A Study On The Alkylation And Amination Of Arenes Catalzyed By Iron And Copper Salts Via C-H Activation Strategy

Aromatics and heteroaromatics are a kind of important organic chemicals,widely used in pharmaceutical,pesticide,textile,fine chemicals,and so on. Research towards the synthesis of aromatic compounds is a continuous interest in organic chemistry. To modify the traditional synthetic methods and make them more efficient and simple is an effective strategy to access complex aromatic compounds. Alternatively, direct C-H functionalization of simple aromatic compounds has been proved to be a greener, atom economic and efficient way to synthesize structural diverse aromatic compounds.Therefore, there is great importance to carried out researches in this field.In this thesis,alkylation and amination of aromatic compounds via sp2 C-H activation were studied. The reactions were optimized by systematic screen and the substrates scope was investigated with the optimal condition and the results were discussed and summarized.In the first part, we can use Fe(OTs)3 as a catalyst and acyl peroxides as alkylation reagents to realized the aromatic and heterocyclic aromatic C-H bond activation followed by alkylation reaction. The optimal condition is decribed as following: 0.5 mmol acyl peroxide, 5 mL arene, 2.5 mol% Fe(OTs)3, were heated to 100? and in nitrogen protected condition for reaction for 5h. The experiment result showed that the reaction preferred electron-withdrawing aromatics, which was complementary to the traditional Friedel-Crafts alkylation reaction, and the reaction tend to generate ortho substitution product.In the second part, the amination of aromatic C-H bond was realized by using CuBr2 as the catalyst, PhI(OAc)2 as the oxidant, and N-chlorophthalimide as nitrogen source.Reaction parameters including solvents, catalysts, reaction time, and arene scope were investigated. The optimal condition was decribed as following: 0.5 mmol N-chlorophthalimide, 2 mL neat arene and 2 mmol iodobenzene diacetate in the presence of 10 mol% copper bromide was stirred and heated to 130? for 8 h. And the result revealed that the electronic effect controlled the reaction, electron-rich arene has a higher activity in the amination reaction.