solution triggered a decrease in the pH of the medium due to the hydrolysis (and or solvolysis) of the metal cation, impacting the conversion and reaction selectivity. The highest activity of FeCl3 was assigned to the greatest Lewis acidity strength, as demonstrated by the acidity measurements. This inexpensive, low-corrosive, and commercially affordable catalyst has advantages over traditional liquid mineral acid catalysts and provides an alternative route to synthesize alkyl terpene acetals.

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References

  1. Lenardão EJ, Botteselle GV, De Azambuja F, Perin G, Jaco RG (2007) Citronellal as a key compound in organic synthesis. Tetrahedron 63:6671–6712. https://doi.org/10.1016/j.tet.2007.03.159

    Article  CAS  Google Scholar 

  2. Tsolakis N, Bam W, Srai JS, Kumar M (2019) Renewable chemical feedstock supply network design: The case of terpenes. J Clean Prod 222:802–822. https://doi.org/10.1016/j.jclepro.2019.02.108

    Article  CAS  Google Scholar 

  3. Wu L, Moteki T, Gokhale AA, Flaherty DW, Toste FD (2016) Production of fuels and chemicals from biomass: condensation reactions and beyond. Chem 1:32–58. https://doi.org/10.1016/j.chempr.2016.05.002

    Article  CAS  Google Scholar 

  4. Sanchez LM, Thomas HJ, Climent MJ et al (2016) Heteropolycompounds as catalysts for biomass product transformations. Catal Rev 58:497–586. https://doi.org/10.1080/01614940.2016.1248721

    Article  CAS  Google Scholar 

  5. Hamada N, Kazahaya K, Shimizu H, Sato T (2004) An efficient and versatile procedure for the synthesis of acetals from aldehydes and ketones catalyzed by lithium tetrafluoroborate. Synlett. https://doi.org/10.1055/s-2004-820038

    Article  Google Scholar 

  6. Dong J-L, Yu L-S-H, Xie J-W (2018) A Simple and versatile method for the formation of Acetals/Ketals Using trace conventional acids. ACS Omega 3:4974–4985. https://doi.org/10.1021/acsomega.8b00159

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  7. Corma A, García H (2003) Lewis acids: from conventional homogeneous to green homogeneous and heterogeneous catalysis. Chem Rev 103:4307–4366. https://doi.org/10.1021/cr030680z

    Article  PubMed  CAS  Google Scholar 

  8. Wegenhart BL, Liu S, Thom M, Stanley D, Abu-Omar MM (2012) Solvent-free methods for making acetals derived from glycerol and furfural and their use as a biodiesel fuel component. ACS Catal 2:2524–2530. https://doi.org/10.1021/cs300562e

    Article  CAS  Google Scholar 

  9. Umbarkar SB, Kotbagi TV, Biradar AV, Pasricha R, Chanale J, Dongare MK, Mamede A-S, Lancelot C, Payen E (2009) Acetalization of glycerol using mesoporous MoO3/SiO2 solid acid catalyst. J Mol Catal A 310:150–158. https://doi.org/10.1016/j.molcata.2009.06.010

    Article  CAS  Google Scholar 

  10. Leonard NM, Oswald MC, Freiberg DA, Nattier BA, Smith RC, Mohan RS (2002) A simple and versatile method for the synthesis of Acetals from aldehydes and ketones using bismuth triflate. J Org Chem 67:5202–5207. https://doi.org/10.1021/jo0258249

    Article  PubMed  CAS  Google Scholar 

  11. Smith BM, Graham AE (2011) Indium triflate mediated tandem acetalisation-acetal exchange reactions under solvent-free conditions. Tetrahedron Lett 52:6281–6283. https://doi.org/10.1016/j.tetlet.2011.09.087

    Article  CAS  Google Scholar 

  12. Smith BM, Kubczyk TM, Graham AE (2012) Indium(III) triflate catalysed transacetalisation reactions of diols and triols under solvent-free conditions. Tetrahedron 68:7775–7781. https://doi.org/10.1016/j.tet.2012.07.048

