Synthesis Of Some Heterocyclic Compounds Using 5-substituted-1,3-cyclohexanedione As Block

To begin with, the thesis summarizes the application of 1,3-cyclohexanedione in the synthesis of heterocyclic compounds. Then some heterocyclic compounds were synthesized from 5-substituted-1,3-cyclohexanedione.In this work, firstly, a series of novel 10-amino-9-aryl-2,3,4,5,6,7,9,10-octahydro- acridine-1,8-dione derivatives were synthesized in solvent-free condition by hydrazine or phenylhydrazine and 9-aryl-1,8-dioxo-2,3,4,5,6,7,9-heptahydroxanthene derivatives which were prepared by 5-substituted-1,3-cyclohexanedione and aromatic aldehydes in the presence of concentrated H2SO4 as catalyst in water. This method achieved green synthesis. Due to the introduction of amino group into N-position, the title compounds can be modified easily. And the lone pair electrons on N atom is relatively easy to delocalize, so that the absorption wavelength of the title compounds occur red shift. During the experiment, it is found that the dichloromethane solutions of 10-amino-9-aryl-2,3,4,5,6,7,9,10-octahydro- acridine-1,8-dione derivatives can emit strong fluorescence with the excitation of ultraviolet. And therefore, we test the fluorescence of two compounds at room temperature. Results reveal that the Stokes shift both are over 120nm, which are accordant with the expectation aim. In addition, this method supplies a new route for the synthesis of acridine derivatives with amino group on N-position.Secondly, a series of novel benzopyran[2,3-b]quinoline-1,10-dione derivatives and intermediate compounds enamine were obtained from 5-substituted-1,3-cyclohexanedione andβ-dicyanostyrenes which were prepared by Knoevenagel condensation with different aromatic aldehydes and malononitrile. And as the six-membered tetracyclic compounds, benzopyran[2,3-b]quinoline-1,10-dione derivatives contain simultaneously oxygen and nitrogen atoms on their carbon frameworks. They not only possess the structure of benzopyran and quinoline, but also contain a pyranopiperidine ring. Additionally, the title compounds can be modified easily due to the introduction of carbonyl group on the outer cyclohexane ring. This achieve the aim to enrich the tetracyclic compounds and modify the structures according to the need. In the synthesis of benzopyran[2,3-b]- quinoline-1,10-dione derivatives, the target compounds are obtained via a one-step spirocyclization through the improvement of the traditional two-step reaction. This method supplies a convenient route for synthesis of the similar compounds. Finally, we synthesized a class of 4,7-diaryl-5-oxo-4H-benzo[b]pyran derivatives from appropriate aromatic aldehydes and 5-aryl-1,3-cyclohexanedione with malononitrile in the presence of dilute HCl as catalyst (30 mmol/L). This method achieves green synthesis. Due to the exsitance of chiral carbons, the title compounds have stereoisomers. In order to confirm the sterostructure of 4,7-diaryl-5-oxo-4H-benzo[b]pyran derivatives, 2-amino-3- cyano-4-phenyl-7-(4-methoxypheny)-5-oxo-5,6,7,8-tetrahydro-4H-benzopyran is chosen to train its single crystal.A series of new acridine derivatives, enamine, benzopyran[2,3-b]quinoline-1,10-dione derivatives and benzopyran derivatives are synthesized starting from 5-substituted-1,3- cyclohexanedione. All compounds have not been reported. And the structures of all compounds were characterized by elemental analysis, IR, MS and 1H NMR spectra.