Novel Carbon-based Solid Acid from Green Pistachio Peel as an Efficient Catalyst for the Chemoselective Acylation, Acetalization and Thioacetalization of Aldehydes, Synthesis of Biscoumarins and Antimicrobial Evaluation

Author(s): Fatemeh Ghorbani, Seied Ali Pourmousavi*, Hamzeh Kiyani.

Journal Name: Current Organocatalysis

Volume 7 , Issue 1 , 2020

Become EABM
Become Reviewer

Graphical Abstract:


Abstract:

Background: Much attention has been focused on heterogeneous catalysts. Reactions with these recoverable and reusable catalysts are clean, selective with high efficiency. Among the heterogeneous solid acid catalyst in organic synthesis, Carbon-Based Solid Acids (CBSAs), which are important solid acid with many practical and research applications have been extensively studied. In this work, green Pistachio peel, a biomass waste, was converted into a novel carbon-based solid acid catalyst (Pis-SO3H).

Objective: The aim of this work is to synthesize highly sulfonated carbon as an efficient, recyclable, nontoxic solid acid catalyst by simultaneous sulfonation, dehydration and carbonization of green Pistachio peel as biomass and investigate the catalytic activity of Pis-SO3H in acetalization, thioacetalization, acylation of aldehydes and synthesis of 3,3'-Arylmethylene-bis(4-hydroxycoumarin) derivatives.

Methods: Pis-SO3H was synthesized by an integrated fast one-step hydrothermal carbonization and sulfonation process in the presence of sulfuric acid. The characterization of the physicochemical properties of Pis-SO3H was achieved by XRD, FT-IR, FE-SEM, and elemental analysis.

Results: The result of acid-base titration showed that the total acidity of the catalyst was 7.75 mmol H+g−1. This new heterogeneous catalyst has been efficiently used for the chemoselective thioacetalization, acetalization and acylation of aldehyde and the synthesis of biscoumarins under solvent-free conditions. All the reactions work easily in high yields. The antimicrobial activity of some of the biscoumarins was evaluated in screening by disk diffusion assay for the zone of inhibition.

Conclusion: The catalytic activity of the Pis-SO3H was investigated during acetalization, thioacetalization, acylation and synthesis of biscoumarins. The results of protection of carbonyl groups and synthesis of biscoumarins in the present work offer effective alternatives for environmentally friendly utilization of abundant biomass waste.

Keywords: Catalyst, biomass, carbon-based solid acid, carbonyl protecting groups, biscoumarin, pistachio peel.

