Silicon carbide passive heating elements in microwave-assisted organic synthesis

Journal of Organic Chemistry

Volumn 71, Issue 12, 2006, Pages 4651-4658

  Kremsner, Jennifer M ^a   Kappe, C Oliver ^a  

^a INSTITUTE FOR MICROELECTRONICS   (Austria)

Author keywords

[No Author keywords available]

Indexed keywords

HEATING; MICROWAVES; SYNTHESIS (CHEMICAL); THERMAL EFFECTS; TOLUENE;

ORGANIC SYNTHESIS; PASSIVE HEATING ELEMENTS (PHES); TETRAHYDROFURAN;

SILICON CARBIDE;

CARBON TETRACHLORIDE; DIOXANE; HEXANE; IONIC LIQUID; REAGENT; SILICON CARBIDE; SOLVENT; TETRAHYDROFURAN; TOLUENE;

ALKYLATION; ARTICLE; CLAISEN REARRANGEMENT; CONDUCTANCE; DIELS ALDER REACTION; ENERGY TRANSFER; HEATING; MICHAEL ADDITION; MICROWAVE RADIATION; SYNTHESIS;

EID: 33744941827     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo060692v     Document Type: Article

References (97)

1. Books: (a) Microwave-Enhanced Chemistry. Fundamentals, Sample Preparation and Applications: Kingston, H. M., Haswell, S. J., Eds.; American Chemical Society: Washington, DC, 1997.
2. (b) Microwaves in Organic Synthesis; Loupy, A., Ed.; Wiley-VCH: Weinheim, Germany, 2002.
3. (c) Hayes, B. L. Microwave Synthesis: Chemistry at the Speed of Light; CEM Publishing: Matthews, NC, 2002.
4. (d) Microwave-Assisted Organic Synthesis: Lidström, P., Tierney, J. P., Eds.; Blackwell Publishing: Oxford, UK, 2005.
5. (e) Kappe, C. O.; Stadler, A. Microwaves in Organic and Medicinal Chemistry: Wiley-VCH: Weinheim, Germany, 2005.
6. Recent reviews: (a) Kappe, C. O. Angew. Chem., Int. Ed. 2004, 43, 6250 and references therein.
7. (b) Hayes, B. L. Aldrichim. Acta 2004, 37, 66.
8. (c) Roberts B. A.; Strauss C. R. Acc. Chem. Res. 2005, 38, 653.
9. (a) De La Hoz, A.; Diaz-Ortiz, A.; Moreno, A. Chem. Soc. Rev. 2005, 34, 164.
10. (b) Ferreux, L.; Loupy, A. Tetrahedron 2001, 57, 9199.
11. (c) Kuhnert, N. Angew. Chem., Int. Ed. 2002, 41, 1863.
12. (d) Strauss, C. R. Angew. Chem., Int. Ed. 2002, 41, 3589.
13. For reviews, see: (a) Larhed, M.; Hallberg, A. Drug Discovery Today 2001, 6, 406.
14. (b) Wathey, B.; Tierney, J.; Lidström, P.; Westman, J. Drug Discovery Today 2002, 7, 373.
15. (c) Al-Obeidi, F.; Austin, R. E.; Okonya, J. F.; Bond, D. R. S. Mini-Rev. Med. Chem. 2003, 3, 449.
16. (d) Shipe, W. D.; Wolkenberg, S. E.; Lindsley, C. W. Drug Disovery Today: Technol. 2005, 2, 155.
17. (e) Kappe, C. O.; Dallinger, D. Nature Rev. Drug Discovery 2006, 5, 51.
18. For reviews, see: (a) Bogdal, D.; Penczek, P.; Pielichowski, J.; Prociak, A. Adv. Polym. Sci. 2003, 163, 193.
19. (b) Wiesbrock, F.; Hoogenboom, R.; Schubert, U. S. Macromol. Rapid Commun. 2004, 25, 1739.
20. For reviews, see: (a) Barlow, S.; Marder, S. R. Adv. Funct. Mater. 2003, 13, 517.
21. (b) Zhu, Y.-J.; Wang, W. W.; Qi, R.-J.; Hu, X.-L. Angew. Chem., Int. Ed. 2004, 43, 1410.
22. For a review, see: Tsuji, M.; Hashimoto, M.; Nishizawa, Y.; Kubokawa, M.; Tsuji, T. Chem. Eur. J. 2005, 11, 440.
23. (a) Orrling, K.; Nilsson, P.; Gullberg, M.; Larhed, M. Chem. Commun. 2004, 790.
24. (b) Zhong, H.; Zhang, Y.; Wen, Z.; Li, L. Nature Biotechnol. 2004, 22, 1291.
25. (c) Zhong, H.; Marcus, S. L.; Li, L. J. Am. Soc. Mass Spectrom. 2005, 16, 471.
26. (a) Gabriel, C.; Gabriel, S.; Grant, E. H.; Halstead, B. S.; Mingos, D. M. P. Chem. Soc. Rev. 1998, 27, 213.
27. (b) Mingos, D. M. P.; Baghurst, D. R. Chem. Soc. Rev. 1991, 20, 1. See also refs 1-3.
