Box-Behnken experimental design for optimizing process parameters in carbonate-promoted direct thiophene carboxylation reaction with carbon dioxide

doi:10.1016/j.cjche.2022.09.007

Abstract

Abstract: A feasible synthesis route is developed for achieving the direct carboxylation of thiophene and CO₂ in a relatively mild solvent-free carboxylate-assisted carbonate (semi) molten state. The effects of reaction factors on the carboxylate yield are investigated in the preliminary screening experiments, and the phase behavior analysis of the reaction medium is detected through the thermal characterization analysis of in-situ high temperature X-ray diffraction measurement (in-situ XRD). The application of response surface methodology (RSM) based on the Box-Behnken design (BBD) is conducted to investigate the effect of the reaction parameters, such as reaction temperature, carbonate proportion, CO₂ pressure and thiophene amount, on the product yield. The regressed second-order polynomial model equation well correlates all the independent variables. The analysis of variance (ANOVA) results reveal that the quadratic effect of reaction temperature is the most effective parameter in this carboxylation reaction owing to it’s the highest contribution to the sum of square (30.18%). The optimum reaction conditions for maximum product yield are the reaction temperature of 287 ℃, carbonate proportion of 32.20%, CO₂ pressure of 1.0MPa and thiophene amount of 9.35 mmol. Operating under these selected experimental conditions, a high product yield (50.98%) can be achieved.

Key words: Carboxylation, Solvent-free medium, Molten salt, Optimization, Response surface methodology

摘要： A feasible synthesis route is developed for achieving the direct carboxylation of thiophene and CO₂ in a relatively mild solvent-free carboxylate-assisted carbonate (semi) molten state. The effects of reaction factors on the carboxylate yield are investigated in the preliminary screening experiments, and the phase behavior analysis of the reaction medium is detected through the thermal characterization analysis of in-situ high temperature X-ray diffraction measurement (in-situ XRD). The application of response surface methodology (RSM) based on the Box-Behnken design (BBD) is conducted to investigate the effect of the reaction parameters, such as reaction temperature, carbonate proportion, CO₂ pressure and thiophene amount, on the product yield. The regressed second-order polynomial model equation well correlates all the independent variables. The analysis of variance (ANOVA) results reveal that the quadratic effect of reaction temperature is the most effective parameter in this carboxylation reaction owing to it’s the highest contribution to the sum of square (30.18%). The optimum reaction conditions for maximum product yield are the reaction temperature of 287 ℃, carbonate proportion of 32.20%, CO₂ pressure of 1.0MPa and thiophene amount of 9.35 mmol. Operating under these selected experimental conditions, a high product yield (50.98%) can be achieved.

关键词: Carboxylation, Solvent-free medium, Molten salt, Optimization, Response surface methodology

Qingjun Zhang, Youguang Ma, Xigang Yuan, Aiwu Zeng. Box-Behnken experimental design for optimizing process parameters in carbonate-promoted direct thiophene carboxylation reaction with carbon dioxide[J]. Chinese Journal of Chemical Engineering, 2022, 50(10): 222-234.

