对α-四芳氧基取代酞菁溴化位置的思考

为了研究α 四芳氧基取代酞菁在溴化反应中溴原子的取代位置问题,本文合成了1,8,15,22 四(4 甲基苯氧基)酞菁钯(Pc～1)、1,8,15,22 四(2,6 二溴 4 甲基苯氧基)酞菁钯(Pc～2)、1,8,15,22 四(2,4 二特丁基苯氧基)酞菁钯(Pc～3)和1,8,15,22 四(2,4 二特丁基苯氧基)酞菁铜(Pc～4),并对它们分别进行了相同条件下的溴化,得到相应的溴化产物Pc～5、Pc～6、Pc～7和Pc～8.综合对比研究酞菁Pc～1—4及其溴化产物Pc～5—8的最大吸收波长,推测酞菁溴化反应发生在酞菁大共轭体系的苯环上,而不是芳氧取代基的苯环上,并从电子结构的角度简要的说明了原因.

A SPECULATION ON BROMINE SUBSTITUTED POSITION OF TETRAPHENOXYPHTHALOCYANINES

1,8,15,22 tetrakis(4 methylphenoxy)phthalocyaninatopalladium(Pc～1),1,8,15,22 tetrakis(2,6 dibromo 4 methylphenoxy)phthalocyaninatopalladium(Pc～2),1,8,15,22 tetrakis(2,4 ditertbutylphenoxy)phthalocyaninatopalladium(Pc～3)and 1,8,15,22 tetrakis(2,4 ditertbutylphenoxy)(Pc～4)phthalocyaninatocopper were synthesized in order to study the substituted position in the process of bromization reaction.The comparison of maximum absorbance wavelength(λmax)of Pc～1—4 and bromophthalocyanines Pc～5 7 leads to the conclusion that the bromization took place not in the benzene ring of outer substituted phenoxy groups,but in the benzene ring of the big conjugated system.From the point of electronic structure,the reasons were also presented and discussed.