28. Loones, K. T. J.; Maes, B. U.; Rombouts, G.; Hostyn, S.; Diels, G. Tetrahedron 2005, 61, 10338.
29. Nüchter, M.; Müller, U.; Ondruschka, B.; Tied, A.; Lautenschläger, W. Chem. Eng. Technol. 2003, 26, 1207.
30. Neas, E.; Collins, M. Introduction to Microwave Sample Preparation: Theory and Practice; Kingston, H. M., Jassie, L. B., Eds.; American Chemical Society: Washington, DC, 1988.
31. Kremsner, J. M.; Kappe, C. O. Eur. J. Org. Chem. 2005, 17, 3672.
32. (a) Ley, S. V.; Leach, A. G.; Storer, R. I. J. Chem. Soc., Perkin Trans 1 2001, 358.
33. (b) Baxendale, I. R.; Lee, A.-L.; Ley, S. V. Synlett 2001, 1482.
34. Leadbeater, N. E.; Torenius, H. M. J. Org. Chem. 2002, 67, 3145.
35. Hoffman, J.; Nüchter, M.; Ondruschka, B.; Wasserscheid, P. Green Chem. 2003, 5, 296.
36. Van der Eycken, E.; Appukkuttan, P.; De Borggraeve, W.; Dehaen, W.; Dallinger, D.; Kappe, C. O. J. Org Chem. 2002, 67, 7904.
37. For recent reviews, see: (a) Leadbeater, N. E.; Torenius, H. M.; Tye, H. Comb. Chem. High Throughput Screening 2004, 7, 511.
38. (b) Habermann, J.; Ponzi, S.; Ley, S. V. Mini-Rev. Org. Chem. 2005, 2, 125.
39. 6) used as doping reagent led to complete decomposition of the starting material and therefore inhibited the desired reaction pathway.
40. Glenn, A. G.; Jones, P. B. Tetrahedron Lett. 2004, 45, 6967.
41. (a) Nüchter, M.; Ondruschka, B.; Fischer, B.; Tied, A.; Lautenschläger, W. Chem. Eng. Technol. 2005, 77, 171.
42. (b) Nichkova, M.; Park, E.-K.; Koivunen, M. E.; Kamita, S. G.; Gee, S. J.; Chuang, J.; Van Emon, J. M.; Hammock, B. D. Talanta 2004, 63, 1213.
43. (c) Björklund, E.; von Holst, C.; Anklam, E. Trends Anal. Chem. 2002, 21, 39.
44. (d) Camel, V. Trends Anal. Chem. 2000, 19, 229.
45. (e) For applications in microwave drying, see: Link, D. D.; Kingston, H. M.; Havrilla, G. J.; Colletti, L. P. Anal. Chem. 2002, 74, 1165.
46. (f) For applications in microwave digestion, see: Han, Y.; Kingston, H. M.; Richter, R. C.; Pirola, C. Anal. Chem. 2001, 73, 1106.
47. To the best of our knowledge, the utilization of such heating inserts (generally made out of fluoropolymers doped with graphite or carbon black, ref 29) in the context of microwave synthesis has to date only been mentioned in footnotes in three recent publications dealing with microwave-assisted pericyclic rearrangements in nonpolar solvents by the groups of Davies and Barriault, respectively (ref 23).
48. (a) Davies, H. M. L.; Beckwith, R. E. J. J. Org. Chem. 2004, 69, 9241.
49. (b) Barriault, L.; Denissova, I. Org. Lett. 2002, 4, 1371.
50. (c) Morency, L.; Barriault, L. J. Org. Chem. 2005, 70, 8841.
51. Garbacia, S.; Desai, B.; Lavastre, O.; Kappe, C. O. J. Org. Chem. 2003, 68, 9136.
52. A similar observation was made by Maes and co-workers with reaction vessels used in a multimode microwave instrument. See ref 10 for details.
53. Leadbeater, N. E.; Pillsbury, S. J.; Shanahan, E.; Williams, V. A. Tetrahedron 2005, 61, 3565.
