聚亚胺醇(醌)前驱体的合成、表征与机理分析

由傅-克酰基化反应合成了1,4-双-(4′-溴苯酰基)苯(1)。以(1)和苯胺为单体,通过钯催化的胺化反应合成了1,4-双-(4′-氨基苯酰基)苯(2),其中叔丁醇钠(NaOt-Bu)为基体,1.1′-联萘-2.2′-二苯膦(BINAP)为配体。以(2)和锂化苯为底物,通过亲核加成反应得到1,4-双-[苯基-(4′-苯氨基)醇基]苯(3),此反应通过锂化苯对(2)中羰基的攻击实现。对(3)进行消除反应得到1,4-双-[(4-苄叉基-环己基-2,5-二烯苄基)苯(4)的粗产物,由氯仿萃取得到紫色溶液,通过水洗,蒸发,真空干燥制得紫色粉末精制品(4)。

Synthesis and Characterization of Poly(imino alcohol/quinone) Precursor

1,4-Bis(4′-bromobenzoyl)benzene(1) was synthesized using a modified method.1,4′-bis(4′-anilinobenzoyl)benzene(2) was synthesized by a palladium-catalyzed amination of 1,4-bis(4′-bromobenzoyl)benzene(1) with aniline as a primary aromatic amine using NaOt-Bu as a base and BINAP as a ligand.Both of the two carbonyl groups of 1,4-bis(4-anilinobenzoyl)benzene(2) were attacked by phenyllithium as a carbanion with a high nucleophilicity to afford 1,4′-bis{(phenyl-(4-anilinophenyl)methanol)}benzene(3) in 93% yield.Di-tertiary alcohol 1,4′-bis{(phenyl-(4-anilinophenyl)methanol)}benzene(3) forms 1,4-bis{(4-benzylidene-cyclohexa-2,5-dienylidene)-anilino}benzene(4) in an elimination reaction.The resulting compound(4) was extracted to a deeply purple solution using chloroform.The solution was washed with water,evaporated,and dried in vacuum,with a yield as purple powders.