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Related to the issue of nonthermal microwave effects is the concept that simultaneous external cooling of the reaction mixture (or maintaining subambient reaction temperatures) while heating by microwaves can in some cases lead to an enhancement of the overall process. Here, the reaction vessel is cooled from the outside by compressed air or with the aid of a cooling fluid while being irradiated by microwaves. This allows a higher level of microwave power to be directly administered to the reaction mixture thereby potentially enhancing nonthermal microwave effects that rely on the electric field strength. At the same time, overheating will be prevented by continuously removing heat. For recent examples using this technique. see ref 17 and references cited therein
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Related to the issue of nonthermal microwave effects is the concept that simultaneous external cooling of the reaction mixture (or maintaining subambient reaction temperatures) while heating by microwaves can in some cases lead to an enhancement of the overall process. Here, the reaction vessel is cooled from the outside by compressed air or with the aid of a cooling fluid while being irradiated by microwaves. This allows a higher level of microwave power to be directly administered to the reaction mixture thereby potentially enhancing nonthermal microwave effects that rely on the electric field strength. At the same time, overheating will be prevented by continuously removing heat. For recent examples using this technique. see ref 17 and references cited therein.
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Solvents used for microwave synthesis can be classified as high (tan δ > 0.5; for example, ethanol, DMSO, methanol, formic acid), medium (tan δ 0.1-0.5; for example, acetic acid, 1,2-dichlorobenzene, NMP, DMF, water), and low microwave absorbing (tan δ < 0.1; for example, chloroform, ethyl acetate, THF, dichloromethane, toluene, o-xylene, hexane). Other common solvents without a permanent dipole moment such as carbon tetrachloride, benzene, p-xylene and dioxane can be considered as microwave transparent.
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Pérez, E.R.1
Loupy, A.2
Liagre, M.3
de Guzzi Plepis, A.M.4
Cordeiro, P.J.5
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(b) Abenhaim, D.; Diez-Barra, E.; de la Hoz, A.; Loupy, A.; Sánchez-Migallón, A. Heterocycles 1994, 38, 793.
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83
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37549032913
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By microwave irradiating a biphasic system consisting of immiscible solvents/reagents with vastly different loss tangents, differential heating of the two phases will occur. Depending on where and how the reaction temperature is measured, different values will be obtained. A case in point are biphasic mixtures of strongly microwave abosorbing ionic liquids and nearly microwave transparent organic solvents. See ref 16 for more details
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By microwave irradiating a biphasic system consisting of immiscible solvents/reagents with vastly different loss tangents, differential heating of the two phases will occur. Depending on where and how the "reaction temperature" is measured, different values will be obtained. A case in point are biphasic mixtures of strongly microwave abosorbing ionic liquids and nearly microwave transparent organic solvents. See ref 16 for more details.
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86
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37549060848
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Ab initio calculations at the B3LYP/6-31G* level confirmed that the N1 isomer (11, Ar = phenyl) is more stable than the N4 isomer (10, Ar = phenyl) by ca. 8 kcal/mol.
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Ab initio calculations at the B3LYP/6-31G* level confirmed that the N1 isomer (11, Ar = phenyl) is more stable than the N4 isomer (10, Ar = phenyl) by ca. 8 kcal/mol.
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87
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33746658962
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Difficulties reproducing this reaction in a solvent-free regime under microwave conditions have been recently reported. For more information, see: Lebouvier, N, Giraud, F, Corbin, T, Na, Y.-M, Le Baut, G, Marchand, P, Le Borgne, M. Tetrahedron Lett. 2006, 47, 6479
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Difficulties reproducing this reaction in a solvent-free regime under microwave conditions have been recently reported. For more information, see: Lebouvier, N.; Giraud, F.; Corbin, T.; Na, Y.-M.; Le Baut, G.; Marchand, P.; Le Borgne, M. Tetrahedron Lett. 2006, 47, 6479.
