The Research On Diels-Alder Reactions Of Arynes And Intramolecular N-H Insertion Reactions Of Alkynes

Alynes are one of the highly active intermediates in organic synthesis for the formation of the C-C bonds, which can be widely applied in the synthesis of natural products, biological alkaloids and functional materials. Recently, a new discovery that alkyne building blocks can effectively generate benzyne under mild conditions, causes widespread concern.In this thesis, alkyne building blocks as a reactive component, we focused on the Diels-Alder reaction, N-H and O - H bond insertion reaction, and the transition metal-catalyzed reaction based on aryl alkyne. The main works include:1. The Diels-Alder reactions of various arynes generated directly from bis-1,3-diynes with cyclopentadiene, furan, N-methyl pyrrole and thiophene are described, and the reactions can be reacted at the condition of 80 ℃ for 5 h at medium or above the yield of the desired product, wherein the thiophene found desulfurization reaction product obtained with moderate yields and the structure was confirmed by single crystal diffraction. When the temperature was increased to 140 ℃, four alkynyl precursors may react with furans via domino Diels-Alder reaction to give some product, and the exact structure of the three-furan was determined by single crystal diffraction. These products can be obtained through deoxidation of the furan and benzene complexes and the application of these products may be expected to be applied in the field of optoelectronic materials.2. Ortho amino, hydroxy-substituted alkynyl four modules can be achieved by the N —H, O—H insertion reactions, which developted an efficient synthetic methods of the carbazole and dibenzofuran. The reaction can be carried out at 90℃ for 5 h, at moderate or above yield of the desired product. When increasing the amount of the catalytic AgNO3, it only needed one step to synthesize the compounds which contains carbazole ring and the indole ring, and has a good yield. A possible mechanism is proposed:the firstly, silver react with alkynyl to generate silver complex, and then, amino group to give affinity attack to form indole salt, the last, the title compound will be given by further reaction.