N-Aroylbenzimidazoles as efficient new reagents for a greener esterification reaction under solvent-free conditions
Keywords:N-aroylbenzimidazoles, aroylation reagent, esterification, grinding.
Due to the increasing demand for green technology and its numerous advantages over conventional methodologies, this work has received interest for the development of a facile and efficient method for the synthesis of esters using benzimidazole chemistry. N-aroylbenzimidazole derivatives 2a-d synthesized herein were found to be highly active acylation reagents, readily leading to high-yielding syntheses of ester products under solvent-free conditions without the need for a catalyst. A wide variety of esterification reactions between alcohols 1a-e and N-aroylbenzimidazoles 2a-d were carried out by grinding the mixtures, which were converted to their ester products 3a-t in a simple synthetic procedure with yields in the range of 84% to 96% and recovery of the by-product benzimidazole (4) (80-93%). Compound 4 can be reused for the preparation of N-aroylbenzimidazoles 2a-d without significant loss of efficiency. The advantages of this current methodology are the simple procedure; the absence of hazardous organic solvents; catalyst- and solvent-free conditions with high yields, low reaction temperatures, and short reaction times; and eco-friendly reactions generating no waste and allowing reagents to be recovered and reused.
Ageshina, A. A., Sterligov, G. K., Rzhevskiy, S. A., Topchiy, M. A., Chesnokov, G. A., Gribanov, P. S., Melnikova, E. K., Nechaev, M. S., Asachenko, A. F. & Bermeshev, M. V. (2019). Mixed er-NHC/phosphine Pd(II) complexes and their catalytic activity in buchwald-hartwig reaction under solvent-free conditions. Dalton Transactions, 48(10), 3447–3452. DOI: 10.1039/c9dt00216b
Asachenko, A. F. (2020). Transition Nazari etal-catalyzed synthesis of functionalized arenes under solvent-free condition. Journal of Nesmeyanov Institute of Organoelement Compounds
of the Russian Academy of Sciences, 3(3), 80–91. DOI: 10.32931/io2014r
Asif, M. (2019). Calcium sensitizing and phosphodiesterase-III inhibitory activity of pyridazine compounds: A review. Journal of Chemical Reviews, 1(1), 47-65. DOI: 10.33945/SAMI/JCR.2019.1.4765
Förtsch, S., & Bäuerle, P. (2017). Synthesis and characterization of two isomeric dithienopyrrole series and the corresponding electropolymers. Polymer Chemistry, 8(23), 3586–3595. DOI:10.1039/c7py00764g
Gautam, N. & Chourasia, O. P. (2012). Synthesis, characterization, antimicrobial, insecticidal and anthelmintic screening of some new s-triazine derivatives of pyrazoline, pyrimidine, isoxazoline and isothiazoline moiety. Indian Journal of Chemistry, 51(9), 1400-1410.
Gribanov, P. S., Chesnokov, G. A., Dzhevakov, P. B., Kirilenko, N. Y., Rzhevskiy, S. A., Ageshina, A. A., Topchiy, M. A., Bermeshev, M. V., Asachenko, A. F. & Nechaev, M. S. (2019). Solvent-free Suzuki and Stille cross-coupling reactions of 4- and 5-halo-1,2,3-triazoles. Mendeleev Communications, 29(2), 147–149. DOI:10.1016/j.mencom.2019.03.009
Gribanov, P. S., Golenko, Y. D., Topchiy, M. A., Minaeva, L. I., Asachenko, A. F. & Nechaev, M. S. (2018). Stannylation of aryl halides, stille cross-coupling, and one-pot two-step stannylation/stille cross-coupling reactions under solvent-free conditions. European Journal of Organic Chemistry, 2018(1). 120–125. DOI: 10.1002/ejoc.201701463
