2 - Chloro - 4 - (4 - Chlorophenoxy) - Of Acetophenone Synthesis And Study Of The Ullmann Reaction

The preparation of 1-[2-chloro-4-(4-chlorophenoxy)phenyl]ethanone and diaryl ether derivatives were discussed.The mechanism of Ullmann reaction was studied.(1)The optimal condition of synthetic technology in two-step method was determined.The synthesis of 1-chloro-3-(4-chlorophenoxy)-benzene was from 4-chlorophenol and 1,3-Dichlorobenzene by ullmann reaction. Then 1-[2-chloro-4-(4-chlorophenoxy)phenyl]-ethanone could be prepared by F-C acylation.The optimal condition in the first step was:the ratio of reactant 1:1.2,and CuCl/K₂CO₃/18h/NMP/160℃,the yield of 65%.The optimal condition in the second step was:the ratio of AlCl₃ and acidylation reagent 1:1.8,1,2-dichloroethane,3h,the yield of 70%.(2)The optimal condition of synthetic technology in one-step method was determined.The optimal condition under not add ligand was:CuCl/isopropyl benzene/K₂CO₃/160℃/18h,the ratio of reactant 1:1.2,the yield of 78%.A variety of ligands were examined using 4-chlorophenol and 1-(2,4-dichloro-phenyl)-ethanone as substrates. 1,2-Propanediol was found to be an efficient ligand for this reaction.It was able to reduce reaction temperature and shorten reaction time successfully.The optimal condition by adding ligand was: CuCl/toluene/KOH/115℃/12h,the ratio of reactant 1:1.2,the ligand was 1,2-propanediol,the yield of 77%.(3)This catalyst system was effective in the synthesis of etherderivatives.A variety of hindered and functionalized aryl chlorideswere transformed in good to excellent yields under mild conditions.In the end,the mechanism of Ullmann reaction was studied.