54. While investigating the behavior of ionic liquids under microwave irradiation conditions we discovered one additional problem of using these materials in conjunction with nonpolar solvents. In many instances the ionic liquid will not be soluble in the nonpolar solvent, even at higher temperatures. While this may be of advantage for subsequent product isolation (the product being extracted to the nonpolar solvent), this creates a significant problem in terms of temperature measurement and reproducibility under microwave conditions. By heating a biphasic system consisting of immiscible solvents with vastly different loss tangents, differential heating will occur (ref 28). Depending on where and how the "reaction temperature" is measured, different values will be obtained (Figure S8 in the Supporting Information). The problem is aggravated by the fact that (single-mode) microwave reactors from different vendors either measure the temperature by IR sensor from the bottom or from the side, therefore in one case measuring the temperature of the (very hot) ionic liquid phase, in the other case monitoring the temperature of the (cooler) organic layer for the same process. We therefore recommend to use ionic liquids that are soluble in the solvent system of choice in order to avoid these problems (see refs 17 and 24).
55. For a case of differential microwave heating involving a chloroform/water biphasic system, see: Raner, K. D.; Strauss, C. R.; Trainor, R. W.; Thorn, J. S. J. Org. Chem. 1995, 60, 2456.
56. Weflon and Carboflon are commercially available heating inserts from Milestone s.r.l. (www.milestonesci.com) and CEM Corp. (www.cem.com).
57. (a) Nüchter, M.; Ondruschka, B.; Weiss, D.; Beckert, R.; Bonrath, W.; Gum, A. Chem. Eng. Technol. 2005, 28, 871.
58. (b) For a detailed discussion of commercially available microwave reactors and the difference between single-mode and multimode cavities, see ref 1e, Chapter 3, pp 29-55.
59. (a) Bogdal, D.; Lukasiewicz, M.; Pielichowski, J.; Miciak, A.; Bednarz, Sz. Tetrahedron 2003, 59, 649.
60. (b) Lukasiewicz, M.; Bogdal, D.; Pielichowski, J. Adv. Synth. Catal. 2003, 345, 1269.
61. (a) Properties of Silicon Carbide; Harris, G. L., Ed.: Institute of Electrical Engineers: London, UK, 1995.
62. (b) Silicon Carbide: Recent Major Advances: Choyke, W. J., Matsunami, H., Pensl, G., Eds.; Springer: Berlin, Germany, 2004.
63. (c) Advances in Silicon Carbide Processing and Applications: Saddow, S. E., Agarwal, A., Eds.; Artech House Inc.: Norwood, MA, 2004.
64. Dong, C.; Guo, J.; Fu, G. C.; Yang, L. H.; Chen, H. Supercond. Sci. Technol. 2004, 17, L55.
65. Lasri, J.; Ramesh, P. D.; Schachter, L. J. Am. Ceram. Soc. 2000, 83, 1465.
66. Sturcken, E. F. Ceram. Trans. 1991, 21, 433.
67. SiC passive heating elements are available from Anton Paar GmbH (www.anton-paar.com).
68. Martín Castro, A. M. Chem. Rev. 2004, 104, 2939.
69. Baxendale, I. R.; Lee, A.-I.; Ley, S. V. J. Chem. Soc., Perkin Trans. 1 2002, 16, 1850.
70. (a) Tsai, T.-W.; Wang, E.-C.; Li, S.-R.; Chen, Y.-H.; Lin, Y.-L.; Wang, Y.-F.; Huang, K.-S. J. Chin. Chem. Soc. 2004, 51, 1307.
71. (b) Van, T. N.; Debenedetti, S.; Kimpe, N. D. Tetrahedron Lett. 2003, 44, 4199.
72. A safety feature of the single-mode reactor aborts the experiment if the preset temperature cannot be reached after a few minutes with full power. This also prevents overheating and damage of the magnetron.
73. Similar to the results by Ley (ref 38) we find that pulsed microwave heating (6 cycles of 15 min irradiation at 250 °C) gave better results (>99% conversion) than one continuous irradiation cycle for 90 min (92% conversion). This microwave pulsing effect was not investigated further, however.
74. Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. Angew. Chem., Int. Ed. 2002, 41, 1668.
75. Pindur, U.; Lutz, G.; Otto, G. Chem. Rev. 1993, 93, 741.