[1]
M.G.. Porter D.M. Taxonomic revision of the genus pistacia. Am. J. Plant Sci., 2012, 3, 12-32.
[http://dx.doi.org/10.4236/ajps.2012.31002]
[2]
Sawaya, W.N.; Khatchadourian, H.A.; Safi, W.M.; Al-Hammad, H.A. Chemical characterization of prickly pear pulp, Opuntia ficus indica, and the manufacturing of prickly pear jam. J. Food Technol., 1983, 18, 183-193.
[http://dx.doi.org/10.1111/j.1365-2621.1983.tb00259.x]
[3]
Bohluli Ghaen, A. Chemical composition and digestibility of pistachio byproducts and their effects on Holstein cows’ nutrition.. MSc thesis, Animal Science Department Ferdowsi University of Mashhad, Iran.,, 2006.
[4]
Gyerard, V.S.; Notheisz, F. Heterogeneous catalyst in organic chemistry. San Diago; Elsevier, 2000, pp. 1-96.
[5]
Wang, X.; Liu, R.; Waje, M.M.; Chen, Z.; Yan, Y.; Bozhilov, V.; Feng, P. Sulfonated ordered mesoporous carbon as a stable and highly active protonic acid catalyst. Chem. Mater., 2007, 19, 2395-2397.
[http://dx.doi.org/10.1021/cm070278r]
[6]
Chang, B.; Fu, J.; Tian, Y.; Dong, X. A novel highly ordered mesoporous carbon-based solid acid for synthesis of bisphenol-A. RSC Advances, 2013, 3, 1987-1994.
[7]
Chang, B.; Fu, J.; Tian, Y.; Dong, X. Multifunctionalized ordered mesoporous carbon as an efficient and stable solid acid catalyst for biodiesel preparation. J. Phys. Chem., 2013, 117, 6252-6258.
[8]
Clod, D.M. Carbohydrate cyclic acetal formation and migration. Chem. Rev., 1979, 79, 491-513.
[http://dx.doi.org/10.1021/cr60322a002]
[9]
Chang, B.; Tian, Y.; Shi, W.; Liu, J.; Xi, F.; Dong, X. Magnetically separable porous carbon nanospheres as solid acid catalysts. RSC Advances, 2013, 3, 20999-21006.
[http://dx.doi.org/10.1039/c3ra43208d]
[10]
Xuezheng, L.; Chunqing, L.; Chenze, Q. Novel carbon-based strong acid catalyst from starch and its catalytic activites for acetalization. J. Mater. Sci., 2011, 46, 5345-5349.
[http://dx.doi.org/10.1007/s10853-011-5472-1]
[11]
Greene, T.W.; Wuts, P.G.M. Book Reviews: Protective Groups in Organic Synthesis In: Wiley ; 3rd ed; New York, 1999; pp. 329-344.
[http://dx.doi.org/10.1002/0471220574]
[12]
Jafari, F.; Khodabakhshi, S. Mg(HSO4)2/SiO2 as a highly efficient catalyst for the green preparation of 2-aryl-1,3-dioxalanes/dioxanes and linear acetals. Org. Chem. Int., 2012, 475301, 1-5.
[http://dx.doi.org/10.1155/2012/475301]
[13]
Brown, J.J.; Lenhard, R.H.; Brestein, S. Greene’s Protective Groups in Organic Synthesis. J. Am. Chem. Soc., 1964, 86, 2183-2187.
[http://dx.doi.org/10.1021/ja01065a016]
[14]
Lu, Y.; Liang, X.; Qi, C. Synthesis of novel carbon/silica composites based strong acid catalyst and its catalytic activities for acetalization. Bull. Mater. Sci., 2012, 35, 419-424.
[http://dx.doi.org/10.1007/s12034-012-0292-8]
[15]
Firouzabadi, H.; Iranpoor, N.; Karimi, B. Zirconium tetrachloride (zrcl4) catalyzed highly chemoselective and efficient acetalization of carbonyl compounds. Synlett, 1999, 3, 321-323.
[http://dx.doi.org/10.1055/s-1999-2605]
[16]
Yus, M.; Najera, C.; Foubelo, F. The role of 1,3-dithianes in natural product synthesis. Tetrahedron, 2003, 59, 6147-6212.
[http://dx.doi.org/10.1016/S0040-4020(03)00955-4]
[17]
