Synthesis And Luminescence Of Coupled 1, 4-Dihydropyridine Derivative

1,4-dihydropyridine(1,4-DHP) is one family of organic compound which has important physiological function and pharmacology activity, and was widely applied in biology and medicine, such as the clinical medicine to prevent and control cardiovascular disease, stomach disease and Reynold sick, and the auxiliary medicine to treat pulmonary artery high pressure and the insane epilepsy. Therefore, great effort has been devoted to the research of 1,4-DHP. In recent years, the design and synthesis of new DHP derivatives based on the structure-activity relationship (QSAR) attract much interest, and there has two main aspects on the 1, 4-dihydropyridine compounds: One is named diethyl 2, 6-dimethyl-1, 4-dihydropyridine-3, 5-dicarboxylate served as the feed additive with physiological activity. The other is a series medicine from substituted 1,4-DHP compounds. Up to date, there is much research on the synthetic methodology of DHP, but the system synthesis is still being optimized. On the other hand, the dihydropyridine as the fluorescent probes has several reports, but as fluorescent materials nearly has not been well exploited. In this thesis a new series of coupled 1, 4-dihydrylpyridine derivatives have been designed and synthesized. The main results include the following:1. Several coupled dihydropyridine compounds have been designed using semiempirical method and density functional theory (DFT) at B3LYP/6-31G level in Gaussian programme;2. Nine coupled arylaldehydes and seven coupled dihydropyridines have been synthesized by the reaction of hydroxyl substitution arylaldehydes, dibromoalkane and ethyl acetoacetate, and confirmed by 1H NMR;3. The structures of three compounds have been characterized by single-crystal X-ray diffraction. The crystal structure of diethyl 4-(3-hydroxyphenyl)-2, 6-dimethyl-1, 4-dihydropyridine-3, 5-dicarboxylate reveals that the molecular stacking structure is centrosymmetric, the dihedral angle between the pyridine and the phenyl ring is 90.0(2)°, and the dimer with a hydrogen-bonded R22 (18) ring is constructed through intermolecular hydrogen bonds. An interesting one-dimensional supramolecular chain with an infinite channel is built up from the dimers as the second structural units through other hydrogen bonds.In the coupled flexible diaromatic aldehyde 1, 4-di(p-formylphenoxyl)butane crystal lattice, there are several kinds of supramolecular structures constructed by intermolecular C-H···O hydrogen bonds andπ-πinteractions, namely one-dimensional chain, two-dimensional layer and three-dimensional network. Moreover two kind of hydrogen-bonded R22 (8) and R44 (42) ring exists in the crystal structure.The single crystal study of the coupled 1, 4-dihydrylpyridine from salicylaldehye and 1, 2-dibromethane reveals that the nano-sized molecular length is 1.6 nm, and there have variform supramolecular structures. The tetramer with a large hydrogen-bonded R44(46) ring is constructed from four molecules via intermolecular N-H...O hydrogen bonds. Five single molecules generated a pentamer with a Z-type motif in which the centered molecule contacts with four separate molecules through hydrogen bonding. The pentamers served as the supramolecular second building units (SSBUs) built up a infinite three-connected two-dimensional (2-D) network;4. The preliminary fluorescent spectrum analysis of two dihydropyridine derivatives was performed. The photoluminescence of the coupled 1, 4-dihydrylpyridine from salicylaldehye and 1, 2-dibromethane was investigated in solid state at room temperature. The fluorescent spectra of diethyl 1,4-dihydro-4-hydroxyphenyl-2, 6-dimethylpyridine-3, 5-dicarboxylate in the organic solution of different metal ions were tested.