Decarboxylative Bromination Of ?,?-unsaturated Carboxylic Acids Via An Anodic Oxidation

Organic electrolytic synthesis is an interdiscipline,which combines organic synthesis and electrochemical techniques.In this system,gaining and losing electron directly realize redox reaction,thus realizing the organic synthesis and obtaining the desired product.The basic type of electrochemical synthesis includes formation of carbon-carbon bonds and functional groups of addition,substitution,cracking,elimination,coupling,oxidation and reduction reactions by using the media.In the background of ever-graving environmental problems in living,production and scientific field stepping by the development of science and technology,we now pay more attention to the protection of the environment.Therefore,chemists make their best efforts to realize green chemistry.So chemists have been making efforts to develop reactions which are under mild reaction conditions.Organic electrolytic synthesis,electron transferring can directly realize the redox reactions without adding redox.So organic electrochemical synthesis is green and more conform to the requirements of the development of the green chemistry and has the promising development prospect.This thesis mainly studies the decarboxylative bromination of ?,?-unsaturated carboxylic acids via an anodic oxidation by employing ammonium bromide as a bromine source and the electrochemical polymerization of diallyldimethylammonium chloride(DMDAAC).The thesis altogether includes two parts,the first part summarizes the recent chemists' achievements about the decarboxylative functionalization of ?,?-unsaturated carboxylic acids.The second part details the decarboxylative bromination of a,p-unsaturated carboxylic acids via an anodic oxidation.First,on the basis of our laboratory's previous work about decarboxylation via an electrochemical oxidation,we realized the decarboxylative bromination of ?,??unsaturated carboxylic acids.Although the decarboxylative bromination of ?,?-unsaturated carboxylic acids via chemical methods has made good progress,it mainly limited to involving heavy metal salts with a little slow process.However,we successfully realized the decarboxylative bromination of ?,?-unsaturated carboxylic acids under electrochemical conditions with the advance of transition-metal-free,short time,no additional supporting electrolyte.And the processing is simple,which are accorded with the requirement of green chemistry.Then,on account of the poor tolerance of decarboxylative chlorination of the reaction,we developed the the electrochemical polymerization of diallyldimethylammonium chloride(DMDAAC).As we know,poly(diallyldimethylammonium chloride)(PDDA)are usually applied to prepare the screen-printed electrode(SPCE).We think that PDDA-modified electrode have potential value in the anodic oxidative reactions as the nitrogen ions on the film can speed up the diffusion of anions via an electrostatic interaction.Then,we realized PDDA-modified glassy carbon electrode via an electrochemical polymerization of diallyldimethylammonium chloride.In summary,we successfully developed a decarboxylative bromination of a,(3-unsaturated carboxylic acids via an anodic oxidation and the preparation of PDDA-modified glassy carbon electrode via an electrochemical polymerization.Compared with the traditional chemical methods,this method is more green,the operation is simple,and this method provides a new direction for the green organic synthesis.