Substituent Effects on an Inverse Electron Demand Hetero Diels−Alder Reaction in Aqueous Solution and Organic Solvents: Cycloaddition of Substituted Styrenes to Di(2-pyridyl)-1,2,4,5-tetrazine

Substituent Effects on an Inverse Electron Demand Hetero Diels−Alder Reaction in Aqueous Solution and Organic Solvents: Cycloaddition of Substituted Styrenes to Di(2-pyridyl)-1,2,4,5-tetrazine

The kinetics of the Diels−Alder reactions of di(2-pyridyl)-1,2,4,5-tetrazine (1) with substituted styrenes 2 was investigated in aqueous media and in organic solvents. The second-order rate constants of this reaction increase dramatically in water-rich media. A decrease in pH accelerates the aqueous...

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Veröffentlicht in:Journal of organic chemistry 1996-03, Vol.61 (6), p.2001-2005
Hauptverfasser: Wijnen, Jan W, Zavarise, Silvia, Engberts, Jan B. F. N, Charton, Marvin
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container_end_page 2005
container_issue 6
container_start_page 2001
container_title Journal of organic chemistry
container_volume 61
creator Wijnen, Jan W
Zavarise, Silvia
Engberts, Jan B. F. N
Charton, Marvin
description The kinetics of the Diels−Alder reactions of di(2-pyridyl)-1,2,4,5-tetrazine (1) with substituted styrenes 2 was investigated in aqueous media and in organic solvents. The second-order rate constants of this reaction increase dramatically in water-rich media. A decrease in pH accelerates the aqueous Diels−Alder reaction even more. The Hammett ρ-values and also the electronic demand η-values of the reaction are solvent sensitive. In protic solvents the dipolar character of the activated complex is increased, but simultaneously hydrogen-bond interactions stabilize the activated complex. These effects are most pronounced in 2,2,2-trifluoroethanol, which shows that the aqueous accelerations cannot be solely attributed to solvent-induced changes of the reaction mechanism.
doi_str_mv 10.1021/jo9518563
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title Substituent Effects on an Inverse Electron Demand Hetero Diels−Alder Reaction in Aqueous Solution and Organic Solvents: Cycloaddition of Substituted Styrenes to Di(2-pyridyl)-1,2,4,5-tetrazine
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