The Study Of A New Aminating Agent And The Synthesis Of M-TMXDI

In this paper,the feas ibility of the reaction of benzhydrylamine as a new aminating agent to prepare primary amine with aldehydes,ketones,halohydrocarbons and alkyl tosylates was studied,and the synthesis process of1,3-bis(1-isocyanato-1-methylethyl)benzene(m-TMXDI)was optimized.Part I The feasibility study on the preparation of primary amines with benzhydrylamine as an aminating agent.The schiff bases were obtained by the condensation of aldehydes and ketones with benzhydrylamine.Then,C=N double bond transfer occurred in the catalysis of potassium tert-butoxide.Finally,hydrolysis under acidic conditions were used to obtain the corresponding primary amines.N-benzhydrylamines were obtained by the reaction of halohydrocarbons or alkyl tosylates with benzhydrylamine,and converted to C=N double bonds by the dehydrogenation with 2,3-dichloro-5,6-dicyano-para-benzoquinone(DDQ).After completion of the hydrolys is under acidic conditions,the corresponding primary amines were obtained.The experimental results show that benzhydrylamine is a kind of good aminating agent with higher activity than benzylamine,which was cheap and easy to obtain.It has the advantages of moderate to excellent yield of primary amines with aldehydes,ketones,halohydrocarbons and alkyl tosylates and without byproducts of secondary amines and tertiary amines.Halohydrocarbons and alkyl tosylates were also easy to prepare primary amines by dehydrogenation of DDQ,which greatly increased the substrate range.The samples were identified by ~1H-NMR and FTIR.Part II Optimization of m-TMXDI synthesis process1,3-bis(1-methylethenyl)benzene(m-DIPEB)was used as raw material to react with HCl to obtain 1,3-bis(1-chloro-1-methylethyl)benzene(m-TMXDC)with a yield of 97%,and then the target product m-TMXDI was obtained by reaction with sodium cyanate in a yield of 67%.The molecular distillation was used to separate and purify m-TMXDI,and the content was 94%.The process is simple,mild and suitable for industrial production.