Synthesis of β,β′‐Porphyrin Dimer Linked by Vinylene

Abstract

Synthesis of a novel β,β′‐tetraalkylporphyrin dimer linked by vinylene was discribed, in which the dimer was readily prepared from a porphyrin‐derived Wittig reagent and a mono‐formylated porphyrin via Wittig reaction. No π‐conjugation between the two porphyrin rings was obserbed, and the dimer was in trans form.

Conjugated porphyrin arrays: synthesis, properties and applications for functional materials

“…[71][72][73] Although the reaction of 69a with formylated TPP 70a failed to provide the desired ethene-bridged dimer, the same reaction of tetraalkylporphyrin 70b with porphyrin phosphonium salt 69b has recently been accomplished, giving ethene-bridged porphyrin dimer 71b in 65% yield. 74 This success has been ascribed to less steric congestion at the meso position of 70b.…”

Oligoporphyrins with One-and Two-Atom Covalent Bridges: Synthesis and Reactivity, Solid-State, Solution and Electronic Structures, Spectroscopy and Applications

“…51,52 In 2012, Shi and coworkers reported the synthesis of the β-β C 2 H 2 5,10,15,20-tetrapropylporphyrin dimer 52, using thermal decomposition of the corresponding porphyrinylmethylphosphonium salt 53 in the presence of DBU (1,8-diazabicycloundec-7-ene) as base. 71 A pure compound with an appropriate proton NMR spectrum was obtained in 65% yield, and the chemical shifts confirmed the (E) configuration. The =CH− protons resonated at 6.13 ppm, while those in Zhilina's TPP dimer appeared at 7.02 ppm.…”

“…The authors made no comment on the features of the UV/visible spectrum of 52, and only the peak maxima were included. 71 Mironov and coworkers reported in a short communication the only claimed examples of (E)-2,3-bis(porphyrinyl)butenes, namely the Ni 2 and Cu 2 dimers 54a and 54b, formed in high yield by TFA-induced dimerization of the 2-(1-hydroxyethyl)heptaethylporphyrin complexes. 72 However, the presence of eight separate singlets for the meso Hs in the NMR spectrum of 54a is strange, as a singlet is present for the bridge methyl groups.…”

Solvent-Free Aldol Reaction of β-Porphyrin Formaldehyde with Ketone

“…The β-substituted TPP are interesting compounds and have been used in many recent studies, namely, as starting units for the synthesis of elaborated porphyrins or as precursors of photodynamic pharmaceuticals. [7 ～ 10] Following our own research in this field, [11] in this paper we present a new method of the aldol reaction of designed β-substituted TPP with α,β-unsaturated carbonyl compound (Scheme 1), which is a more efficient and economical way to get β-substituted α,β-unsaturated carbonyl porphyrin compounds.…”