Sulfonamides amines, alcohols, and phenols were efficiently acylated with carboxylic acid anhydrides and chlorides using ZSM-5-SO3H as catalyst under mild and solvent-free conditions. Also, direct esterification of alcohols with carboxylic acids occurred readily in the presence of this catalyst. Different types of amides and esters were obtained in moderate to high yields and purity after a simple workup. No chromatographic separation is needed for isolation of the acylated product. The catalyst was recovered and reused for up to four times without a noticeable decrease in catalytic activity. 1. Introduction The acylation of alcohols, phenols, and amines is one of the most frequently used processes in organic chemistry. It provides an economical and efficient method for protecting hydroxyl groups during oxidation, peptide coupling, and glycosidation reactions [1]. Acylation is usually carried out by treatment of an alcohol or amine with carboxylic acid chlorides or anhydrides in the presence of an acid or a base catalyst in a suitable organic solvent. Basic catalysts such as 4-(dimethylamino) pyridine (DMAP) [2], tributylphosphines [3], 4-pyrrolidinopyridine [4], and acidic catalysts like Sc(OTf)3 [5], Gd(OTf)3 [6], lanthanide(III) tosylates [7], RuCl3 [8], Al(HSO4)3 [9], Bi(OTf)3 [10], and LiClO4 [11] catalyze acylation reactions with acid chloride or anhydride as the acylating agent under homogenous conditions. Use of homogenous catalysts poses serious problems, such as difficulty in the separation and recovery of the catalyst, disposal of the spent catalyst, and corrosion problems. Solid acid catalysts such as commercial zeolites [12] and montmorillonite K-10 or KSF clay [13] and ZnO [14] have been reported for the acylation of alcohols with acetic anhydride. Though acylation of alcohols can also be brought about by the action of Lewis acid reagents in conjunction with carboxylic acids, the Lewis acid is destroyed in the workup procedure resulting in substantial waste production [15]. Some heterogenized homogenous catalysts have also been reported for the acylation of alcohols and amines [16]. Most of the methods have some disadvantages, such as exothermic reaction, formation of by-products, complicated conditions, and excess acylating agents, and require longer reaction times, use of halogenated solvents, and expensive moisture-sensitive toxic reagents. Apart from these difficulties, some of the above methods do not satisfy the requirements of green synthesis due to the inability to recover and reuse the catalyst. Thus, due to high importance of the
References
[1]
T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, Wiley, New York, NY, USA, 3rd edition, 1999.
[2]
W. Steglich and G. Hofle, “N,N-dimethyl-4-pyridinamine a very effective acylation catalyst,” Angewandte Chemie, vol. 8, no. 12, pp. 980–981, 1969.
[3]
E. Vedejs and S. T. Diver, “Tributylphosphine: a remarkable acylation catalyst,” Journal of the American Chemical Society, vol. 115, no. 8, pp. 3358–3359, 1993.
[4]
E. F. V. Scriven, “4-Dialkylaminopyridines: super acylation and alkylation catalysts,” Chemical Society Reviews, vol. 12, no. 2, pp. 129–161, 1983.
[5]
K. Ishihara, M. Kubota, H. Kurihara, and H. Yamamoto, “Scandium trifluoromethanesulfonate as an extremely active Lewis acid catalyst in acylation of alcohols with acid anhydrides and mixed anhydrides,” The Journal of Organic Chemistry, vol. 61, no. 14, pp. 4560–4567, 1996.
[6]
R. Alleti, W. S. Oh, M. Perambuduru, Z. Afrasiabi, E. Sinn, and V. P. Reddy, “Gadolinium triflate immobilized in imidazolium based ionic liquids: a recyclable catalyst and green solvent for acetylation of alcohols and amines,” Green Chemistry, vol. 7, no. 4, pp. 203–206, 2005.
[7]
T. N. Parac-Vogt, K. Deleersnyder, and K. Binnemans, “Lanthanide(III) tosylates as new acylation catalysts,” European Journal of Organic Chemistry, vol. 2005, no. 9, pp. 1810–1815, 2005.
[8]
K. D. Surya, “Ruthenium(III) chloride catalyzed acylation of alcohols, phenols, thiols, and amines,” Tetrahedron Letters, vol. 45, no. 14, pp. 2919–2922, 2004.
[9]
F. M. Shirini, M. A. Zolfigol, M. Abedini, and P. Salehi, “Al(HSO4)3 catalyzed acetylation and formylation of alcohols,” Bulletin of the Korean Chemical Society, vol. 24, no. 11, pp. 1683–1685, 2003.
[10]
A. Orita, C. Tanahashi, A. Kakuda, and J. Otera, “Highly powerful and practical acylation of alcohols with acid anhydride catalyzed by Bi(OTf)3,” Journal of Organic Chemistry, vol. 66, no. 26, pp. 8926–8934, 2001.
[11]
Y. Nakae, I. Kusaki, and T. Sato, “Lithium perchlorate catalyzed acetylation of alcohols under mild reaction conditions,” Synlett, vol. 2001, no. 10, pp. 1584–1586, 2001.
[12]
R. Ballini, G. Bosica, S. Carloni, L. Ciaralli, R. Maggi, and G. Sartori, “Zeolite HSZ-360 as a new reusable catalyst for the direct acetylation of alcohols and phenols under solventless conditions,” Tetrahedron Letters, vol. 39, no. 33, pp. 6049–6052, 1998.
[13]
B. M. Choudary, V. Bhaskar, M. L. Kantam, K. Koteswara Rao, and K. V. Raghavan, “Acylation of alcohols with carboxylic acids via the evolution of compatible acidic sites in montmorillonites,” Green Chemistry, vol. 2, pp. 67–70, 2000.