Gribanov, P. S., Topchiy, M. A., Karsakova, I. V., Chesnokov, G. A., Smirnov, A. Y., Minaeva, L. I., Asachenko, A. F. & Nechaev, M. S. (2017). General Method for the Synthesis of 1,4-Disubstituted 5-Halo-1,2,3-triazoles. European Journal of Organic Chemistry, 2017(35). 5225–5230. DOI: 10.1002/ejoc.201700925
Hatit, M. Z. C., Seath, C. P., Watson, A. J. B., & Burley, G. A. (2017). Strategy for conditional orthogonal sequential CuAAC reactions using a protected aromatic ynamine. The Journal of Organic Chemistry, 82(10), 5461–5468. DOI: 10.1021/acs.joc.7b00545
Heller, S. T., Fu, T. & Sarpong, R. (2012). Dual brønsted acid/nucleophilic activation of carbonylimidazole derivatives. Organic Letters, 14(8), 1970–1973. DOI: 10.1021/ol300339q
Heravi, M. M., Hamidi, H., Karimi, N. & Amouchi, A. (2018). Caro’s acid-silica gel catalyzed regioselective ring opening of epoxides with indoles and imidazoles under solvent-free conditions. Advanced Journal of Chemistry-Section A, 1(1), 1-6. DOI: 10.29088/SAMI/AJCA.2018.1.16
Höfle, G., Steglich, W., & Vorbrüggen, H. (1978). 4‐Dialkylaminopyridines as highly active acylation catalysts. Angewandte Chemie International Edition in English, 17(8), 569-583. DOI: 10.1002/anie.197805691
Jia, J., Jiang, Q., Zhao, A., Xu, B., Liu, Q., Luo, W. & Guo, C. (2016). Copper-catalyzed O-methylation of carboxylic acids using DMSO as a methyl source. Synthesis, 48(3), 421-428. DOI: 10.1055/s-0035-1560967
Jing, L., Li, X. J., Han, Y. C., & Chu, Y. (2008). The esterification in cyclohexane/DBSA/water microemulsion system. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 326(1-2), 37-41. DOI: 10.1016/j.colsurfa.2008.05.008
Karthikeyan, P., Kumar, S. S., Jagadeesh, R. V. & Bhagat, P. R. (2012). Solvent-free synthesis of substituted-2-pyrazolines using imidazolium based ionic liquid as a solvent and catalyst: A green route approach. Asian Journal of Chemistry, 24(3), 1351-1353.
Kazemi, E., Davoodnia, A., Basafa, S., Nekhaei, A. & Tavakoli-Hoseini, N. (2018). Investigating effect of cerium (IV) sulfate tetrahydrate as reusable and heterogeneous catalyst for the one‐pot multicomponent synthesis of polyhydroquinolines. Advanced Journal of Chemistry-Section A, 1(2), 96-104. DOI: 10.29088/SAMI/AJCA.2018.1.96104
Lawrence Jr, W. W. (1971). Boric acid-catalyzed esterification of phenols. Tetrahedron Letters, 12(37), 3453-3454. DOI: 10.1016/S0040-4039(01)97203-X
Li, A. J., Pal, V. K. & Kannan, K. (2021). A review of environmental occurrence, toxicity, biotransformation and biomonitoring of volatile organic compounds. Environmental Chemistry and Ecotoxicology, 3, 91–116. DOI: 10.1016/j.enceco.2021.01.001
Liu, H., Shi, G., Pan, S., Jiang, Y. & Zhang, Y. (2013). Palladium-catalyzed benzylation of carboxylic acids with toluene via benzylic C-H activation. Organic Letters, 15(16), 4098-4101. DOI: 10.1021/ol401687f
Manabe, K., Iimura, S., Sun, X. & Kobayashi, S. (2002). Dehydration reactions in water. Bronsted acid-surfactant-combined catalyst for ester, ether, thioether, and dithioacetal formation in water. Journal of American Chemical Society, 124(40), 11971-11978. DOI: 10.1021/ja026241j
Manabe, K., Sun, X. & Kobayashi, S. (2001). Dehydration reactions in water. Surfactant-type Bronsted acid-catalyzed direct esterification of carboxylic acids with alcohols in an emulsion system. Journal of the American Chemical Society, 123(41), 10101-10102. DOI: 10.1021/ja016338q
Marvaniya, H. M., Modi, K. N. & Sen, D. J. (2011). Greener Reactions under solvent free conditions. International Journal of Drug Development & Research, 3(2), 42-51.
