The Syntheses, Characterization and Crystal Structures of a Series of Heterocyclic β-Diketones and Their Isoxazole Compounds
In the field of coordination chemistry, the introduction of heterocyclic substituents into the structure of β-diketone enables ligand to produce multiple coordination sites. The adoption of small steric oxime group into the structure of heterocyclic β-diketone by Schiff-base condensation will furthe...
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Published in | Current organic synthesis Vol. 16; no. 8; p. 1174 |
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Main Authors | , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
United Arab Emirates
01.01.2019
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Subjects | |
Online Access | Get more information |
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Summary: | In the field of coordination chemistry, the introduction of heterocyclic substituents into the structure of β-diketone enables ligand to produce multiple coordination sites. The adoption of small steric oxime group into the structure of heterocyclic β-diketone by Schiff-base condensation will further increase coordination sites and facilitate the generation of polynuclear structures.
A series of β-diketones (2a-2c) containing different heterocycles such as pyridine, thiophene and furan and their corresponding isoxazole compounds (3a-3c) were synthesized.
The Claisen condensations were investigated in a solvent-free rheological phase system at room temperature to obtain heterocyclic β-diketones 2a-2c, which further reacted with hydroxylamine hydrochloride to obtain heterocyclic isoxazoles 3a-3c. All these compounds were well characterized by EA, IR, 1H NMR and X-ray crystal diffraction to confirm the structures. Synthetic mechanisms of compounds and the effects of different heterocycles on reactivity were discussed deeply.
1H NMR indicated that these β-diketones do not exist as a total diketonic form but an equilibration between diketone and enol forms in CDCl3 solvent, in which the enol form accounts for 98.0% in 2a, 94.3% in 2b, 95.5% in 2c. While the crystal structures of 2a-2c showed that the reaction allows to isolate diketones in solid state. Crystal structures of 3a-3c showed that the neutral β-ketone oximes resonate and cyclize to form the target heterocyclic isoxazoles.
SN1 nucleophilic substitution mechanism of Claisen ketoester condensation was proposed for the syntheses of 2a-2c, and SN1 single molecule nucleophilic substitution reaction mechanism was put forward for 3a-3c. |
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ISSN: | 1570-1794 |
DOI: | 10.2174/1570179416666191022113022 |