Benzyne C-O,C-N Insertion Reaction

Because aryne has highly active intermediates, in recent years, it has been extensively studied by researchers. Aryne with strong electron affinity, when Aryne react with nucleophile, containing N-C,O-C bond, it can occur σ- bond insertion and insertion- Cyclization reaction.Quinolone derivative has medicinal biological characteristic,which is antibacterial and anti-tumor. The fluorine-containing aromatic ether derivatives are widely used in Pharmaceuticals, Pesticides, Materials in fields.This paper research the insertion reaction of aryne and C-O bond, including the following two parts:1.Synthesis of Quinolone derivative.i This experiment synthesized 25 kinds of Aza-MBH productsii Firstly, this experiment filter the different aromatic amines and different acrylate, which is used for the synthesis of Aza-MBH products. When the aromatic amine is anisidine and acrylate is methyl acrylate, insert- cyclization product’s yield is more higher, then, filter the reaction conditions. Under the optimal reaction conditions, we had compounded 22 kinds of quinolones, the yield is 18%-54%. The study found substituent electronegativity weakened, the yield will increase, but not much affect insert and insert-cyclization ratio, insert still dominate. After that, according to the research literature, we presume the mechanism of quinolones from Aza-MBH products with aryne.2.Synthesis of The fluorine-containing aromatic ether.Insertion reaction using 1-substituted 2,2,2-trifluoroethanol and aryne, this paper synthesized 12 kinds of fluorine-containing aromatic ether compound. The yield is 18%-91%. According to the literature survey, we speculated insertion reaction mechanism of 1-substituted 2,2,2-trifluoroethanol and aryne.In summary, based aryne insertion and insertion – cyclization, developing a new method for the synthesis of quinolone derivative, a fluorine-containing aromatic ether.