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Study on the Copper-Catalyzed Replacement of Bromine by Fluorine and Chlorine in Aromatic Compounds

Author: HanYanLei
Tutor: FengXiuJuan
School: Dalian University of Technology
Course: Fine Chemicals
Keywords: Copper catalyst Bromides Fluoroalkyl reaction Chlorination reaction
CLC: O643.32
Type: Master's thesis
Year: 2011
Downloads: 77
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Abstract


Fluorinated aromatic and chlorinated aromatic hydrocarbons is an important chemical intermediates, widely used in the synthesis of pharmaceuticals, pesticides , as well as functional dyes , the radioactive 18F labeled organic or positron emission tomography technology commonly used tracer . Conventional fluorination method typically requires relatively harsh reaction conditions , the functional group compatibility Poor ; the traditional chlorination method exists differential selectivity of the reaction , the electron-deficient substrates difficult Chloride , inconvenient operation and other shortcomings . This article uses inexpensive and environmentally friendly copper as a catalyst , respectively bromine on the aromatic ring the fluorinated reaction and chlorinated reaction in-depth exploration and research , and the successful realization of efficient chlorinated aromatic ring bromine under mild conditions . Fluorinated reaction Bromoacetophenone as a model reaction , from the source of fluorine , catalysts , ligands, solvent and phase transfer catalyst five aspects of fluorinated reaction were discussed , but ultimately failed to achieve fluorinated the smooth progress of the reaction , we hypothesized that is not designed to meet the reductive elimination ligand . 2 the use of cuprous oxide as the catalyst , L - proline as the ligand , under 110 ° C , the model substrate bromo- toluene and tetramethyl ammonium chloride in an ethanol solvent in a chlorinated reaction , to a yield of 98% rate generates chlorotoluene . Expand under the reaction conditions , the reaction substrate , bromo include heterocyclic and fused ring aromatic hydrocarbons can be a high yield of conversion into the corresponding chlorinated product yield is between 81-99 % . The first time we realized chlorinated efficient copper -catalyzed aromatic ring bromine . The chlorinated reaction with mild reaction conditions, functional group compatibility , and a wide range of substrates , green , provides a new method for the synthesis of some complex structure with special functions chlorinated aromatic ring compounds , is now chloride method as an important complement .

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Chemical kinetics,catalysis > Catalytic > Catalytic reaction
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