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Synthesis of Polyenic 1,4-diones Directly from α,β-unsaturated Methyl Ketones and Studies on the Mechanism of the Self-sorting Tandem Reaction

Author: WangZiHua
Tutor: WuAnXin
School: Central China Normal University
Course: Organic Chemistry
Keywords: Since Category cascade reaction 1,4 - dione α, β- unsaturated methyl ketone Iodide 1,4 - dihydropyridines
CLC: O621.25
Type: Master's thesis
Year: 2009
Downloads: 18
Quote: 0
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Abstract


Environmentally friendly, easy, efficient and atom economical method is the inevitable trend of development of organic synthesis. Cascade reactions and multicomponent reaction is to consider the requirements of the atom economy, high efficiency, and green chemistry pot multi-step synthesis of complex target compounds can be rapidly developed a novel synthetic strategy. Cluster molecular self-classification behavior in the natural and life of the system is a very common phenomenon, it is a complex system of intermolecular interactions distinction between self and non-self-ability. In this thesis, molecular self-sorting behavior as the starting point of a new multi-line parallel cascade the synthesis reaction Policy - self-classification Cascade reaction in order to establish α, β-unsaturated methyl ketone dimerization even Liancheng polyene group 1,4 - diketones reaction. Meanwhile, in the study of the reaction mechanism of the process of establishment of α, β-unsaturated carbonyl compounds, α 'bits selectivity iodinated reaction. In addition, the study of the reaction mechanism of Hantzsch synthesis of 1,4 - dihydropyridines process, which further proved that the idea of ​​self-classification cascade reaction mechanism. The specific contents are as follows: the first chapter, the 1,4 - diketones are important intermediates in organic synthesis, can be used for synthesis of some five-membered heterocyclic compounds (e.g., furan, thiophene, pyrrole, etc.), these 5-membered heterocyclic compounds tend to be the main skeleton of the natural product, or itself has a good biological activity. Therefore, we have outlined the method of synthesis of 1,4 - diketone compounds, and based on self-classification of molecules in chemical reactions, the ideas of this thesis. Significantly different patterns of response for the second chapter, based on our group on cluster molecular understanding of self-classification of phenomena, a traditional cascade reaction and multi-component reaction - self-classification Cascade reaction, we first classic hydroxyl aldehyde condensation reaction to prepare 12 kinds of α, β-unsaturated methyl ketone Ⅱ -2 and realized of CuO / I 2 / DMSO under conditions intermolecular SP 3 methyl carbon is directly coupled into the ethylenically II -3, wherein the compound (E) - the Ⅱ-3J the structure by X-ray single crystal diffraction verified. Chapter III, on the basis of our group study, CuO / I 2 combination system of α, β-unsaturated ketone, α 'position of the selective iodide, while the carbon-carbon double bond and the aromatic ring is not affected. The chapter first systematic study of α, β-unsaturated ketone to the important intermediate α, β-unsaturated α'-iodoketone direct conversion. Chapter Hantzsch reaction synthesized 1,4 - dihydropyridine compounds IV -2. In the course of study of the reaction mechanism, found substrate IV-1a / IV-1c, IV-1a / IV-1d, IV-1b / the-1c IV, IV-1b / IV-1d when mixed with meta nitro The reaction of benzaldehyde and ammonium acetate, to obtain mainly asymmetric 1,4 - dihydro-pyridine compounds, almost no symmetrical 1,4 - dihydro-pyridine compounds generated, showed significant self-classification phenomenon. From the reaction mechanism of the synthesis of 1,4 - dihydropyridines further evidence we found that self-classification cascade reaction mode.

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CLC: > Mathematical sciences and chemical > Chemistry > Organic Chemistry > Organic Chemistry general issues > Properties of organic compounds > Chemical properties of organic reactions
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