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https://hdl.handle.net/10442/18468
Εξειδίκευση τύπου : | Άρθρο σε επιστημονικό περιοδικό |
Τίτλος: | Self Cycloaddition of o-Naphthoquinone Nitrosomethide to (±) Spiro{naphthalene(naphthopyranofurazan)}-one Oxide: An Insight into its Formation |
Δημιουργός/Συγγραφέας: | [EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter Gerontitis, Ioannis E [EL] Πετσαλάκης, Ιωάννης Δ.[EN] Petsalakis, Ioannis D. Tsoungas, Petros G. Varvounis, George |
Ημερομηνία: | 2022-11-23 |
Γλώσσα: | Αγγλικά |
ISSN: | 2192-6506 2192-6506 |
DOI: | 10.1002/cplu.202200313 |
Άλλο: | 36479609 |
Περίληψη: | 2-Hydroxy-1-naphthaldehyde oxime was oxidized by AgO (or Ag2 O), in presence of N-methyl morpholine N-oxide (NMMO), to the title spiro adduct-dimer (±)-Spiro{naphthalene-1(2H),4'-(naphtho[2',1':2,3]pyrano[4,5-c]furazan)}-2-one-11'-oxide by a Diels-Alder(D-A) type self-cycloaddition, through the agency of an o-naphthoquinone nitrosomethide (o-NQM). Moreover, 2-hydroxy-8-methoxy-1-naphthaldehyde oxime was prepared and subjected to the same oxidation conditions. Its sterically guided result, 9-methoxynaphtho[1,2-d]isoxazole, was isolated, instead of the expected spiro adduct. The peri intramolecular H bonding in the oxime is considered to have a key contribution to the outcome. Geometry and energy features of the oxidant- and stereo-guided selectivity of both oxidation outcomes have been explored by DFT, perturbation theory and coupled cluster calculations. The reaction free energy of the D-A intermolecular cycloaddition is calculated at -82.0 kcal/mol, indicating its predominance over the intramolecular cyclization of ca. -37.6 kcal/mol. The cycloaddition is facilitated by NMMO through dipolar interactions and hydrogen bonding with both metal complexes and o-NQM. The 8(peri)-OMe substitution of the reactant oxime sterically impedes formation of the spiro adduct, instead it undergoes a more facile cyclodehydration to the isoxazole structure by ca. 4.9 kcal/mol. |
Τίτλος πηγής δημοσίευσης: | ChemPlusChem |
Τόμος/Κεφάλαιο: | 87 |
Τεύχος: | 12 |
Θεματική Κατηγορία: | [EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry |
Λέξεις-Κλειδιά: | DFT calculations cycloaddition oxidation oximes spiro naphthoquinone |
Κάτοχος πνευματικών δικαιωμάτων: | © 2022 The Authors. ChemPlusChem published by Wiley-VCH GmbH |
Όροι και προϋποθέσεις δικαιωμάτων: | This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. |
Ηλεκτρονική διεύθυνση στον εκδότη (link): | https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202200313 |
Σημειώσεις: | Supporting information supplied by the authors is available here: https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202200313 |
Εμφανίζεται στις συλλογές: | Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο
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