苯酚钠对2-NO₂-TPP及其金属配合物的亲核取代

苯酚钠对2-NO 2 -TPP及其金属配合物的亲核取代 The Nucleophilic Substitution Reaction of 2-nitro-5,10,15,20-tetraphenylporphyrin With Sodium Phenoxide 陈彰评 CHEN Zhang\|ping 1 first-author 翟保评 ZAI Bao\|ping 1 陈阳生 CHEN Yang\|sheng 1 姜中兴 JIANG Zhong\|xing 1 端木传嵩 DUAN MU Quan\|song 1 武汉大学化学与环境科学学院,武汉,430072 武汉大学化学与环境科学学院,武汉,430072 College of Chemistry and Environment Science, Wuhan University College of Chemistry and Environment Science, Wuhan University 研究了苯酚钠对2-NO2 -5,10,15,20-四苯基卟啉（2-NO2-TPP）1 及其铜（Ⅱ）2、镍（Ⅱ）3、铁（Ⅲ）4、钴（Ⅱ）5等金属配合物的亲核取代. 在苯酚中反应, 主要产物分别为2-（2-羟基苯基）-5,10,15,20-四苯基卟啉6（44% ）及相应金属配合物7（50% ）、8（52% ）、9（51% ）、10（51% ）, 2-（4-羟基苯基）-5,10,15,20-四苯基卟啉11（33% ）及相应金属配合物12（28% ）,13（26% ）,14（23% ）、15（26% ）. 对-二硝基苯（P-DNB）能抑制反应的进行.如化合物2 反应加入p-DNB, 反应由4 h 延长到10 h,同时得到70% 的2-苯氧基-5,10,15,20-四苯基卟啉铜16.实验结果由SRN1 和SN Ar的竞争来解释,其中碳碳键取代产物经SRN1 生成,醚键产物经SNAr生成. The nucleophiic substitutions of 2\|nitro\|5,10,15,20\|tetraphenylporphyrin 1, and Cu （Ⅱ）2, Ni（Ⅱ）3, Fe（Ⅲ）4, Co（Ⅱ）5 complex with Phenoxide ion as nucleophilic reagent are investigated. 2\|（2\|Hydroxyphenyl）\|5,10,15,20\|tetraphenylporphyrin M and 2\|（4\|Hydroxyphenyl）\|5,10,15,20\|tetra\| phenyl\|porphyrin M are obtained as the major products in phenol. The reaction can be inhibited by adding p \|DNB, as example, reaction of 2 is delayed from 4 h to 10 h and also the yield of 2\|phenoxy 5,10,15,20\|tetraphenylporphyrin M 16 increases from 3% to 70%. The reactions are explained via the competition of the S RN 1 and S NAr reaction. The formation of C—C bond via S RN 1 and the C—O bond via the S NAr. 2-取代卟啉合成 亲核取代 SRN1 SNAr Q5-33 国家自然科学基金!(29872033;29871024) 1999-06-01 2021-04-01 6