Metallkomplexe mit Tetrapyrrol‐Liganden, XLVIII. Vilsmeier‐Formylierung von Metallporphyrinen mit CoII, NiII, PdII, PtII, CuII, ZnII, CoIII, CrIII, MnIII, FeIII, AlIII, SiIV und PtIV in Abhängigkeit vom Zentralmetall

Buchler, Johann W.; Dreher, Christine; Herget, Gerhard

doi:10.1002/jlac.198819880110

Cited by 30 publications

(15 citation statements)

References 49 publications

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“…The Vilsmeier formylation of porphyrins using DMF/POCl 3 followed by treatment with aqueous base introduces a formyl group at the meso - or the β-position of porphyrin macrocycles [182-185]. The use of a sterically hindered Vilsmeier reagent, such as that prepared from N , N -diisobutylformamide/POCl 3 favors substitution at the β-positions [186] whereas N , N -(dimethylamino)acrolein (3-DMA)/POCl 3 produces 2-formylvinylporphyrins in good yields [187, 188].…”

Section: Porphyrin Functionalizationmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

110

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Porphyrin macrocycles have been the subject of intense study in the last century because they are widely distributed in nature, usually as metal complexes of either iron or magnesium. As such, they serve as the prosthetic groups in a wide variety of primary metabolites, such as hemoglobins, myoglobins, cytochromes, catalases, peroxidases, chlorophylls, and bacteriochlorophylls; these compounds have multiple applications in materials science, biology and medicine. This article describes current methodology for preparation of simple, symmetrical model porphyrins, as well as more complex protocols for preparation of unsymmetrically substituted porphyrin macrocycles similar to those found in nature. The basic chemical reactivity of porphyrins and metalloporphyrin is also described, including electrophilic and nucleophilic reactions, oxidations, reductions, and metal-mediated cross-coupling reactions. Using the synthetic approaches and reactivity profiles presented, eventually almost any substituted porphyrin system can be prepared for applications in a variety of areas, including in catalysis, electron transport, model biological systems and therapeutics.

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Section: Porphyrin Functionalizationmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

110

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“…[8,29] It is also known that nickel complexes are subjected to of VilsmeierHaack formylation with the highest reaction rate. [30] Synthesis To obtain N-substituted hydrazones of metal complexes of β-octaethylporphyrin and coproporphyrin I we used a method based on the interaction of meso-formyl derivatives of metal porphyrins with N-substituted hydrazines. meso-Formyl metal porphyrin derivatives were synthesized by formylation with the Vilsmeier-Haack reaction (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Study of New N-Substituted Hydrazones of Ni(II) Complexes of β-Octaethylporphyrin and Coproporphyrin I Tetraethyl Ester

Shkirdova¹,

Zamilatskov²,

Stanetskaya³

et al. 2017

MHC

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N-Substituted hydrazones of nickel complexes of β-octaethylporphyrin and tetraethyl ester of coproporphyrin I were obtained. These compounds can serve as intermediate compounds for the preparation of meso-functionalized derivatives of porphyrins by means of various reactions. In the first stage Vilsmeier-Haack reaction was carried out by the interaction of nickel complexes of β-octaethylporphyrin and tetraethyl ester of coproporphyrin I with N,N-dimethylformamide and phosphorus(V) oxochloride forming the so-called "phosphorus complex", which was hydrolyzed with saturated solution of sodium acetate. The corresponding meso-formyl derivatives of metal porphyrins were obtained as a result. Synthesis of the hydrazones was carried out by the reactions of meso-formyl derivatives with the hydrazines using trifluoroacetic acid as a catalyst. The result of the reaction was formation of hydrazones in the form of a mixture of E-and Z-isomers, which were separated using preparative thin layer chromatography. Thus a series of hydrazoneswith different substituents at the nitrogen atom was obtained. The structures of all obtained compounds were determined using the methods of NMR spectroscopy, electronic absorption spectroscopy and mass spectrometry. For nickel complex of tosylhydrazone derivative of β-octaethylporphyrin the crystal structure was determined using X-ray diffraction. X-ray analysis shows that porphyrin molecules in the crystal form dimers bonded by two hydrogen bonds between the hydrogen atom of the NH-group of hydrazone and the oxygen atom of the sulfonate groups.

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“…The electron-rich Mg(II) and Zn(II) complexes are easily demetallated under Vilsmeier conditions, while trivalent complexes such as Mn(III) and Fe(III) are less reactive towards electrophilic formylation reactions, affording lower yields of the formylated products. In contrast, metallo-meso-tetra-aryl porphyrins under Vilsmeier conditions form the 2-formyl derivative (65) in good yield [72].…”

Section: Formylationmentioning

confidence: 97%

“…Compound 61 further reacts with Grignard and aryllithium reagents to produce the corresponding alcohol derivatives, such as phenyl hydroxy methyl (72) or methyl hydroxy methyl (73) derivative [75]. Dehydration of 73 in the presence of p-TSA gives the vinylporphyrin (71), which is further converted into the ethyl derivative (74) by catalytic hydrogenation.…”

Section: Reactions Of Formyl Porphyrinsmentioning

confidence: 99%