    Article  CAS  Google Scholar 

  13. Cooks RG, Chen H, Eberlin MN, Zheng X, Tao WA (2006) Polar acetalization and transacetalization in the gas phase: the Eberlin reaction. Chem Rev 106:188–211. https://doi.org/10.1021/cr0400921

    Article  PubMed  CAS  Google Scholar 

  14. Zhu Z, Espenson JH (1997) Organometallic catalysis: formation of 1,3-dioxolanes and their analogs catalyzed by methylrhenium trioxide (MTO). Organometallics 16:3658–3663. https://doi.org/10.1021/om970225r

    Article  CAS  Google Scholar 

  15. Clerici A, Pastori N, Porta O (2001) Mild acetalisation of mono and dicarbonyl compounds catalysed by titanium tetrachloride. Facile synthesis of β-keto enol ethers. Tetrahedron 57:217–225. https://doi.org/10.1016/S0040-4020(00)01001-2

    Article  CAS  Google Scholar 

  16. da Silva MJ, de Oliveira CM (2021) Metal nitrate-catalyzed one-pot oxidative esterification of benzaldehyde with hydrogen peroxide in alcoholic solutions at room temperature. New J Chem 45:3683–3691. https://doi.org/10.1039/D0NJ05671E

    Article  Google Scholar 

  17. da Silva MJ, Ayala DAM (2016) Unravelling transition metal-catalyzed terpenic alcohol esterification: a straightforward process for the synthesis of fragrances. Catal Sci Technol 6:3197–3207. https://doi.org/10.1039/C5CY01538C

    Article  CAS  Google Scholar 

  18. Martins FP, Rodrigues FA, da Silva MJ (2018) Fe2(SO4)3-catalyzed Levulinic acid esterification: production of fuel bioadditives. Energies 11:1263. https://doi.org/10.3390/en11051263

    Article  CAS  Google Scholar 

  19. da Silva MJ, Julio AA, Ayala DAM, de Miranda LMP (2018) Fe2(SO4)3-catalyzed synthesis of terpenic alcohols esters: a simple and bifunctional reusable solid catalyst. ChemSelect 3:5742–5748. https://doi.org/10.1002/slct.201800643

    Article  CAS  Google Scholar 

  20. da Silva MJ, Carari DM, da Silva AM (2015) Fe(III)-catalyzed α-terpinyl derivatives synthesis from β-pinene via reactions with hydrogen peroxide in alcoholic solutions. RSC Adv 5:10529–10536. https://doi.org/10.1039/C4RA13112F

    Article  CAS  Google Scholar 

  21. Carari DM, da Silva MJ (2014) Fe(NO3)3-catalyzed monoterpene oxidation by hydrogen peroxide: an inexpensive and environmentally benign oxidative process. Catal Lett 144:615–622. https://doi.org/10.1007/s10562-013-1189-x

    Article  CAS  Google Scholar 

  22. da Silva MJ, Teixeira MG (2018) Assessment on the double role of the transition metal salts on the acetalization of furfural: Lewis and Brønsted acid catalysts. Mol Catal 461:40–47. https://doi.org/10.1016/j.mcat.2018.10.002

    Article  CAS  Google Scholar 

  23. da Silva M, Silva G, Sampaio V et al (2020) One-pot synthesis of benzaldehyde derivatives in PdCl2-catalyzed reactions with H2O2 in alcoholic solutions. Chem Pap. https://doi.org/10.1007/s11696-020-01408-7

    Article  Google Scholar 

  24. da Silva MJ, de Ávila RF, Júlio AA (2017) SnF2-catalyzed glycerol ketalization: a friendly environmentally process to synthesize solketal at room temperature over on solid and reusable Lewis acid. Chem Engin J 307:828–835. https://doi.org/10.1016/j.cej.2016.09.002