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For recent reviews, see: a
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For recent reviews, see: (a) Leadbeater, N. E.; Torenius, H. M.; Tye, H. Comb. Chem. High Throughput Screen. 2004, 7, 511.
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Comb. Chem. High Throughput Screen
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Leadbeater, N.E.1
Torenius, H.M.2
Tye, H.3
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(b) Habermann, J.; Ponzi, S.; Ley, S. V. Mini-Rev. Org. Chem. 2005, 2, 125.
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Habermann, J.1
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Ley, S.V.3
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(a) Gelens, E.; Smeets, L.; Sliedregt, L. A. J. M.; Van Steen, B. J.; Kruse, C. G.; Leurs, R.; Orru, R. V. A. Tetrahedron Lett. 2005, 46, 3751.
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(2005)
Tetrahedron Lett
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Gelens, E.1
Smeets, L.2
Sliedregt, L.A.J.M.3
Van Steen, B.J.4
Kruse, C.G.5
Leurs, R.6
Orru, R.V.A.7
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(b) Perreux, L.; Loupy, A.; Volatron, F. Tetrahedron 2002, 58, 2155.
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(2002)
Tetrahedron
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Perreux, L.1
Loupy, A.2
Volatron, F.3
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(c) Massicot, F.; Plantier-Royon, R.; Portella, C.; Saleur, D.; Sudha, A. V. Synthesis 2001, 2441.
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(2001)
Synthesis
, pp. 2441
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Massicot, F.1
Plantier-Royon, R.2
Portella, C.3
Saleur, D.4
Sudha, A.V.5
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94
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Ianelli, M.; Alupei, V.; Ritter, H. Tetrahedron 2005, 61, 1509.
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Tetrahedron
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, pp. 1509
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Ianelli, M.1
Alupei, V.2
Ritter, H.3
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95
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(a) Goretzki, C.; Krlej, A.; Steffens, C.; Ritter, H. Macromol. Rapid Commun. 2004, 25, 513.
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Macromol. Rapid Commun
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Goretzki, C.1
Krlej, A.2
Steffens, C.3
Ritter, H.4
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97
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In order to mimic the rapid heating profiles observed under microwave conditions, the conventionally heated experiments were conducted using a differential calorimetric scanning (DSC) apparatus
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In order to mimic the rapid heating profiles observed under microwave conditions, the conventionally heated experiments were conducted using a differential calorimetric scanning (DSC) apparatus.
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98
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For further discussion on this reaction, see also the follwowing references: (a) Koopmans, C.; Ianelli, M.; Kerep, P.; Klink, M.; Schmitz, S.; Sinwell, S.; Ritter, H. Tetrahedron 2006, 62, 4709.
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For further discussion on this reaction, see also the follwowing references: (a) Koopmans, C.; Ianelli, M.; Kerep, P.; Klink, M.; Schmitz, S.; Sinwell, S.; Ritter, H. Tetrahedron 2006, 62, 4709.
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99
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Reference 12c, pp 162-164
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(b) Reference 12c, pp 162-164.
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Reference 12d, pp 254-256
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(c) Reference 12d, pp 254-256.
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101
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For a recent study on microwave effects, see
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For a recent study on microwave effects, see: Dressen, M. H. C. L.; van de Kruijs, B. H. P.; Meuldijk, J.; Vekemans, J. A. J. M.; Hulshof, L. A. Org. Process Res. Dev. 2007, 11, 865.
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Org. Process Res. Dev
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Dressen, M.H.C.L.1
van de Kruijs, B.H.P.2
Meuldijk, J.3
Vekemans, J.A.J.M.4
Hulshof, L.A.5
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102
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Kondolff, I.; Doucet, H.; Santelli, M. Organometallics 2006, 25, 5219.
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(2006)
Organometallics
, vol.25
, pp. 5219
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Kondolff, I.1
Doucet, H.2
Santelli, M.3
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