Abstract
This article reports a novel procedure to prepare pyrroles using a modification of the Paal–Knorr reaction. Water is a safe solvent meeting environmental considerations, but most organic substrates are not soluble in water. A possible solution to improve the solubility of substrates is the use of surface-active reagents that can form micelles. For instance, combined Lewis acid–surfactant catalyst acts both as a Lewis acid to activate the substrate molecules and as a surfactant to form emulsions in water. Here, we prepared and used aluminum tris(dodecyl sulfate)trihydrate to condense various amines to 2,5-hexadione at room temperature. The sole solid pyrrole was separated by a simple filtration. Our findings thus show a novel and improved modification of the Paal–Knorr reaction in terms of mild reaction conditions and clean reaction profiles, using a simple workup procedure and improved yields with excellent chemo-selectivity.
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References
Abid M, Spaeth A, Török B (2006) Solvent-free solid acid-catalyzed electrophilic annelations: a new green approach for the synthesis of substituted five-membered N-heterocycles. Adv Synth Catal 348:2191–2196
Ballini R, Barboni L, Bosica G, Petrini M (2000) 2,5-Dialkylfurans and Nitroalkanes as Source of 2,3,5-Trialkylpyrroles. Synlett 391–393
Banik BK, Samajdar S, Banik IJ (2004) Simple synthesis of substituted pyrroles. J Org Chem 69:213–216
Banik BK, Banik I, Renteria M, Dasgupta SK (2005) A straightforward highly efficient Paal–Knorr synthesis of pyrroles. Tetrahedron Lett 46:2643–2645
Boger DL, Boyce CW, Labrili MA, Sehon CA, Lin QJ (1999) Total syntheses of Ningalin A, Lamellarin O, Lukianol A, and permethyl storniamide a utilizing heterocyclic azadiene Diels—Alder reactions. Am Chem Soc 121:54–62
Chen J, Wu H, Zheng Z, Jin C, Zhang X, Su W (2006) An approach to the Paal–Knorr Pyrroles synthesis catalyzed by Sc(OTf)3 under solvent-free conditions. Tetrahedron Lett 47:5383–5387
Chen JX, Liu MC, Yang XL, Ding JC, Wu HY (2008) Indium(III)-catalyzed synthesis of N-substituted pyrroles under solvent-free conditions. Braz J Chem Soc 19:877–883
Cramer CJ, Truhlar DG (1994) Structure and reactivity in aqueous solution. American Chemical Society, Washington
Curini M, Montanari F, Rosati O, Lioy E, Margarita R (2003) Layered zirconium phosphate and phosphonate as heterogeneous catalyst in the preparation of pyrroles. Tetrahedron Lett 44:3923–3925
Darabi HR, Aghapoor K, Darestani Farahani A, Mohsenzadeh F (2012a) Vitamin B1 as a metal-free organocatalyst for greener Paal–Knorr pyrrole synthesis. Environ Chem Lett. doi:10.1007/s10311-012-0361-7
Darabi HR, Poorheravi MR, Aghapoor K, Mirzaee A, Mohsenzadeh F, Asadollahnejad N, Taherzadeh H, Balavar Y (2012b) Silica-supported antimony(III) chloride as a mild and reusable catalyst for the Paal–Knorr pyrrole synthesis. Environ Chem Lett 10:5–12
Domingo VM, Aleman C, Brillas E, Julia LJ (2001) Diradical dications of m- and p-phenylenebis[2,5-di(2-thienyl)-1-pyrrole]: weakly coupled diradicals. Org Chem 66:4058–4061
Dwars T, Schmidt U, Fischer C, Grassert I, Kempe R, Frohlich R, Drauz K, Oehme G (1998) Synthesis of optically active α-aminophosphinic acids by catalytic asymmetric hydrogenation in organic solvents and aqueous micellar media. Angew Chem 37:2851–2853
Ferreira VF, De Souza MCBV, Cunha AC, Pereira LOR, Ferreira MLG (2001) Recent advances in the synthesis of pyrroles. Org Prep Proced 33:411–454
