Synthesis and Characterization of New Non-aromatic Texaphyrin-type Expanded Porphyrins

Abstract

<jats:p> The synthesis and X-ray diffraction-based characterization of a texaphyrin-type non-aromatic expanded porphyrin, 13,18,22,27-tetraethyl-14,17,23,26-tetramethyl-20-p-nitrophenyl-3,10,28,29,30,31-hexaazahexacyclo[23.2.1.0<jats:sup>4,9</jats:sup>.1<jats:sup>12,15</jats:sup>.1<jats:sup>16,19</jats:sup>.1<jats:sup>21,24</jats:sup>]untriaconta-2, 4, 5, 7, 10,12,14,16,18,-20,22,24(30),25,27-tetradecaene (1), is reported. This Schiff base macrocycle was prepared in good yield via the 1:1 HCl -catalyzed condensation of a tetrapyrrole dialdehyde precursor, (di(5-formyl-4,4'-diethyl-3,3'-dimethyl-2,2'-bipyrrole)-p-nitrophenylmethine), with 1,2-phenylenediamine. Compound 1 was assigned as being a 26 π-electron non-aromatic benzannulene on the basis of both proton NMR and single-crystal X-ray diffraction analyses. The latter studies, in particular, revealed a non-planar macrocyclic structure co-crystallized with a molecule of water. By varying either the diamine used in the cyclization step and/or the substituent in the meso-position of the tetrapyrrolic precursor, a range of other systems analogous to 1 could be obtained. The resulting systems were found to present good stability both in the solid state and in solution. </jats:p>

New polyethyleneglycol-functionalized texaphyrins: synthesis and in vitro biological studies

“…Such solubility features were considered critical since they would allow for direct comparisons with MGd 1 in cell culture. Nonetheless, it was also recognized that the presence of these meso substituents might make compounds 2 and 3 less than ideal electronic analogues of 1; they could engender deviations from ring planarity, [20][21][22][23] which, in turn, could lead to altered interactions with biological targets. [24][25][26] In light of this potential concern, we prepared a simpler analog of 3, namely, the mesophenyl substituted system 10.…”

Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications

“…For further information, the reader can refer to a recent review which covers the field comprehensively. 153 Even though there are many other types of expanded porphyrins, 153 only grandephyrin 154 showed successful complexation with lutetium: bis(trimethylsilyl)amide of Lu III was added into the free-base macrocycle in THF solution and in the absence of water and oxygen. Unfortunately, the resulting Lu IIIgrandephyrin adduct was unstable and slowly decomposed upon exposure to air and moisture (Fig.…”

New chloroamide-steroid derivative with biological activity on a casein kinase 2 (CK2)

“…Several azahexacyclo analogs have been using different methods which use some reagents such an oligoether derivative [30] [32], benzyl amine [33], thiourea/hydrochloric acid [34], α-cyanocinnamonitriles [35] and others. However, some of these reagents are expensive and require special conditions for their management.…”