Studies On Oxidative Cyanation Of N-benzyl Anilines By DDQ

?-Amino nitrile compounds have long been the focus of organic researchers and are not to be overlooked in organic synthesis.Among them,various conversions of cyano functional groups in ?-amino nitrile compounds are the most common ones,and are widely used in industries such as medicines,dyes,perfumes,agrochemicals,liquid crystal materials and polymer materials.In recent decades,chemists have been exploring the efficient and concise synthesis of such compounds.The cyanation reaction under oxidation provides an efficient way to construct C-CN bonds.However,in the currently published cyanation strategy,such reactions relyed on metal catalysis or rely on complex oxidants,which are high-cost and are not conductive to mass production.Therefore,the development of a new type of efficient and simple cyanation method is of great value.In this thesis,the metal-free catalytic cyanation of DDQ as an oxidant is studied and the oxidative cyanation reaction of various aromatic and heterocyclic substituted aniline secondary amine substrates with TMSCN is efficiently achieved.The reaction condition are mild and benign to the environment.At the same time,the strategy possesses low requirements of production equipment,simple process,safe preparation reaction,easy to operate and short reaction time,which is favorable for industrialization.We initially used N-benzyl aniline as a standard substrate to study the cyanation process,and investigated the type of reaction solvent,the amount of solvent,the amount of TMSCN,the amount of DDQ,the temperature,time and additives.The optimal reaction conditions were obtained: secondary alkyl aniline(0.5 mmol),DDQ(0.5 mmol),TMSCN(0.9 mmol),dissolved in acetonitrile(2 mL),and reacted at 30 ° C for 8 hours.Then,the generality of the substrate was investigated under the optimal reaction conditions.It was found that most of the N-arylmethylaniline derivatives led to production of a series of ?-amino nitrile derivatives by this method,and the yield reached to high yield of 91%.The oxidative cyanation reaction of secondary alkyl aniline by DDQ provides a new efficient and simple strategy for the synthesis of ?-amino nitrile derivatives,which is beneficial to the rapid construction of carbon-carbon bonds in complex structural molecules.