References

[1] Yano Hiroshi, Okamoto Tetsuhiko. Preparation of thiophenecarboxylic acid, JP Pat., 58029783(1983)
[2] George C., Johnson, Woodbury, John W. Production of thiophenecarboxylic acid, US Pat.,2492645 (1949)
[3] H.C. Guo, The environmental-friendly synthesis of 2-thiophenecarboxylic acid, Chem. Intermed. (2007) (12)13-14, 7, 20
[4] T. Sakakura, J.C. Choi, H. Yasuda, Transformation of carbon dioxide, Chem. Rev. 107 (6) (2007) 2365-2387. https://pubmed.ncbi.nlm.nih.gov/17564481/
[5] J.F. Luo, I. Larrosa, C-H carboxylation of aromatic compounds through CO₂ fixation, ChemSusChem 10 (17) (2017) 3317-3332. https://pubmed.ncbi.nlm.nih.gov/28722818/
[6] J.T. Hong, M. Li, J.N. Zhang, B.Q. Sun, F.Y. Mo, C-H bond carboxylation with carbon dioxide, ChemSusChem 12 (1) (2019) 6-39. https://pubmed.ncbi.nlm.nih.gov/30381905/
[7] A.H. Liu, B. Yu, L.N. He, Catalytic conversion of carbon dioxide to carboxylic acid derivatives, Greenh. Gases Sci. Technol. 5 (1) (2015) 17-33. http://dx.doi.org/10.1002/ghg.1461
[8] G.A. Olah, B. Török, J.P. Joschek, I. Bucsi, P.M. Esteves, G. Rasul, G.K. Surya Prakash, Efficient chemoselective carboxylation of aromatics to arylcarboxylic acids with a superelectrophilically activated carbon dioxide-Al(2)Cl(6)/Al system, J. Am. Chem. Soc. 124 (38) (2002) 11379-11391. https://pubmed.ncbi.nlm.nih.gov/12236753/
[9] P. Munshi, E.J. Beckman, Effect of incubation of CO₂ and lewis acid on the generation of toluic acid from toluene and CO₂, Ind. Eng. Chem. Res. 48 (2) (2009) 1059-1062. https://doi.org/10.1021/ie801524e
[10] P. Munshi, E.J. Beckman, S. Padmanabhan, Combined influence of fluorinated solvent and base in Friedel-Crafts reaction of toluene and CO₂, Ind. Eng. Chem. Res. 49 (14) (2010) 6678-6682. https://doi.org/10.1021/ie100533c
[11] K. Nemoto, H. Yoshida, N. Egusa, N. Morohashi, T. Hattori, Direct carboxylation of arenes and halobenzenes with CO₂ by the combined use of AlBr₃ and R₃SiCl, J. Org. Chem. 75 (22) (2010) 7855-7862. https://pubmed.ncbi.nlm.nih.gov/21033692/
[12] K. Nemoto, S. Onozawa, N. Egusa, N. Morohashi, T. Hattori, Carboxylation of indoles and pyrroles with CO₂ in the presence of dialkylaluminum halides, Tetrahedron Lett. 50 (31) (2009) 4512-4514. http://dx.doi.org/10.1016/j.tetlet.2009.05.076
[13] K. Nemoto, S. Onozawa, M. Konno, N. Morohashi, T. Hattori, Direct carboxylation of thiophenes and benzothiophenes with the aid of EtAlCl₂, Bull. Chem. Soc. Jpn. 85 (3) (2012) 369-371. https://doi.org/10.1246/bcsj.20110335
[14] S. Tanaka, K. Watanabe, Y. Tanaka, T. Hattori, EtAlCl₂/2, 6-disubstituted pyridine-mediated carboxylation of alkenes with carbon dioxide, Org. Lett. 18 (11) (2016) 2576-2579. https://pubmed.ncbi.nlm.nih.gov/27187716/
[15] X.B. Zhang, Z.M. Cheng, Performance of combined use of chlorosilanes and AlCl₃ in the carboxylation of toluene with CO₂, Aiche J. 63 (1) (2017) 185-191. http://dx.doi.org/10.1002/aic.15519
[16] I.I. Boogaerts, S.P. Nolan, Carboxylation of C-H bonds using N-heterocyclic carbene gold(I) complexes, J. Am. Chem. Soc. 132 (26) (2010) 8858-8859. https://pubmed.ncbi.nlm.nih.gov/20540522/
[17] I.I. Boogaerts, G.C. Fortman, M.R. Furst, C.S. Cazin, S.P. Nolan, Carboxylation of N-H/C-H bonds using N-heterocyclic carbene copper(I) complexes, Angewandte Chemie Int. Ed Engl. 49 (46) (2010) 8674-8677. https://pubmed.ncbi.nlm.nih.gov/20886489/
[18] W.J. Yoo, M.G. Capdevila, X. Du, S. Kobayashi, Base-mediated carboxylation of unprotected indole derivatives with carbon dioxide, Org. Lett. 14 (20) (2012) 5326-5329. https://pubmed.ncbi.nlm.nih.gov/23035967/
[19] S. Fenner, L. Ackermann, C-H carboxylation of heteroarenes with ambient CO₂, Green Chem. 18 (13) (2016) 3804-3807. https://doi.org/10.1039/c6gc00200e
[20] M. Shigeno, K. Hanasaka, K. Sasaki, K. Nozawa-Kumada, Y. Kondo, Direct carboxylation of electron-rich heteroarenes promoted by LiO-tBu with CsF and[18]crown-6, Chemistry 25 (13) (2019) 3235-3239. https://pubmed.ncbi.nlm.nih.gov/30637844/