    Article  CAS  Google Scholar 

  25. Cardoso AL, Neves SCG, da Silva MJ (2009) Kinetic study of alcoholysis of the fatty acids catalyzed by tin chloride(II): an alternative catalyst for biodiesel production. Energ Fuels 23:1718–1722. https://doi.org/10.1021/ef800639h

    Article  CAS  Google Scholar 

  26. Karamé I, Alamé M, Kanj A, Baydoun GN, Hazimeh H, el Masri M, Christ L (2011) Mild and efficient protection of diol and carbonyls as cyclic acetals catalysed by iron (III) chloride. C R Chim 14:525–529. https://doi.org/10.1016/j.crci.2010.12.001

    Article  CAS  Google Scholar 

  27. Zaher S, Christ L, Abd El Rahim M, Kanj A, Karamé I (2017) Green acetalization of glycerol and carbonyl catalyzed by FeCl3·6H2O. Mol Catal 438:204–213. https://doi.org/10.1016/j.mcat.2017.06.006

    Article  CAS  Google Scholar 

  28. da Silva MJ, Ribeiro CJA, Vilanculo CB (2023) How the content of protons and vanadium affects the activity of H3+nPMo12-nVnO40 (n = 0, 1, 2, or 3) catalysts on the oxidative esterification of benzaldehyde with hydrogen peroxide. Catal Lett 153:2045–2056. https://doi.org/10.1007/s10562-022-04132-x

    Article  CAS  Google Scholar 

  29. da Silva MJ, Teixeira MG, Natalino R (2019) Highly selective synthesis under benign reaction conditions of furfural dialkyl acetal using SnCl2 as a recyclable catalyst. New J Chem 43:8606–8612. https://doi.org/10.1039/C9NJ01284B

    Article  Google Scholar 

  30. Krompiec S, Penkala M, Szczubiałka K, Kowalska E (2012) Transition metal compounds and complexes as catalysts in the synthesis of acetals and orthoesters: theoretical, mechanistic and practical aspects. Coordin Chem Rev 256:2057–2095. https://doi.org/10.1016/j.ccr.2012.05.006

    Article  CAS  Google Scholar 

  31. Teixeira MG, Natalino R, da Silva MJ (2020) A kinetic study of heteropolyacid-catalyzed furfural acetalization with methanol at room temperature via ultraviolet spectroscopy. Catal Today 344:143–149. https://doi.org/10.1016/j.cattod.2018.11.071

    Article  CAS  Google Scholar 

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Acknowledgements

The authors are grateful for the financial support from CNPq and FAPEMIG (Brazil). This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES)—Finance Code 001.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior,001,Marcio Silva

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Authors and Affiliations

  1. Chemistry and Physics Department, Federal University of Espírito Santo, Alto Universitário S/N, Bairro Guararema, Alegre, Espírito Santo, 29500-000, Brazil

    Aldino Neto Venâncio, Armanda Aparecida Júlio, Luciana Alves Parreira & Gustavo Rodrigues de Souza

  2. Chemistry Department, Federal Institute of Education, Science and Technology of Minas Gerais, São João Evangelista, Minas Gerais, 39705-000, Brazil

    Cláudio Junior Andrade Ribeiro

  3. Federal Institute of Espírito Santo, BR-482, KM 47, Cachoeiro, Alegre, Espírito Santo Brasil, 29520-000, Brazil

    Luciano Menini

  4. Chemistry Department, Federal University of Viçosa, University Campus, Avenue P.H. Rolfs, Viçosa, Minas Gerais, 36590-000, Brazil

    Márcio José da Silva

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  1. Aldino Neto Venâncio
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Venâncio, A.N., Ribeiro, C.J.A., Júlio, A.A. et al. Assessments on the transition metal salt-catalyzed β-citronellal condensation reactions with alkyl alcohols. Reac Kinet Mech Cat 137, 149–161 (2024). https://doi.org/10.1007/s11144-023-02528-3

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