Hajipour, A.R.; Zarei, A.L. Khazdooz.; Pourmousavi, S.A.; Zahmatkesh, S.; Ruoho, A.E. Silica sulfuric acid as a mild and chemoselective catalyst for dithioacetalization under solvent-free conditions. J. Sulfur Chem., 2004, 25, 389-393.
[http://dx.doi.org/10.1080/17415990412331320645]
[18]
Fieser, L.F. Preparation of ethylenethioketals. J. Am. Chem. Soc., 1954, 76, 1945-1947.
[http://dx.doi.org/10.1021/ja01636a063]
[19]
Tamami, B.; Parvanak Borujeny, K. Chemoselective protection of carbonyl compounds as dithioacetals using polystyrene and silica gel supported AlCl3. Iran. Polym. J., 2003, 12, 507-513.
[20]
Muthusamy, S.; Arulananda, S.; Gunanathan, C. Indium (III) chloride as an efficient, convenient catalyst for thioacetalization and its chemoselectivity. Tetrahedron Lett., 2001, 42, 359-362.
[http://dx.doi.org/10.1016/S0040-4039(00)01966-3]
[21]
Patney, H.K. A rapid mild and efficient method of thioacetalization using anhydrous iron (III) chloride dispersed on silica gel. Tetrahedron Lett., 1991, 32, 2259-2260.
[http://dx.doi.org/10.1016/S0040-4039(00)79696-1]
[22]
Patney, H.K. Zirconium (IV) chloride-silica catalyzed thioacetalization of carbonyl compounds. Tetrahedron Lett., 1996, 37, 4621-4622.
[http://dx.doi.org/10.1016/0040-4039(96)00892-1]
[23]
Fahid, F.; Pourmousavi, S.A. Sulfonated polyanthracene-catalyzed highly efficient and chemoselective thioacetalization of carbonyl compounds and transthioacetalization of acetals and acylals. J. Sulfur Chem., 2014, 6, 16-29.
[24]
Kochhar, K.S.; Bal, B.S.; Deshpande, R.P. Protecting groups in organic synthesis. Part 8. Conversion of aldehydes into geminal diacetates. J. Org. Chem., 1983, 48, 1765-1767.
[http://dx.doi.org/10.1021/jo00158a036]
[25]
Niknam, Kh.; Saberi, D.; Sefat, M.N. Silica-bonded S-sulfonic acid as a recyclable catalyst for chemoselective synthesis of 1,1-diacetates. Tetrahedron Lett., 2009, 50, 4058-4062.
[http://dx.doi.org/10.1016/j.tetlet.2009.04.096]
[26]
Sajjadifar, S.; Rezayati, S. Synthesis of 1,1-diacetates catalysed by silica-supported boron sulfonic acid under solvent-free conditions and ambient temperature. Chem. Pap., 2014, 68, 531-539.
[http://dx.doi.org/10.2478/s11696-013-0480-z]
[27]
Bandgar, B.P.; Joshi, S.N.; Kamble, V.T. A versatile and practical synthesis of 1,1-diacetates from aldehydes catalyzed by cyanuric chloride. J. Chin. Chem. Soc. (Taipei), 2007, 54, 489-492.
[http://dx.doi.org/10.1002/jccs.200700069]
[28]
Wang, M.; Song, Z.; Gong, H.; Jiang, H. Synthesis of 1,1‐diacetates using a new combined catalytic system: copper p‐toluenesulfonate/HOAc. Synth. Commun., 2008, 38, 961-966.
[http://dx.doi.org/10.1080/00397910701845720]
[29]
Satam, J.R.; Jayaram, R.V. (NH4)3PW12O40 as an efficient and reusable catalyst for the synthesis and deprotection of 1,1‐diacetates. Synth. Commun., 2008, 38, 595-602.
[http://dx.doi.org/10.1080/00397910701798002]
[30]
Yadav, J.S.; Reddy, B.V.S.; Sreedhar, P. Mild and efficient conversion of aldehydes to gem-diacetates using 2nd generation ionic liquids. Catal. Commun., 2007, 9, 590-593.
[http://dx.doi.org/10.1016/j.catcom.2007.02.031]
[31]
Hajipour, A.R.; Nasreesfahani, A.E.; Ruoho, Z. An efficient and chemoselective synthesis of aldehyde 1,1-diacetates using morpholinium bisulfate as a bronsted acidis ionic liquid under solvent-free conditions. Org. Prep. Proced. Int., 2008, 40, 385-390.
