Expansion of a Pyrrole in meso-Tetraphenylporphyrin to a Pyrazine Imide Moiety Using a Beckmann Rearrangement

被引：19

作者：

Akhigbe, Joshua ^{[1
]}

Brueckner, Christian ^{[1
]}

机构：

[1] Univ Connecticut, Dept Chem, Storrs, CT 06269 USA

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2013年 / 2013卷 / 18期

基金：

美国国家科学基金会;

关键词：

Synthetic methods; Nitrogen heterocycles; Porphyrinoids; Rearrangement; Ring expansion; PORPHYRIN DERIVATIVES; CHLORIN; BACTERIOPURPURINIMIDES; TETRAPHENYLSECOCHLORIN; CARBAPORPHYRINOIDS; OXYPYRIPORPHYRINS; PHOTOSENSITIZERS; COORDINATION; FLUORESCENCE; RESORCINOL;

D O I：

10.1002/ejoc.201300274

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The group 10 metal complexes of ,-dioxoporphyrin monooxime 10M (M = NiII, PdII, PtII) are susceptible to a Beckmann rearrangement to produce the corresponding ring-expanded metallopyrazinoporphyrin imides 11M in good yields. These chromophores possess metallochlorin-like optical properties. Demetalation of the NiII complex furnishes the free-base porphyrinoid 11, which possesses a porphyrin-like optical spectrum. The monooximes are ultimately derived from meso-tetraphenylporphyrin, and the formal replacement of the porphyrin ,-double bond by an imide functionality is thus demonstrated. The imide functionality serves as a synthetic handle for further modification of the chromophore.

引用

页码：3876 / 3884

页数：9