A range of solvent-free organic reactions performed under microwave irradiation is reported and the advantages with respect to the corresponding thermal protocols outlined. Good assets like the dramatic shortening of the reaction times, the higher efficiency, and the absence in a number of cases of toxic or polluting reagents are highlighted.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
G. W. V. Cave, C.L. Raston, and J. L. Scott, Recent advances in solventless organic reactions: towards benign synthesis with remarkable versatility, Chem. Commun. 2159–2169 (2001).
Rajagopal, D., Narayan, R., and Swaminathan, S., Proceedings of Indian Academy of Sciences, Chemical Sciences, 2159–2169 (2001).
G. W. V. Cave and C. L. Raston, Towards benign syntheses of pyridines involving sequential solvent free aldol and Michael addition reactions, Chem. Commun. 2199–2200 (2000).
R. S. Varma and D. Kumar, Microwave-accelerated solvent-free synthesis of thioketones, thiolactones, thioamides, thionoesters, and thioflavonoids, Org. Lett. 1, 697–700 (1999).
S. Paul, M. Gupta, and A. Loupy, Microwave assisted synthesis of 1, 5-disubstituted hydantoins and thiohydantoins in solvent-free conditions, Synthesis 75–78 (2002).
R. S. Varma and R. Dahiya, An expeditious and solvent-free synthesis of 2-amino-substituted isoflav-3-enes using microwave irradiation, J. Org. Chem. 63, 8038–8041 (1998).
L. Blackburn and R. J. K. Taylor, In situ oxidation-imine formation-reduction routes from alchols to amines, Org. Lett. 3, 1637–1639 (2001).
S. A. Raw, C. D. Wilfred, and R. J. K. Taylor, Preparation of quinoxalines, dihydropyrazines, pyrazines and piperazines, using tandem oxidation processes, Chem. Commun. 2286–2287 (2003).
S. Y. Kim, K. H. Park, and Y. K. Chung, Manganese (IV) dioxide-catalyzed synthesis of quinoxalines under microwave irradiation, Chem. Commun. 1321–1323 (2005).
A. Stadler, B. H. Yousefi, D. Dallinger, P. Walla, E. Van der Eycken, N. Kaval, and C. O. Kappe, Scalability of microwave-assisted organic synthesis. From single-mode to multimode parallel batch reactors, Org. Proc. Res Dev. 7, 707–716 (2003).
J. Cleophax, M. Liagre, A. Loupy, and A. Petit, Application of focused microwaves to the scale-up of solvent-free organic reactions, Org. Proc. Res. Dev. 4, 498–504 (2000), and references therein.
Green Industrial Applications of Ionic Liquids, Kluwer Academic, Dordrecht, 2003; Ionic liquids in Synthesis, 2003, Wiley-VCH Verlag, Weinheim.
M. Deetlefs and K. R. Seddon, Improved preparation of ionic liquids using microwave irradiation, Green Chemistry 5, 181–186 (2003).
For a comprehensive review on this topic, see: S. Deshayes, M. Liagre, A. Loupy, J.-L. Luche, and A. Petit, Microwave activation in phase transfer catalysis, Tetrahedron 55, 10851–10870 (1999).
C. Villa, M. T. Genta, A. Bargagna, E. Mariani, and A. Loupy, Microwave activation and solvent-free phase transfer catalysis for the synthesis of new benzylidene cineole derivatives as potential UV sunscreens, Green Chemistry 3, 196–200 (2001).
S. Chatti, M. Bortolussi, and A. Loupy, Synthesis of diethers derived from dianhydrohexitols by phase transfer catalysis under microwave, Tetrahedron Lett. 41, 3367–3370 (2000).
For an exhaustive review on the use of clay-supported reagents in organic synthesis see: Clay and clay-supported reagents in organic synthesis, R.S. Varma, Tetrahedron 58, 1235–1255 (2002).
Varma, R. S., Kumar, D., and Liesen, J.-P. Solid state synthesis of 2-aroylbenzo(b(furans, 1, 3-thiazoles and 3-aryl-5, 6-dihydroimidazo(2, 1-b(thiazoles from (α-tosyloxy-ketones using microwave irradiation, J. Chem. Res., Perkin Trans. 1 4093–4096 (1998).
S. Varma, and R. Dahida, Sodium borohydride on wet clay: solvent–free reductive amination of carbonyl compounds using microwaves, Tetrahedron 54, 6293–6298 (1998).
R. S. Varma, M. Varma, and A. K. Chatterjee, Microwave-assisted deacetylation on alumina: a simple deprotection method, Perkin Trans. 1999–1001 (1993).
R. S. Varma, A. K. Chatterjee, and M. Varma, Alumina-mediated microwave thermolysis: a new approach to deprotection of benzyl esters, Tetrahedron Lett. 34, 4603–4606 (1993).
(a) D. S. Bose and V. Lakshminarayana, An effcient and highly selective cleavage of N-tert-butoxycarbonyl group under microwave irradiation, Tetrahedron Lett. 39, 5631–5634 (1998); (b) R. S. Varma, Solvent-free organic syntheses using supported reagents and microwave irradiation, Green Chemistry 43–55 (1999).
R. S. Varma and R. K. Saini, Microwave-assisted isomerization of 2’-aminochalcones on clay: an easy route to 2-aryl-1, 2, 3, 4-tetrahydro-4-quinolones, Synlett 857–858 (1997).
