Light-Induced Reactions of Diazotetrahydrofuranone without Elimination of Nitrogen: Experimental and Mechanistic Study
| Autor: | Liudmila L. Rodina, Nina L. Tonogina, Victor I. Baranovskii, Valerij A. Nikolaev, Alexey Povolotskiy, Olesia S. Galkina |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Organic Chemistry Hydrazone Wolff rearrangement 010402 general chemistry Photochemistry 01 natural sciences 0104 chemical sciences chemistry.chemical_compound chemistry Excited state Singlet fission Diazo Singlet state Multiplicity (chemistry) Isomerization |
| Zdroj: | The Journal of Organic Chemistry. 82:11399-11405 |
| ISSN: | 1520-6904 0022-3263 |
| DOI: | 10.1021/acs.joc.7b01848 |
| Popis: | The energies and lifetimes of the excited states (S1, S2, S5, T1) of a diazotetrahydrofuranone were determined using experimental and computational methods. It was shown that direction of the diazoketone photochemical transformations without elimination of nitrogen is determined by multiplicity and energy of the excited state, generated by UV irradiation of diazo compound: isomerization to α-ketodiazirine proceeds from the singlet S1 state, whereas the alternative process of C–H insertion with hydrazone formation occurs through the triplet T1 state. The most probable excited state that leads to elimination of nitrogen and Wolff rearrangement is one of the highest singlet excited states of diazotetrahydrofuranone. |
| Databáze: | OpenAIRE |
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