Mohamadpour, F. & Feilizadeh, M. (2021). Green and easy synthesis of xanthenes using formic acid as bio-based and green catalyst under solvent-free conditions. Advanced Journal of Chemistry-Section A, 4(1), 58-67. DOI: 10.22034/AJCA.2021.121940
Nazari, S. & Shabanian, M. (2014). Novel heterocyclic semi-aromatic polyamides: synthesis and characterization. Designed Monomers and Polymers, 17(1), 33-39. DOI: 10.1080/15685551.2013.771316
Nishihara, A., & Kubota, I. (1968). Oxidation of aldehyde in alcoholic media with the Caro acid. The Journal of Organic Chemistry, 33(6), 2525-2526. DOI: 10.1021/jo01270a082
Otera, J. (2003). Esterification: Methods, Reactions, and Applications. Wiley-VCH, Weinheim. DOI: 10.1021/op034191c
Phungpis, B. & Hahnvajanawong, V. (2021a). 1-Butyl-3-methylimidazol-2-ylidene as an efficient catalyst for cross-coupling between aromatic aldehydes and N-aroylbenzotriazoles. Asian Journal Chemistry, 33(3), 651-657. DOI: 10.14233/ajchem.2021.23113
Phungpis, B. & Hahnvajanawong, V. (2021b). N-aroylbenzotriazoles as efficient reagents for O-aroylation in the absence of organic solvent. Asian Journal Chemistry, 33(3), 2671-2674. DOI: 10.14233/ajchem.2021.23358
Phungpis, B., Hahnvajanawong, V. & Theramongkol, P. (2016). The N-heterocyclic carbene-catalyzed cross-coupling of aromatic aldehydes with N-aroylbenzotriazoles: A novel approach to synthesis of diaryl 1,2-diketones. Der Pharma Chemica, 8, 167-175.
Rajbongshi, K. K., Sarma, M. J. & Phukan, P. (2014). A Catalyst-free protocol for direct oxidative esterification of alcohols and aldehydes. Tetrahedron Letters, 55(39), 5358–5360.
Rodriguez, A., Nomen, M., Spur, B. W., & Godfroid, J. J. (1998). A selective method for the preparation of aliphatic methyl esters in the presence of aromatic carboxylic acids. Tetrahedron letters, 39(47), 8563-8566. DOI: 10.1016/S0040-4039(98)01958-3
Safaei-Ghomi, J., & Ghasemzadeh, A. M. (2012). Synthesis of some 3, 5-diarylisoxazoline derivatives in ionic liquids media. Journal of the Serbian Chemical Society, 77(6), 733-739. DOI: 10.2298/JSC110831001S
Sakakura, A., Kawajiri, K., Ohkubo, T., Kosugi, Y. & Ishihara, K. (2007). Widely useful DMAP-catalyzed esterification under auxiliary base- and solvent-free conditions. Journal of the American Chemical Society, 129(47), 14775-14779. DOI: 10.1021/ja075824w
Sekhar, K. V. G. C., Sasank, T. V. N. V. T., Nagesh, H. N., Suresh, N., Naidu, K. M. & Suresh, A. (2013). Synthesis of 3,5-diarylisoxazoles under solvent-free conditions using iodobenzene diacetate. Chinese Chemical Letters, 24(12), 1045-1048. DOI: 10.1016/j.cclet.2013.07.022
Zeng, J-C., Xu, H., Yu, F. & Zhang, Z. (2017). Manganese (III) acetate mediated synthesis of polysubstituted pyrroles under solvent-free ball milling. Tetrahedron Letters, 58(7), 674-678. DOI: 10.1016/j.tetlet.2017.01.016
Zhu, Y. F. & Wei, Y. Y. (2013). Solvent-controlled copper-catalyzed oxidation of benzylic alcohols to aldehydes and esters. European Journal of Organic Chemistry, 2013(21), 4503–4508. DOI: 10.1002/ejoc.201300668
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