[http://dx.doi.org/10.1080/00304940809458098]
[32]
Zhang, F. Silica phosphoric acid: An efficient and recyclable catalyst for the solvent-free synthesis of acylals and their deprotection in MeOH. Synth. Commun., 2010, 40, 3240-3250.
[http://dx.doi.org/10.1080/00397910903398650]
[33]
Shirini, F.; Mamaghani, M.; Abedini, M. Saccharin sulfonic acid as an efficient catalyst for the preparation and deprotection of 1, 1-diacetates. Bull. Korean Chem. Soc., 2010, 31, 2399-2401.
[http://dx.doi.org/10.5012/bkcs.2010.31.8.2399]
[34]
Hoseien abadi, Z.; Pourmousavi, S.A.; Zamani, M. Synthesis of sulfonated carbon-based solid acid as a novel and efficient nanocatalyst for the preparation of highly functionalized piperidines and acylals: a DFT study. Res. Chem. Intermed., 2016, 42, 6105-6124.
[http://dx.doi.org/10.1007/s11164-016-2448-4]
[35]
Qu, D.; Li, J.; Yang, X.H.; Zhang, Z.D.; Luo, X.X.; Li, M.K.; Li, X. New biscoumarin derivatives: synthesis, crystal structure, theoretical study and antibacterial activity against Staphylococcus aureus. Molecules, 2014, 19(12), 19868-19879.
[http://dx.doi.org/10.3390/molecules191219868] [PMID: 25460310]
[36]
Choudhary, M.I.; Fatima, N.; Khan, K.M.; Jalil, S.; Iqbal, S. Atta-Ur-Rahman, New biscoumarin derivatives-cytotoxicity and enzyme inhibitory activities. Bioorg. Med. Chem., 2006, 14(23), 8066-8072.
[http://dx.doi.org/10.1016/j.bmc.2006.07.037] [PMID: 16919464]
[37]
Manolov, I.; Maichle-Moessmer, C.; Nicolova, I.; Danchev, N. Synthesis and anticoagulant activities of substituted 2,4-diketochromans, biscoumarins, and chromanocoumarins. Arch. Pharm. (Weinheim), 2006, 339(6), 319-326.
[http://dx.doi.org/10.1002/ardp.200500149] [PMID: 16649158]
[38]
Talhi, O.; Schnekenburger, M.; Panning, J.; Pinto, D.G.; Fernandes, J.A.; Almeida Paz, F.A.; Jacob, C.; Diederich, M.; Silva, A.M. Bis(4-hydroxy-2H-chromen-2-one): synthesis and effects on leukemic cell lines proliferation and NF-κB regulation. Bioorg. Med. Chem., 2014, 22(11), 3008-3015.
[http://dx.doi.org/10.1016/j.bmc.2014.03.046] [PMID: 24775915]
[39]
Khan, K.M.; Rahim, F.; Wadood, A.; Kosar, N.; Taha, M.; Lalani, S.; Khan, A.; Fakhri, M.I.; Junaid, M.; Rehman, W.; Khan, M.; Perveen, S.; Sajid, M.; Choudhary, M.I. Synthesis and molecular docking studies of potent α-glucosidase inhibitors based on biscoumarin skeleton. Eur. J. Med. Chem., 2014, 81, 245-252.
[http://dx.doi.org/10.1016/j.ejmech.2014.05.010] [PMID: 24844449]
[40]
Ammar, H.; Abid, S.; Fery-Forgues, S. Synthesis and spectroscopic study of new biscoumarin dyes based on 7-(4-methylcoumarinyl) diesters. Dyes Pigments, 2008, 78, 1-5.
[http://dx.doi.org/10.1016/j.dyepig.2007.09.008]
[41]
Kiyani, H.; Darbandi, H.; Tazari, M. Green synthesis of biscoumarins using phthalimide-n-sulfonic acid. Jordan J. Chem, 2016, 11, 77-84.
[42]
Shirini, F.; Esmaeeli-Ranjbar, S.; Seddighi, M. Poly(4‐vinylpyridinium) perchlorate as an efficient and recyclable catalyst for the synthesis of biscoumarins and bisindoles. Chin. J. Catal., 2014, 35, 1017-1023.
[http://dx.doi.org/10.1016/S1872-2067(14)60061-9]
[43]
