Study On The Methods Of Transformation Of Nitriles

Nitrogen-containing compounds are important,which are prevalent in natural products,pharmaceutical agents,agrochemicals,fine chemicals,and functional materials.Nitriles are a kind of inexpensive nitrogen-containing compounds.Nitriles are important organic synthetic materials and intermediates,and they are easily converted into other useful functional group compounds such as aldehydes,ketones,carboxylic acids,amines and amides.In this paper,a series of nitrogen-containing compounds are synthesized by the transformation of nitriles.The results are as follows:1.Mn-catalyzed oxidative amination of benzylic C(sp3)-H bonds with nitriles.A Mn-catalyzed oxidative amination of benzylic C(sp3)-H bonds with nitriles is disclosed,which enables the synthesis of a broad range of secondary amides in moderate to excellent yields under mild conditions.The interaction between Mn(III)and DDQ(2,3-Dichloro-5,6-dicyano-1,4-benzoquinone)facilitates the oxidation and makes it highly efficient and selective.The nitrile source is broad,including various nitriles of primary,secondary and tertiary alkyl groups,alkenyl groups,benzyl groups and aryl nitriles,and a series of amides are obtained in good yields.The optimum reaction conditions are as follows:under the nitrogen atmosphere,0.2 mmol of diphenylmethane,2.0 equivalents of DDQ,10.0 equivalents of trifluoroacetic acid,20 mol%of Mn(OAc)3,1.0 mL of acetonitrile at 90 °C for 12 h to achieve the highest yield.With the optimized reaction conditions in hand,a variety of substituted substrates are examined for this system,and the yields of the desired products are 40%-93%.A plausible mechanism is proposed.2.Study on the synthesis of aryl nitriles by Cu-mediated nitrogen atom transfer via C=N Bond Cleavage.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 methanol in high yields.Next,the optimum reaction conditions are determined:benzyl alcohol and CuCl(molar ratio 1:1.5)were added under oxygen,1 mL of mixed solvent,[acetonitrile:N,N-dimethylacetamide(DMAc)(3:2)],reacted at 130 °C for 24 h.With the optimized reaction conditions in hand,11 kinds of substituted substrates were examined for this system.The method shows good tolerance of functional groups and broad range of substrates,and is practical in the synthesis of useful organic intermediates.