A highly efficient synthesis of 2-formyl-5,10,15,20-tetraarylporphyrins, 1 and 2, that can be carried out on multi-gram scales is reported. The key steps in the sequence involve use of copper(II) chelation to ensure very efficient electrophilic substitution, and the demetalation of the intermediate iminium salt that results from Vilsmeier-Haack formylation of the copper(II) porphyrins prior to base-catalyzed hydrolysis of the salt to the corresponding free-base 2-formylporphyrin. This sequence avoids the formation of by-products that inevitably result when the formyl group is subjected to acidic conditions. Borohydride reduction of (metallo)-2-formylporphyrins give the corresponding 2-hydroxymethyl-porphyrins in quantitative yield. Catalytic reduction of copper(II) 2-hydroxymethyl-5,10,15,20-tetraphenylporphyrin 15 with hydrogen under acidic conditions affords 2-methyl-5,10,15,20-tetraphenylporphyrin 20 in 60% yield. Treatment of 2-hydroxymethyl-porphyrins with thionyl chloride in dry pyridine yields the corresponding 2-chloromethyl-porphyrins in good yields. The 2-chloromethyl-porphyrins give the corresponding triphenyl[(porphyrin-2-yl)methyl]phosphonium chlorides in 90% yield on treatment with PPh 3 in boiling chloroform. These salts are useful building blocks for the synthesis of conjugated porphyrin dimers and higher oligomers.
The reaction of
((tetraphenylporphyrinyl)methyl)triphenylphosphonium chloride
and benzaldehydes (CHO−C6H4−R; R = H, NO2, NMe2, OMe, Me, CHO) yields the
styryl porphyrin derivatives. These new
styryl-substituted
porphyrins have been studied using electrochemistry, electronic
absorbance, and resonance Raman spectroelectrochemical techniques. The substituents on the styryl group have a
modest perturbation on the electronic spectrum
of the porphyrin core. The resonance Raman data suggest that a
charge-transfer interaction is observed between
the porphyrin core and the NO2 group for the
4-NO2 compound.
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