Padalkar, V.; Phatangare, K.; Takale, S.; Pisal, R.; Chaskar, A. Silica supported sodium hydrogen sulfate and Indion 190 resin: An efficient and heterogeneous catalysts for facile synthesis of bis-(4-hydroxycoumarin-3-yl) methanes. J. Sau Synthesis of biscoumarin derivatives using poly(4-vinylpyridine)-supported dual acidic ionic liquid as a heterogeneous catalyst. Monatsh. Chem., 2014, 145, 1023-1026.
[44]
Li, W.; Wang, Y.; Wang, Z.; Dai, L.; Wang, Y. Novel SO3H-functionalized ionic liquids based on benzimidazolium cation: Efficient and recyclable catalysts for one-pot synthesis of biscoumarin derivatives. Catal. Lett., 2011, 141, 1651-1658.
[http://dx.doi.org/10.1007/s10562-011-0689-9]
[45]
Safaei-Ghomi, J.; Eshteghal, F.; Ghasemzadeh, M.A. Solvent-free synthesis of dihydropyrano[3,2-c]chromene and biscoumarin derivatives using magnesium oxide nanoparticles as a recyclable catalyst. Acta Chim. Slov., 2014, 61(4), 703-708.
[PMID: 25551709]
[46]
Yang, H.; Liu, Y.; Zhang, F.; Zhang, R.; Meng, Y.; Li, M.; Xie, S.; Tu, B.; Zhao, D. A simple melt impregnation method to synthesize ordered mesoporous carbon and carbon nanofiber bundles with graphitized structure from pitches. J. Phys. Chem. B, 2004, 08, 17320-17328.
[http://dx.doi.org/10.1021/jp046948n]
[47]
Ilango, K.; Valentina, P. Text book of Medicinal Chemistry. Chennai: Keerthi Publishers, 2007, 1, pp. 336-352.
[48]
Rajanarendar, E.; Mohan, G.; Shiva Rami Reddy, A. Synthesis and some anti-micobial activity of new isoxazolyl-1,3-benzoxazines. Indian J. Chem., 2008, 47B, 112-116.
[49]
Zong, M.H.; Du, Z.Q.; Lou, W.Y.; Smith, T.J.; Wu, H. Preparation of a sugar catalyst and its use for highly efficient production of biodiesel. Green Chem., 2007, 9, 434-437.
[http://dx.doi.org/10.1039/b615447f]
[50]
Shu, Q.; Gao, J.; Nawaz, Z.; Liao, Y.; Wang, D. Synthesis of biodiesel from waste vegetable oil with large amounts of free fatty acids using a carbon-based solid acid catalyst. J. Appl. Energy, 2010, 87, 2589-2596.
[http://dx.doi.org/10.1016/j.apenergy.2010.03.024]
[51]
Mirkhani, V.; Moghadam, M.; Tangestaninejad, S.; Mohammadpoor-Baltork, I.M.; Mahdavi, M. Preparation of an improved sulfonated carbon-based solid acid as a novel, efficient, and reusable catalyst for chemoselective synthesis of 2-oxazolines and bis-oxazolines. Monatsh. Chem., 2009, 140, 1489-1494.
[http://dx.doi.org/10.1007/s00706-009-0213-8]
[52]
Fahid, F.; Kanaani, A.; Pourmousavi, S.A.; Ajloo, D. Synthesis, tautomeric stability, spectroscopy and computational study of a potential molecular switch of (Z)-4-(phenylamino) pent-3-en-2-one. Mol. Phys., 2017, 115, 795-808.
[http://dx.doi.org/10.1080/00268976.2017.1287439]
[53]
Pourmousavi, S.A.; Kanaani, A.; Fatahi, H.R.; Ghorbani, F.; Ajloo, D. SbCl3 as effective catalyst for the preparation of 2, 3-Dihydroquinazolin-4 (1H)-ones, spectroscopic investigation and DFT study. J. Phys. Chem. Solids, 2017, 10, 82-93.
[http://dx.doi.org/10.1016/j.jpcs.2017.03.008]
[54]
Pourmousavi, S.A.; Moghimi, P.; Ghorbani, F.; Zamani, M. Sulfonated polynaphthalene as an effective and reusable catalyst for the one-pot preparation of amidoalkyl naphthols: DFT and spectroscopic studies. J. Mol. Struct., 2017, 1147, 87-102.
[http://dx.doi.org/10.1016/j.molstruc.2017.05.010]


Rights & PermissionsPrintExport Cite as

Article Details

VOLUME: 7
ISSUE: 1
Year: 2020
Page: [55 - 80]
Pages: 26
DOI: 10.2174/2213337206666190717164606

Article Metrics

PDF: 13
HTML: 2