Synthesis Of Tetraazaparacyclophanes And Green Organic Synthesis, Reaction Of Heterocyclic Compounds

Half of the organic compounds are heterocyclic compounds, which are large in number and numerous in variety. Many of them exist in nature and are related to the process of life. Therefore, the design and synthesis of heterocyclic compounds with biological activities attract great attention of synthesis chemists, and become a hot point in the field of organic synthesis.This thesis mainly focuses on the synthesis of tetraazaparacyclophanes and the green organic synthesis and reaction of some heterocyclic compounds. Sixty-four compounds were prepared, twenty-six compounds of them have not been reported in literatures. The structures of the compounds were determined by 1H NMR, 13C NMR, IR, elemental analysis and MS.Tetraazaparacyclophanes play an important role in cyclophanes, which are also host compounds in host-guest chemistry. Molecular recognition based on host-guest complexes is a fundamental chemical process, which controls many significant biological reactions involved enzyme, antibody, carrier, channel and acceptor, etc. In the recent decades, developing host molecule which can complex with specific guest becomes the base of host-guest chemistry. The structure of tetraazaparacyclophane is a ring with benzene rings connected by nitrogen-containing carbon bridges. It has a well-defined hydrophobic cavity. In addition, the benzene rings are fixed at an angle and "face" conformation, which enables the formation of an inclusion cavity. As an artificial enzyme, tetraazaparacyclophane can be optimized by changing the shape and size of the hydrophobic cavity or being attached with active groups to form new host compounds. Seven of the tetraazacyclophanes with different hydrophobic cavity size were synthesized from 4,4'-diaminodiphenylmethane by protection, cyclization and deprotection. Three of the tetraazacyclophanes were modified on the four nitrogen atoms by using ferrocenoyl chloride, so a new kind of enzyme model was obtained by introducing the side arms of ferrocenoyl group. And four of the tetraazacyclophanes with straight chains were also synthesized through the reaction of 1,8,22,29-tetraazo -[8.1.8.1]paracyclophane with bromoalkane and alkanecarbonyl bromide. Thereported synthesis method was improved in this thesis.Green chemistry brought forward by chemistry pollution of traditional chemical industry is a new kind of science related tightly to environmental protection. It is a new strategy to prevent pollution from the beginning. Green chemistry arose from organic chemistry, and organic synthesis is one of the key problems. Among the methods of realizing green synthesis, methods without solvents or replacing organic solvents by water have been a hot point of organic synthesis, there are a great deal of achievements published every year. Microwave irradiation is a new and convenient synthetic method which has been applied to a variety of reactions resulting in reduction of reaction time, higher yields, easier manipulation, cleaner reaction products and eco-friendly. Therefore, microwave irradiation has been employed widely in organic synthesis. This thesis is also consisted of the following parts focused on these aspects: 1) Three ways for the preparation of compounds containing ferrocenylmethylene group were provided, ten compounds were acquired by the reactions of formylferrocene with compounds containing an active methylene group under microwave irradiation, grinding or heating in water without organic solvents or catalysts. Three of them were new compounds. The influences of reaction temperature, KOH and the power of microwave irradiation on the reaction were discussed. 2) The microwave-enhanced synthesis of 5-acyloxypyrazoles from l-phenyl-3-methyl--pyrazole-5-one and acid chlorides under solvent-free conditions was achieved in moderate to good yield; the 4-acyl-5-acyloxypyrazoles were obtained by reacting with two equivalent acid chlorides in the present of calcium hydroxide. The microwave-enhanced condensation reaction of l-phenyl-3-methylpyrazol-5-ones with aromatic aldehydes under solvent-free conditions without catalyst was studied. Microwave irradiation power affected the reaction results very much. 1-Phenyl-3--methyl-4-aryl-methylenepyrazol-5-ones were achieved under high irradiation power condition and 4,4'-arylmethylene-bis(1-phenyl-3-methylpyrazol-5-ones) were obtained under low irradiation power condition in good yields. Twenty two compounds were gained. Seven of them were new compounds. Effects of microwave irradiation power and time on the reactions were discussed. 3) Themicrowave-enhanced syntheses of thiocarbonohydrazones and 1,2,4-triazole from the reaction of thiocarbonohydrazide with aromatic aldehydes and carboxylic acid respectively under solvent-free conditions without catalyst were achieved. Seven thiocarbonohydrazones and four 1,2,4-triazole derivatives were obtained. 4) The ring-opening reaction of benzimidazolium salts was studied. The effects of reaction condition on the yields of o-phenylenediamine derivatives and the differences of ring-opening reaction mechanism among 2-benzimidazolium salts, 2-imidazoline, and benzimidazoline were discussed. Eight ring opening products of benzimidazolium salts derived from benzimidazoles prepared by microwave irradiation were gained, and five of the products have not been reported in literatures.