两类环加成反应的理论研究-有机化学专业毕业论文.docxVIP

中国科学技术大学硕士学位论文A 中国科学技术大学硕士学位论文 A BSTRACT Since conservation of orbital symmetry developed by Woodward and Hoffmann appeared in 1 960s，a variety of cycloaddition reactions have been developed．At the same time，lots of quantum chemistry software，especially Gaussian，were developed with the introduction of modem computer technology into chemistry domain． In this work，we studied the regioselectivity and its temperature effect of Patem6·Btichi reaction between pyrimidines and carbonyl compounds and the solvent effect on regioselectivity of 1,3一dipole cycloaddtion reaction between azide and acetylene derivatives． Temperature effect the regioselectivity of Patem6-Btichi reaction between dimethyl thymine and dimethyl uracil with benzophenone and its derivatives Patem6．Bachi reaction between dimethyl thymine and dimethyl uracil with benzophenone and its derivatives give two regioisomers．Temperature have significant effect on the regioselectivity．At low temperature，hh type oxetanes are the major products．With the increase of temperature，yields of hh type oxetanes decrease while yields of ht type oxetanes increase．At high temperature，ht type oxetanes are the major products． Quantum chemistry demonstrates EWGs on phenyl ring stabilize diradicals while EDGs can destabilize the diradicals．Methyl at 5 position of dimethylthymine Can stabilize diradicals SO that the major products are B type．Computational results can explain the substitute effect on regioselectivity and reaction efficiency． The relative velocity of ISC and the interchange of conformers of triplet diradicals，the equilibrium constant of the productive conformers and unproductive conformers are the factors that cail effect the regioselectivity．During the increase of temperature，the determining step of regioselectivity changes． 2 Solvent effect on the regioselectivity of 1,3-dipolar cycloaddtion reaction We have explained the experiment observed solvent effect on regioselectivity of 1,3-dipolar cycloaddition reaction be