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研究了溶剂对 2 - NO2 - 5 ,10 ,15 ,2 0 -四苯基卟啉铜 (2 - NO2 - TPPCu( ) ) 1与苯酚钠反应的影响 ,发现反应速度、产物分布与所用溶剂有很大关系 .在苯酚中反应 ,主要产物为碳碳键相连的产物 2 - (2 -羟基苯基 ) - TPPCu( ) 2 (5 0 % )和 2 - (4-羟基苯基 ) - TPPCu( ) 3(2 8% ) ,在非质子极性溶剂中反应 ,主要得到碳氧键相连的产物 2 -苯氧基 - TPPCu( ) 4 .在苯甲腈、DMSO、DMF和吡啶中反应 ,4的产率分别为 5 5 %、 5 2 %、47%和 11.7% .实验结果说明 ,在反应中存在 SRN1和 SNAr的竞争 ,质子性溶剂有利于 SRN1反应 ,并主要生成碳碳键产物 2、3,非质子极性溶剂能加速 SNAr反应 ,生成醚键产物 4.
The effect of solvent on the reaction of 2 - NO2 - 5, 10, 15, 2 0 - tetraphenylporphyrin copper (Ⅱ - NO2 - TPPCu ()) 1 with sodium phenolate was investigated. It was found that the reaction rate, product distribution and solvent In the reaction of phenol, the main product is 2 - (2 - hydroxyphenyl) - TPPCu (2) (50%) and 2 - (4 - hydroxyphenyl) - TPPCu ) 3 (2 8%) in aprotic polar solvents, the main product obtained by the bond of carbon and oxygen 2 - phenoxy - TPPCu () 4 in benzonitrile, DMSO, DMF and pyridine reaction, 4 The results showed that there existed competition between SRN1 and SNAr in the reaction, the proton solvent was favorable to the reaction of SRN1 and the main products were carbon-carbon bond, 3, aprotic polar solvents can accelerate the SNAr reaction, the formation of ether bond products 4.