76. (a) Hall, H. K., Jr.; Padias, A. B.; Li, Y.; Clever, H. A.; Wang, G. J. Chem. Soc., Chem. Commun. 1991, 1279.
77. (b) Li, Y.; Padias, A. B.; Hall, H. K., Jr. J. Org. Chem. 1993, 58, 7049.
78. Stadler, A.; Yousefi, B. H.; Dallinger, D.; Walla, P.; Van der Eycken, E.; Kaval, N.; Kappe, C. O. Org. Process Res. Dev. 2003, 7, 707.
79. The efficiency of the SiC passive heating elements in heating larger amounts (100 mL) of a variety of nonpolar solvents in multimode environments was studied in detail. These data are reproduced in the Supporting Information (Figure S12). There is also an important safety aspect that needs to be considered. It is not advised to heat non- or low-absorbing reaction mixtures for prolonged periods of time in microwave reactors. This leads to the magnetron continuously operating at the maximum power level trying to reach the selected set temperature (cf. Figure S14), and ultimately can result in overheating and damage of the magnetron (see ref 40) or destructive coupling of microwave irradiation with sensitive instrument and/or vessel parts.
80. Varala, R.; Alam, M. M.; Adapa, S. R. Synlett 2003, 720.
81. Almena, I.; Diez-Barra, E.; de la Hoz, A.; Ruiz, J.; Sanches-Migallon, A.; Elguero, J. J. Heterocycl. Chem. 1998, 35, 1263.
82. (a) Strohmeier, G. A.; Kappe, C. O. Angew. Chem., Int. Ed. 2004, 43, 621.
83. (b) Strohmeier, G. A.; Reidlinger, C.; Kappe, C. O. QSAR Comb. Sci. 2005, 24, 364.
84. (a) Zigeuner, G.; Strallhofer, T.; Wede, F.; Lintschinger, W.-B. Monatsh. Chem. 1975, 106, 1469.
85. (b) Glasnov, T. N.; Vugts, D. J.; Koningstein, M. M.; Desai, B.; Fabian, W. M. F.; Orru, R. V. A.; Kappe, C. O. QSAR Comb. Sci. 2006, 25 (published online March 16, 2006; DOI 10.1002/qsar.200540210).
86. For a review on Dimroth rearrangements of this type, see: El Ashry, E. S. H.; El Kilany, Y.; Rashed, N.; Assafir H. Adv. Heterocycl. Chem. 1999, 75, 79.
87. It has to be considered, however, that in many cases of microwave-assisted synthesis with nonpolar media the reaction vessel also functions as a "passive heating element" (self-heating of the glass vessels, see Figures S1 and S14) and that there are several recent examples where the indirect heating of reaction containers by microwaves was achieved by coating the vessel with a thin metal film that proved critical for the success of the investigated transformations. For example, see: (a) He, P.; Haswell, S. J.; Fletcher, P. D. I. Lab Chip 2004, 4, 38.
88. (b) He, P.; Haswell, S. J.; Fletcher, P. D. I. Appl. Catal., A 2004, 274, 111.
89. (c) Comer, E.; Organ, M. G. J. Am. Chem. Soc. 2005, 127, 8160.
90. (d) Stadler, A.; Kappe, C. O. Org. Lett. 2002, 4, 3541.
91. There are also cases where reaction containers, i.e., deep well plates made out of Weflon material, have been used successfully in microwave synthesis: (e) Macleod, C.; Martinez-Teipel, B. I.; Barker, W. M.; Dolle, R. E. J. Comb. Chem. 2006, 8, 132.
92. (f) Nüchter, M.; Ondruschka, B. Mol. Diversity 2003, 7, 253.
93. (g) See also: Lin, Q.; O'Neill, J. C.; Blackwell, H. E. Org. Lett. 2005, 7, 4455.
94. Alberola, A.; Ortega, A. G.; Pedrosa, R.; Bragado, J. L. P.; Amo, J. F. R. J. Chem. Soc., Perkin Trans. 1 1983, 1209.
95. Abe, T.; Baba, H.; Soloshonok, I. J. Fluorine Chem. 2001, 108, 215.
96. Choudary, B. M.; Sridhar, C.; Sateesh, M.; Sreedhar, B. J. Mol. Catal. A: Chem. 2004, 212, 237.
97. Fu, N.-Y.; Yuan, Y.-F.; Cao, Z.; Wang, S.-W.; Wang, J. T.; Peppe, C. Tetrahedron 2002, 58, 4801.