Study On The Halogenated And Sulfonylated Reactions Using Benzotriazole As The Leaving Group

Benzotriazole and its derivatives play an important role in the application of medicine,pesticides,polymer materials and dyes.Therefore,it is one of the most important tasks in organic synthesis to synthesize new compounds using benzotriazole derivatives.After synthesis of 1-(2-iodine-1-oxygen ethyl benzene)1H-benzotriazole compounds,reacting with chlorine,bromine and methyl benzene sulfonyl hydrazine generate new compounds.A beneficial supplement in transformation from 1-hydroxy benzotriazole to other functional groups is made.The paper first discussed the application of benzotriazole and its derivatives in organic synthesis in recent years.By summarizing and innovating,two kinds of reactions with phenyltriazole as the leaving group were studied.Firstly,One-pot prepartion of 1-chloro-2-iodine and 2-bromo-1-iodine compounds was developed.The reaction of olefins with 1-hydroxybenzotriazole and iodine in the presence of tertiary butyl peroxide as an oxidant at 40 ℃ for 5 h generate α-iodide-N-alkoxyl-1H-benzo[d][1,2,3]triazole intermediates,which reacts with acetyl chloride or acetyl bromine directly at room temperature for another 16 h to afford 1-chloro-2-iodide compounds in one pot.Both aromatic and aliphatic alkenes can be readily employed to provide the desired products,the yields varied from 13% to 68%.The reaction is easy to operate,the raw materials are easy to get and the substrates have good applicability.Then,a kind of sulfonylation reaction of benzotriazole olefin compounds was developed.Using toluene sulfonyl hydrazide as sulfonylation reagent,the reaction obtained corresponding alpha sulfonyl ketone products with the yields of 25%～75% in the presence of copper acetate and oxone at 80 ℃ for 8 h.The synthetic process has advantages of mild conditions,simple operation.A novel method for sulfonylation was provided.