[21] M. Shigeno, K. Sasaki, K. Nozawa-Kumada, Y. Kondo, Double-carboxylation of two C-H bonds in 2-alkylheteroarenes using LiO-t-bu/CsF, Org. Lett. 21 (12) (2019) 4515-4519. http://dx.doi.org/10.1021/acs.orglett.9b01386
[22] Shigeno M, Tohara I, Kumada-Nozawa K, Kondo Y. Direct C-2 carboxylation of 3-substituted indoles using a combined Brønsted base consisting of LiO-tBu/CsF/18-crown-6. European Journal of Organic chemistry, 2020, 2020(13) 1987-1991
[23] O. Vechorkin, N. Hirt, X.L. Hu, Carbon dioxide as the C1 source for direct C-H functionalization of aromatic heterocycles, Org. Lett. 12 (15) (2010) 3567-3569. https://pubmed.ncbi.nlm.nih.gov/20670021/
[24] A. Banerjee, G.R. Dick, T. Yoshino, M.W. Kanan, Carbon dioxide utilization via carbonate-promoted C-H carboxylation, Nature 531 (7593) (2016) 215-219. https://pubmed.ncbi.nlm.nih.gov/26961655/
[25] G.R. Dick, A.D. Frankhouser, A. Banerjee, M.W. Kanan, A scalable carboxylation route to furan-2, 5-dicarboxylic acid, Green Chem. 19 (13) (2017) 2966-2972. https://doi.org/10.1039/c7gc01059a
[26] A.W. Lankenau, M.W. Kanan, Polyamide monomers via carbonate-promoted C-H carboxylation of furfurylamine, Chem. Sci. 11 (1) (2019) 248-252. https://pubmed.ncbi.nlm.nih.gov/34040718/
[27] K. Shen, Y. Fu, J.N. Li, L. Liu, Q.X. Guo, What are the pKa values of C-H bonds in aromatic heterocyclic compounds in DMSO? Tetrahedron 63 (7) (2007) 1568-1576. http://dx.doi.org/10.1016/j.tet.2006.12.032
[28] A.D. Frankhouser, M.W. Kanan, Phase behavior that enables solvent-free carbonate-promoted furoate carboxylation, J. Phys. Chem. Lett. 11 (18) (2020) 7544-7551. https://pubmed.ncbi.nlm.nih.gov/32812764/
[29] R.F. Gunst, R.H. Myers, D.C. Montgomery, Response surface methodology:Process and product optimization using designed experiments, Technometrics 38 (3) (1996) 285. https://doi.org/10.2307/1270613
[30] M.V. Gil, M. Martínez, S. García, F. Rubiera, J.J. Pis, C. Pevida, Response surface methodology as an efficient tool for optimizing carbon adsorbents for CO₂ capture, Fuel Process. Technol. 106 (2013) 55-61. http://dx.doi.org/10.1016/j.fuproc.2012.06.018
[31] Yang J. H., Feng J. G., Sun C. C., Chen W., Ma Y. J., Chen Z. Y., Dong S., Deng W. Process optimization for the preparation of beta-cyhalothrin microspheres by using the response surface methodology. Journal of Polymers and the Environment, 2021, 29:3145-3153
[32] S. Polat, P. Sayan, Application of response surface methodology with a Box-Behnken design for struvite precipitation, Adv. Powder Technol. 30 (10) (2019) 2396-2407. http://dx.doi.org/10.1016/j.apt.2019.07.022
[33] S.S. Chen, Z. Zeng, N. Hu, B. Bai, H.L. Wang, Y.R. Suo, Simultaneous optimization of the ultrasound-assisted extraction for phenolic compounds content and antioxidant activity of Lycium ruthenicum Murr. fruit using response surface methodology, Food Chem. 242 (2018) 1-8. https://pubmed.ncbi.nlm.nih.gov/29037664/
[34] Y.G. Wang, C.Y. Guo, J. Shen, Y.Q. Sun, Y.X. Niu, P. Li, G. Liu, X.Y. Wei, A sustainable and green route to furan-2, 5-dicarboxylic acid by direct carboxylation of 2-furoic acid and CO₂, J. CO₂ Util. 48 (2021) 101524. http://dx.doi.org/10.1016/j.jcou.2021.101524
[35] Z.T. Alismaeel, A.H. Abbar, O.F. Saeed, Application of central composite design approach for optimisation of zinc removal from aqueous solution using a Flow-by fixed bed bioelectrochemical reactor, Sep. Purif. Technol. 287 (2022) 120510. http://dx.doi.org/10.1016/j.seppur.2022.120510
[36] E. Ahmadi, B. Shokri, A. Mesdaghinia, R. Nabizadeh, M. Reza Khani, S. Yousefzadeh, M. Salehi, K. Yaghmaeian, Synergistic effects of α-Fe₂O₃-TiO₂ and Na₂S₂O₈ on the performance of a non-thermal plasma reactor as a novel catalytic oxidation process for dimethyl phthalate degradation, Sep. Purif. Technol. 250 (2020) 117185. http://dx.doi.org/10.1016/j.seppur.2020.117185
[37] A. Özer, G. Gürbüz, A. Çalimli, B.K. Körbahti, Biosorption of copper(II) ions on Enteromorpha prolifera:Application of response surface methodology (RSM), Chem. Eng. J. 146 (3) (2009) 377-387. https://doi.org/10.1016/j.cej.2008.06.041