Selective Synthesis Of Vinyl-substituted Heterocyclic Compounds

Vinyl-substituted nitrogen-containing heterocycles are widely used and are common components of drugs.Vinyl-substituted twisted amides are aza bridged compounds.Their amide bond is located at the bridgehead position,and the bicyclic structure causes the amide bond on the same plane to be twisted,so that the amide bond has a twist angle.This unique structure makes twisted amides have special physical and chemical properties Vinyl-substituted oxazoline is an indispensable branch of heterocyclic chemistry and of great significance for bioactive pesticide and pharmaceutical synthesis.This thesis mainly uses the allyl azide rearrangement reaction and intramolecular Schmidt reaction to selectively synthesize vinyl substituted twisted amides and vinyl substituted oxazoline ring compounds.By exploring their physicochemical properties,it is expected to use the presence of vinyl groups to discover new applications of nitrogen-containing heterocyclic compounds in the medical field.This thesis is divided into three chapters:1.Preparation of vinyl substituted twisted amides.Vinyl substituted twisted amides were synthesized by allyl azide rearrangement-intramolecular Schmidt reaction,and two kinds of vinyl substituted twisted amides with different twist angles were prepared by changing the reaction substrate and substituent.Totally,we obtained two olefins(45-53%and 81-95%yield),two azide compounds(47-65%and 63-73%yield),three twisted amides(10-20%yield)and one normal amides(10-20%yield).Moreover,we studied the chemical and physical properties of these twisted amides by the comparison with amine and ketone..2.Preliminary study on the chemical properties of vinyl-substituted twisted amides After studying the physical properties of the twisted amides,we explored its chemical properties.The research object is a twisted amide with a vinyl substituted twist angle of 36.6 degrees.The main research are focused on the breaking or rearrangement of bonds such as C=C,C=O,C(O)-N and the reactions of nitrogen atom.We have successfully carried out hydrosilylation reaction,borane reduction reaction,NaBH4 reduction reaction and esterification reaction,etc.The reactions involved also include rearrangement reaction and salt nucleophilic substitution reaction3.Preliminary investigation of the reaction of compounds containing hydroxyl and allyl azide with carbonyl compounds.We have developed an effective method for preparing allyl azide compounds with hydroxyl groups.In exploring the reaction of hydroxyallyl azide compounds with aldehydes,we obtained three oxazoline compounds with vinyl substitution.In exploring the reaction of hydroxyallyl azide compounds with ketones,we obtained tetrafluoroborate imine ether heterocycles and their ring-opening products.In total,we obtained 3 allyl azide mixtures containing hydroxyl groups and 3 substituted oxazoline ring compounds.