Synthesis Of N-Heterocycle Compounds In Rtils And Study Of The Applications Of Vinyl Zirconium Complexes

In this dissertation, we described the character, synthesis and application of the ionic liquids in systemic, and developed a new way to synthesize the N- hetero -cycle complexes.Comparing with the VOL, ionic liquids as reaction solvent show many virtues, in general, its polarity is more strong than the ordinary solvent, such as methanol, acetonitrile, the solubility of organic or inorganic compounds in ionic liquids is very good, many kinds of ionic liquids are still steady even heated over to 200℃. Generally, ionic liquids as solvent or catalyst carrier can not only shorten reaction time but also improve the output of the reaction.Firstly, we synthesized the 2,3,5-trichloropyridine in ionic liquids successfully, this compound is a valuable intermediate for some insecticides and herbcides, different methods for the preparation of this compound have already been reported, among which the CuCl-catalyzed addition of trichloroaldehyde to the superfluous acrylonitrile is the most attractive method .we developed this method by using ionic liquids as solvent and catalyst, get this compound in one-step with famous output.Secondly, two nucleophilic substitution reaction were acted in ionic liquids, because the ionic liquids were composed of ion completely, it shows so strong polarity that improve the ability of nucleophilic reagent through dissolving more nucleophilic reagent, such as KF, CsF, NaN3. Obviously, the mechanism of the nucleophilic displacement reaction in ionic liquids is SN2, but the ionic liquids surely have a fundamental effect on the reaction kinetics. For example, the 2, 3, 5-trichloropyridine reacted with the KF/CsF at 200℃ in ionic liquids, the difluoropyridine product over the fluoropyridine about 40% compared with the nucleophilic fluorination of 2, 3, 5-trichloropyridine in DMSO or crown ether. NaN3 is a traditional nucleophile resource, however the limited solubility and low nucleophilicity in organic solvents can make the process of nucleophilic substitution difficult. In summary , we have demonstrated facile nucleophilic fluorination and azidonation of the 2, 3, 5-trichloropyridine to corresponding product in ionic liquids, the system could not only enhance the reactivity of KF and NaN3 significantly but also reduce the formation of byproducts.Thirdly, the 1-pyridine-1H-1, 2, 3-triazoles were successfully get by the regiospecific 1, 3-dipolar cycloaddition reaction of azidopyridine with acetyllenic compound in ionic liquids catalyzed by Cu(I) salt. From the 1H NMR figure we can conclude that the ionic liquids can enhance the reaction regioselectivity.At last, the hydrozirconation of terminal alkynes, alkynyl phosphonate, and the reaction of the acylzirconocene chlorides with electron affinity substances were investigated. In the last part, we included the activity of the dydrozirconation of various alkynes and the activity of various electrophiles with organozirconium complexes.