Synthetic studies in the field of the porphyrins. synthesis of a mesoporphyrin and of a diacetyldeuteroporhyrin

A method is proposed for the synthesis of porphyrins based on the cyclization of a tetrapyrrole system with methyl and formyl groups at the ends of the molecule. The synthesis of mesoporphyrin IX and diacetyldeuteroporphyrin IX has been effected.     

Influence of electronegative substituents on the electronic spectra of the porphyrins in the form of dications

The positions of the electronic absorption bands and also the intensities of the Soret bands of the porphyrins with ethoxycarbonyl substituents in the form of dications have been calculated by the LCAO MO method in Huckel's approximation. Comparison with the experimental results shows good agreement.     

Spectral study of the conversion of porphyrins during interaction with molecular negative ions

In the interaction of ethioporphyrin and of several of its metal derivatives with negative ions of pyridine and anthracene in tetrahydrofuran solutions, an electron transfer takes place which results in the conversion of the pyridine and anthracene ions into neutral molecules, whereas the molecules of the pigment are first transformed into monovalent anions and subsequently into the di-, tri-, tetra-, and sometimes even into the hexavalent anions. In the first stage of this interaction, ferriethioporphyrin is reduced to ferro-ethioporphyrin, whereas the unmetallized pigment and its copper complex are transformed into the disodium derivative of ethioporphyrin. When the temperature is lowered, the rate of the electron transfer from pyridine ions to zinc-ethioporphyrin is decreased, and illumination leads to a substantial rate increase. The photochemical sensitivity of this system is possibly linked to the formation of stable complexes between pigment molecules and pyridine ions.     

Investigations in the fie ld of substituted furanurona ldehydes steric directivity of the nitromethane condensation

Summary 1. The condensation of the anomeric methyl 2,3-di-O-benzyl-D-xylofuranosiduronaldehydes with nitromethane has been studied.2. It has been shown that the position of the substituent at the glycosidic center has an influence on the steric directivity of this reaction.3. The structure of the 6-nitro-6-deoxyhexofuranosides synthesized has been confirmed by their conversion into known derivatives of methyl D-glucofuranosides.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 8–12, January–February, 1972.     

Synthesis of o- and m-Carborane-substituted Porphyrins of the Natural Type

Basing on protoporphyrin IX, its monobenzyl ester, deuteroporphyrin IX, 9-hydroxymethyl-m- and 9-hydroxymethyl-p-carboranes, mono- and dicarborane-containing porphyrins were prepared.     

Synthesis of acetyltrialkylpyrroles from 2, 4-pentanediones

The condensation of isonitrosoacetylacetone with 3-alkyl-2,4-pentanediones and reduction with zinc in acetic acid gives-acetyltrialkylpyrroles. The analogous condensation of 3-alkyl-3-nitroso-2,4-pentanediones with acetylacetone leads to-acetyltrialkylpyrroles, and condensation with acetoacetic ester leads to-ethoxycarbonyltrialkylpyrroles. When the- and-acetyltrialkylpyrroles undergo salt formation, the oxygen of the carbonyl group is protonated.