Firouzabadi H, Iranpoor N, Nowrouzi F (2005) The facile and efficient Michael addition of indoles and pyrrole to α,β-unsaturated electron-deficient compounds catalyzed by aluminium dodecyl sulfate trihydrate [Al(DS)3]·3H2O in water. Chem Commun 789–791
Firouzabadi H, Iranpoor N, Khoshnood A (2007) Aluminum tris (dodecyl sulfate) trihydrate Al(DS)3·3H2O as an efficient Lewis acid–surfactant-combined catalyst for organic reactions in water: efficient conversion of epoxides to thiiranes and to amino alcohols at room temperature. J Mol Catal A Chem 274:109–115
Furstner A (2003) Chemistry and biology of roseophilin and the prodigiosin alkaloids: a survey of the last 2,500 years. Angew Chem 42:3582–3603
Goedheijt MS, Hanson BE, Reek JNH, Kamer PCJ, Van Leeuwen PWNMJ (2000) Accelerated biphasic hydroformylation by vesicle formation of amphiphilic diphosphines. Am Chem Soc 122:1650–1657
Jafari AA, Moradgholi F, Tamaddon F (2009a) A highly efficient michael addition of Indoles to α, β-unsaturated electron-deficient compounds in acidic SDS micellar media. J Iran Chem Soc 6:588–593
Jafari AA, Moradgholi F, Tamaddon F (2009b) Pronounced catalytic effect of a micellar solution of sodium dodecylsulfate (SDS) upon a three-component reaction of aldehydes, amines, and ketones under neutral conditions. Eur J Org Chem 2009:1249–1255
Jones RA, Bean GP (1977) The chemistry of pyrroles. Academic Press, London
Kolb HC, Finn MG, Sharpless KB (2001) Click chemistry: diverse chemical function from a few good reactions. Angew Chem 40:2004–2021
Li CJ, Chan TH (2007) Comprehensive organic reactions in aqueous media. Wiley, New York
Luo H, Kang Y, Li Q, Yang L (2008) Sulfamic acid as efficient and reusable catalytic system for the synthesis of pyrrole, furan, and thiophene derivatives. Heteroatom Chem 19:144–148
Manabe K, Aoyama N, Kobayashi S (2001) Friedel–crafts-type conjugate addition of indoles using a lewis acid–surfactant-combined catalyst in water. Adv Synth Catal 343:174–176
Minetto G, Raveglia LF, Sega A, Tadde M (2005) Microwave-assisted Paal–Knorr reaction—three-step regiocontrolled synthesis of polysubstituted furans, pyrroles and thiophenes. Eur J Org Chem 2005:5277–5288
Narayan S, Muldoon J, Finn MG, Fokin VV, Kolb HC, Sharpless KB (2005) “On water”: unique reactivity of organic compounds in aqueous suspension. Angew Chem 44:3275–3279
Otto S, Engberts JBFN (2003) Hydrophobic interactions and chemical reactivity. Org Biomol Chem 1:2809–2820
Rideout DC, Breslow R (1980) Hydrophobic acceleration of diels–alder reactions. J Am Chem Soc 102:7816–7817
Shiri M, Zolfigol MA (2009) Surfactant-type catalysts in organic reactions. Tetrahedron 65:587–598
Tamaddon F, Razmi Z, Jafari AA (2010) Synthesis of 3,4-dihydropyrimidin-2(1H)-ones and 1,4-dihydropyridines using ammonium carbonate in water. Tetrahedron Lett 51:1187–1189
Tas Cioglu S (1996) Micellar solutions as reaction media. Tetrahedron 52:11113–11152
Wang B, Gu Y, Luo C, Yang T, Yang L, Suo J (2004) Pyrrole synthesis in ionic liquids by Paal–Knorr condensation under mild conditions. Tetrahedron Lett 45:3417–3419
Yuan ShZh, Liu J, Xu L (2010) A convenient synthesis of pyrroles catalyzed by acidic resin under solvent-free condition. Chinese Chem Lett 21:664–668
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Jafari, A.A., Mahmoudi, H. Room temperature aqueous Paal–Knorr pyrrole synthesis catalyzed by aluminum tris(dodecyl sulfate)trihydrate. Environ Chem Lett 11, 157–162 (2013). https://doi.org/10.1007/s10311-012-0391-1
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DOI: https://doi.org/10.1007/s10311-012-0391-1