Abstract: Aryl halides are widely used in the synthesis of natural products, functional materials, pharmaceutical pesticides and other functional structural molecules. At present, there are many studies on the structure characterization and application of aryl halides, but there are few ways to construct C-X bond to synthesize aryl halides. As a new type of D-A reaction, the aromatization addition reaction of alkynes （Hexadehydro-Diels-Alder, HDDA）can produce intermediate of phenylacetylene through the cyclization of triynes or tetraynes, and then nucleophilic addition,cyclization addition and other reactions take place, multiple C-C bonds and C-H bonds are constructed in one step to form a complex fused aromatic ring structure. In this study, HDDA reaction was used to explore the synthesis of fused aryl halides. The results show that under the condition of 100 益, DMF and water （V:V = 10:1）were used as the mixed solvent, C-C bonds and C-X bonds were successfully constructed after the reaction of tetrayne and allyl halides for 12 h, and a series of new fused aryl halides were synthesized efficiently. This reaction does not need metal catalyst, auxiliary agent and additive, nor does it need the protection of inert gas atmosphere. It has strong operability, high yield, certain atomic economy, and conforms to the concept of green chemistry. It provides a new method for the synthesis of aryl halides.

Key words: tetraalkyne, C-X coupling, condensed aryl halide structure, HDDA reaction