M. Lahred and A. Hallberg, Microwave-assisted high-speed chemistry: a new technique in drug discovery, Drug Discov. Today 6, 406–416 (2001).
G. W. Kabalka, R. M. Pagni, and M. Hair, Solventless Suzuki coupling reactions on palladium-doped KF/Al2O3, Org. Lett. 1, 1423–1425 (1999).
G. W. Kabalka, L. Wang, V. Namboodiri, and R. M. Pagni, Rapid microwave-enhanced, solventless Sonogashira coupling reaction on alumina, Tetrahedron Lett. 41, 5151–5154 (2000).
B. Westermann and C. Neuhaus, Dihydroxyacetone in amino acid catalyzed Mannich-type reactions, Angew. Chem. Int. Ed. 44, 4077–4079 (2005).
S. Mossé and A. Alexakis, Organocatalyzed asymmetric reactions via microwave activation, Org. Lett. 8, 3577–3580 (2006).
G. Dessole, R. P. Herrera, and A. Ricci, H-Bonding organocatalysed Friedel–Crafts alkylation of aromatic and heteroaromatic systems with nitroolefins, Synlett 2374–2378 (2004).
For an up to date, concise and useful review of MW theory see: B. L. Hayes, Recent Advances in Microwave-Assisted Synthesis, Aldrichimica Acta 37, 66–76 (2004) and references therein.
J. J. Chen and S. V. Deshpande, Rapid synthesis of a-ketoamides using microwave irradiation-simultaneous cooling method, Tetrahedron Lett. 44, 8873–8876 (2003).
J. J. Vanden Eynde and A. Mayence, Synthesis and aromatization of Hantzsch 1, 4-dihydropyridines under microwave irradiation. An overview, Molecules, 8, 381–391 (2003).
L. Bernardi, B. F. Bonini, M. Comes-Franchini, M. Fochi, M. Folegatti, S. Grilli, A. Mazzanti, and A. Ricci, First 1, 3-dipolar cycloaddition of Z-M-phenyl-N-methylnitrone with allylic fluorides: a stereoselective route to enantiopure fluorine-containing isozazolidines and amino polyols, Tetrahedron: Asymmetry 15, 245–250 (2004).
L. Perreux and A. Loupy, A tentative rationalization of microwave effects in organic synthesis according to the reaction medium and mechanistic considerations, Tetrahedron 57, 9199–9223 (2001) and references therein.
L. Marrero-Torrero and A. Loupy, Synlett Synthesis of 2-oxazolines from carboxylic acids and α,α,α-tri(hydroxymethyl) methylamine under microwaves in solvent free conditions, 245–246 (1996).
A. Diaz-Ortiz, A. de la Hoz, M. A. Herrero, P. Prieto, A. Sanchez-Migallon, F. P. Cossio, A. Arrieta, S. Vivanco & Concepcion Foces-Foces, Enhancing stereochemical diversity by means of microwave irradiation in the absence of solvent: synthesis of highly substituted nitroproline esters via 1, 3-dipolar reactions, Molecular Diversity 7, 175–180 ( 2003).
A. Dömling, Recent developments in isocyanide based multicomponent reactions in applied chemistry, Chem. Rev. 106, 17–89 (2006).
(a) C. O. Kappe, D. Kumar, and R. S. Varma, Microwave-assisted high-speed parallel synthesis of 4-aryl-3, 4-dihydropyrimidin-2(1H)-ones using a solventless Biginelli condensation protocol, Synthesis 1799–1803 (1999); (b) U. Bora, A. Saikia and R. C. Boruah, A novel microwave-mediated one-pot synthesis of indolozines via a three-component reaction, Org. Lett. 5, 435–438 (2003).
D. Tejedor, A. Santos-Exposito, D. Gonzales-Cruz, J. J. Marrero-Tellado, and F. Garcia-Tellado, A modular, one-pot, four-component synthesis of polysubstituted 1, 3-oxazolidines, J. Org. Chem. 70, 1042–1045 (2005).
L. Dhar, S. Yadav, and R. Kappor, Solvent-free microwave activated three-component synthesis of thiazolo-s-triazine C-nucleosides, Tetrahedron Lett. 44, 8951–8954 (2003).
U. Bora, A. Saikia, and R. C. Boruah, A novel microwave-mediated one-pot synthesis of indolizines via a three-component reaction, Org. Lett. 5, 435–438 (2003).
V. Bailliez, R. M. de Figueiredo, A. Olesker, and J. Cleophax, A practical large-scale access to 1, 6-anhydro-β-D-hexopyranoses by a solid-supported solvent-free microwave-assisted procedure, Synthesis 1015–1017 (2003).
N. Gospodinova, A. Grelard, M. Jeannin, G. C. Chitanu, A. Carpov, V. Thiery, and T. Besson, Efficient solvent-free microwave phosphorylation of microcrystalline cellulose, Green Chemistry 4, 220–222 (2002).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2008 Springer Science + Business Media B.V
About this paper
Cite this paper
Ricci, A. (2008). Solventless Reactions Under Microwave Activation: Safety and Efficiency at the Service of Customer-friendly Chemistry. In: Mordini, A., Faigl, F. (eds) New Methodologies and Techniques for a Sustainable Organic Chemistry. NATO Science Series II: Mathematics, Physics and Chemistry, vol 246. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-6793-8_10
Download citation
DOI: https://doi.org/10.1007/978-1-4020-6793-8_10
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-6791-4
Online ISBN: 978-1-4020-6793-8
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)