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

作　　者：陈彰评[1] 翟保评[1] 陈阳生 姜中兴[1] 端木传嵩 

机构地区：[1]武汉大学化学与环境科学学院,武汉430072

出　　处：《武汉大学学报（自然科学版）》1999年第6期785-790,共6页Journal of Wuhan University(Natural Science Edition)

基　　金：国家自然科学基金!(29872033;29871024)

摘　　要：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.

关 键 词：亲核取代 苯酚钠 回苯基卟啉 金属配合物 

分 类 号：O626.13[理学—有机化学] O641.4[理学—化学]