The Electron-deficient Olefin/amide/NBS Three Components Synthesize The Corresponding Ortho-amino Bromide

A new protocol for the synthesis of vicinal bromoamines from electron deficient olefin(?,?-Dicyanostyrene and a-cyano ethyl cinnamate)/Amide/NBS was developed in one pot.In the presence of anhydrous base,electron deficient olefins reacted with NBS and amide which can generate the vicinal haloamine compounds smoothly in good to excellent yield(up to 93%yield)at room temperature without the protection of inert gas in CH2Cl2 or CH3OH.26 different structural electron deficient olefins reacted with 7 different structural amides(acrylamide,acetamide,valeramide,isobutyramide,benzamide,nitrobenzamide,ethylurethanm)and NBS have been investigated in this work.The results indicated that the method not only is adapted for Electron deficient olefins in wide scope,but also is suitable for the different types of amide.The structure of all the products were confirmed by nuclear magnetic resonance spectroscopy(NMR)and high resolution mass spectrometry(HRMS),and the possible reaction mechanism was proposed.This study mainly includes the following two parts.1.The reseach for the synthesis of vicinal bromoamine compounds from?,?-dicyanostyrene/NBS/general amideFirst,based on the fact of the N-bromoamide can be produced in-situ from amide and NBS and they can be used as nitrogen/halogen source,A new protocol for the synthesis of vicinal bromoamines from ?,?-dicyanostyrene derivatives/acrylamide/NBS was developed in one pot.Experimental result indicated that the system can generate the vicinal bromoamine compounds smoothly in good yield at room temperature in CH2Cl2.In order to explore the adaptability of the reaction conditions,13 different structural ?,?-dicyanostyrene derivatives reacted with acrylamid and NBS have been investigated in this work.The results indicated that all the ?,?-dicyanostyrene derivatives can get the vicinal bromoamine compounds in good to excellent yield at room temperature in CH2Cl2.Second,In order to explore the applicability of the experimental conditions to amides,in this chapter,the reaction of ?,?-dicyanostyrene reacted with NBS and various structural general amides(acetamide,valeramide,isobutyramide,benzamide,nitrobenzamide)have be investigated under the same reaction conditions,the result indicated that five kinds of amides can been successfully reacted with ?,?-dicyanostyrene and NBS and they can generate the vicinal bromoamine compounds in good to excellent yield,too.The results shown that the new method not only is adapt for the ?,?-dicyanostyrene derivatives widly but also is suitable for various amides.The structure of all the products were confirmed by their corresponding 1H NMR,13C NMR spectra and HRMS(ESI).2.The study on the synthesisof vicinal bromoamine compounds from electron deficient olefins(?,?-Dicyanostyrene and ethyl ?-cyanocinnamate)with ethylurethanm and NBSIn the ethylurethanm,which is a kind of difunctional compounds with ester and amido groups,the ester group not only can be used as a reation groups,amido group also be used as another reation group.So it is a very useful reaction reagent.Based on the above research,we established two kinds of reaction method in this chapter.One is?,?-dicyanostyrene derivatives reacted with ethylurethanm/NBS in one pot.Another is the ethyl ?-cyano-cinnamate derivatives reacted with ethylurethanm/NBS in one pot too.Although the yield is not very high in these reactions,however,the use of ethylurethanm as nitrogen source can introduce three different functional groups to the carbon-carbon double bond which increase the application range of vicinal bromoamine compounds.All product structures from these reactions were confirmed by their 1H NMR and 13C NMR and HRMS(ESI).