[14]
M. H. Sarvari and H. Sharghi, “Zinc oxide (ZnO) as a new, highly efficient, and reusable catalyst for acylation of alcohols, phenols and amines under solvent free conditions,” Tetrahedron, vol. 61, no. 46, pp. 10903–10907, 2005.
[15]
J. Izumi, I. Shiina, and T. Mukaiyama, “An efficient esterification reaction between equimolar amounts of free carboxylic acids and alcohols by the combined use of octamethylcyclotetrasiloxane and a catalytic amount of titanium(iv) chloride tris(trifluoromethanesulfonate),” Chemistry Letters, vol. 2, pp. 141–142, 1995.
[16]
R. Alleti, M. Perambuduru, S. Samantha, and V. P. Reddy, “Gadolinium triflate: an efficient and convenient catalyst for acetylation of alcohols and amines,” Journal of Molecular Catalysis A, vol. 226, no. 1, pp. 57–59, 2005.
[17]
F. Shirini, K. RaMoghadam, and T. Naghdi, “1,3-Dichloro-5,5-dimethylhydantoin: an efficient catalyst for the solvent free synthesis of 1,8-dioxo-octahydro-xanthenes,” Iranian Journal of Catalysis, vol. 2, pp. 55–59, 2012.
[18]
A. Dyer, An Introduction to Zeolite Molecular Sieves, John Wiley & Sons Inc., New York, NY, USA, 1988.
[19]
A. R. Massah, R. J. Kalbasi, and M. Azadi, “Highly selective oxidation of alcohols using MnO2/TiO2-ZrO2 as a novel heterogeneous catalyst,” Comptes Rendus Chimie, vol. 15, no. 5, pp. 428–436, 2012.
[20]
A. R. Massah, R. J. Kalbasi, and M. Toghyani, “Sulfonated polystyrene/montmorillonite nanocomposite as a new and efficient catalyst for the solvent-free Mannich reaction,” Iranian Journal of Catalysis, vol. 2, no. 1, pp. 41–49, 2012.
[21]
R. J. Kalbasi, M. Ghiaci, and A. R. Massah, “Highly selective vapor phase nitration of toluene to 4-nitro toluene using modified and unmodified H3PO4/ZSM-5,” Applied Catalysis A, vol. 353, no. 1, pp. 1–8, 2009.
[22]
R. J. Kalbasi, A. Abbaspourrad, A. R. Massah, and F. Zamani, “Highly selective vapor-phase acylation of veratrole over H3PO4/TiO2-ZrO2: using ethyl acetate as a green and efficient acylating agent,” Chinese Journal of Chemistry, vol. 28, no. 2, pp. 273–284, 2010.
[23]
A. R. Massah, R. J. Kalbasi, and A. Shafiei, “ZSM-5-SO3H as a novel, efficient, and reusable catalyst for the chemoselective synthesis and deprotection of 1,1-diacetates under eco-friendly conditions,” Monatshefte für Chemie, vol. 143, no. 4, pp. 643–652, 2012.
[24]
A. R. Massah, R. J. Kalbasi, and N. Samah, “Highly selective synthesis of β-amino carbonyl compounds over ZSM-5-SO3H under solvent-free conditions,” Bulletin of the Korean Chemical Society, vol. 32, no. 5, pp. 1703–1708, 2011.
[25]
A. R. Massah, F. Kazemi, D. Azadi et al., “A mild and chemoselective solvent-free method for the synthesis of N-aryl and N-alkysulfonamides,” Letters in Organic Chemistry, vol. 3, no. 3, pp. 235–241, 2006.
[26]
A. R. Massah, B. Asadi, M. Hoseinpour, A. Molseghi, R. J. Kalbasi, and H. Javaherian Naghash, “A novel and efficient solvent-free and heterogeneous method for the synthesis of primary, secondary and bis-N-acylsulfonamides using metal hydrogen sulfate catalysts,” Tetrahedron, vol. 65, no. 36, pp. 7696–7705, 2009.
[27]
A. R. Massah, H. Adibi, R. Khodarahmi et al., “Synthesis, in vitro antibacterial and carbonic anhydrase II inhibitory activities of N-acylsulfonamides using silica sulfuric acid as an efficient catalyst under both solvent-free and heterogeneous conditions,” Bioorganic and Medicinal Chemistry, vol. 16, no. 10, pp. 5465–5472, 2008.
[28]
A. R. Massah, M. Dabagh, S. Shahidi, H. J. Naghash, A. R. Momeni, and H. Aliyan, “P2O5/SiO2 as an efficient and recyclable catalyst for N-acylation of sulfonamides under heterogeneous and solvent-free conditions,” Journal of the Iranian Chemical Society, vol. 6, no. 2, pp. 405–411, 2009.
[29]
P. Pushpaletha and M. Lalithambika, “Modified attapulgite: an efficient solid acid catalyst for acetylation of alcohols using acetic acid,” Applied Clay Science, vol. 51, no. 4, pp. 424–430, 2011.
[30]
L. Osiglio, G. Romanelli, and M. Blanco, “Alcohol acetylation with acetic acid using borated zirconia as catalyst,” Journal of Molecular Catalysis A, vol. 316, no. 1–2, pp. 52–58, 2010.
[31]
P. R. Likhar, R. Arundhathi, S. Ghosh, and M. L. Kantam, “Polyaniline nanofiber supported FeCl3: an efficient and reusable heterogeneous catalyst for the acylation of alcohols and amines with acetic acid,” Journal of Molecular Catalysis A, vol. 302, no. 1–2, pp. 142–149, 2009.
