Porphotetramethenes with 1,3-alternate conformation of pyrrole rings from oxidative N-alkylation of porphyrin tetraphenols

Efficient synthesis of aryldipyrromethanes in water and their application in the synthesis of corroles and dipyrromethenes

“…16 The ability to introduce only one substituent per macrocycle molecule reflects the smaller size of the corrole cavity. The distribution of the substituent groups over the core nitrogen atoms (i.e.…”

“…Finally, prompted by the interesting results that were previously obtained on the oxidative Nalkylation of porphyrins, 16 it was reasoned that the same type of reaction could also be carried out with corroles. For that purpose, the synthesis of a meso-hydroxyphenyl substituted corrole 4f was required (Structure Block 1).…”

“…16 The reaction was performed under the general Nalkylation conditions (Scheme 3). Within 15 min of the addition of the alkylating agent (ethyl bromoacetate (6)), the major spot on TLC was still that of the starting corrole 4f, without any spot similar to that of the oxidized intermediate in the analogous reaction with porphyrins.…”

Structures, Spectral and Electrochemical Properties ofN‐(Naphth‐2‐ylmethyl)‐Appended Porphyrinogens

“…The orientations of N-substituents and conformations of the tetrapyrrole are similar to those already reported. [17,18] The most interesting feature of these crystal structures lies in the packing of the molecules, which is strongly influenced by a dipole-dipole interaction between the N-substituents. In fact, molecules of 6 contained within the structure are dimerized through this π-π stacking interaction, while the same effect operating in 8 gives a long-range ordering of the molecules into 1-dimensional arrays, which run parallel with the crystallographic a-axis.…”

“…In fact, many kinds of functional group can be introduced selectively at the nitrogen atoms by variation of the alkylating reagent and subsequent chemical modification of the substituent where appropriate. [16,18] We considered that compound 3 is an excellent precursor for electrochemically active compounds, and we are exploiting this by preparation of several families of derivatives. Previously, the structures and electrochemistry of the N-benzylated derivatives were investigated and revealed stable anion and cation radicals as well as further species in higher and lower oxidation states.…”