Studies On Copper-promoted Cyanation Of Aromatic Compounds Via Complete Cleavage Of C?N Triple Bonds

Cyano compounds have wide applications in pharmaceuticals, agricultural chemicals, spices and dye. Cyano compounds could be easily converted to other compounds such as amines, acylamides, aldehydes, ketones, carboxylic acidsare and their derivatives, imidazole and nitrogen heterocyclic ring compounds, and thus are imporant in ognanic synthesis. Therefore, the development of efficient and facile methods for the synthesis of these compounds is very significant in synthetic chemistry. This thesis mainly represents that CuCl-mediated complete C=N bond cleavage of acetonitrile to reconstruct C=N bond for the synthesis of aryl nitriles under O₂ atmosphere. The results are as follows:?1? CuCl promoted aerobic oxidative N-atom transfer via complete cleavage of C-N triple bond of acetonitrile is developed, which produce a variety of functionalized aryl nitriles from the readily accessible acetonitrile and aromatic aldehydes in high yields. Through the investigation of reaction conditions ?reaction temperature and time, solvent, catalyst, substrate molar ratio?, the optimum reaction conditions were confirmed:under O₂ atmosphere, substrate molar ratio 4-methylbenzaldehyde and CuCl= 1:1.5,1.0 mL mixed solvent and the ratio of CH₃CN to DMAc at 2:1, reaction temperature 130?, reaction time 24 h. With the optimized reaction conditions in hand, a variety of substituted substrates were examined for this system, and the yields of the desired products were 20%-93%. On the basis of trace of GC-MS/GC, control experiments, and ¹³C isotope labeling, a possible mechanism was propsoed. A nitrogen atom transfer to organic molecules via C=N bond cleavage is firstly developed, and the strategy is simple and convenient without any ligands and additives.?2? A novel method for one-pot synthesis 3-indonylnitrile derivatives is developed through three-components coupling reaction, in which tetramethylethylenediamine ?TMEDA? provides the "C" unit of "CN", and "N" unit comes from acetonitrile. The best reaction conditions as follows:under O₂ atmosphere, substrate molar ratio iV-methylindole and CuCl= 1:1.3,1.0 mL mixed solvent and the ratio of CH₃CN to DMAc at 7:3,200 mol% TMEDA, reaction temperature 130?, reaction time 24 h. With the optimized reaction conditions in hand,24 kinds of substituted substrates were examined for this system, and the yields of the desired products were 54%-94%. The method shows good tolerance of functional groups and broad range of substrates, and is practical in the synthesis of useful organic intermediates.