10589-94-3Relevant articles and documents
Synthesis and structure of five or six-coordinate manganese deuteroporphyrin-niacin dyads with intramolecular axial pyridine
Sun, Chengguo,Hu, Bingcheng,Zhao, Donghui,Liu, Zuliang
, p. 130 - 137,8 (2013)
Deuteroporphyrin-niacin dyads with different chain lengths have been synthesized by modification of the propionate side chains of hemin. When a manganese ion was inserted into the porphyrin core, the UV spectral shift of manganese deuteroporphyrin-niacin dyads were experimentally demonstrated to mainly originate from the intramolecular coordination. In order to elaborate the intramolecular coordination, the spectra of single manganese porphyrin complexes in CH2Cl2 solution were measured and compared to that of the addition of axial ligands (pyridine and methyl nicotinate). Among all the synthetic dyads, the compounds of 2,7,12,18-tetramethyl-13,17-di(3- hydroxypropyl nicotinate) porphyrin and 2,7,12,18-tetramethyl-13,17-di(3- aminoethyl nicotinate) porphyrin manganese bearing the short chains did not show intramolecular coordination of the terminal base on the metal ion. Other three compounds of the niacin moiety indirectly bonded to the propionate side chains of manganese porphyrin through the diols linkage exhibited optical spectra characteristic of five or six-coordinate manganese complexes. These results indicate that the niacin groups' access to the Mn(III) center depended on the chain lengths.
Simple and efficient method for synthesis of metallodeutero-porphyrin derivatives bearing symmetrical disulphide bond
Sun, Cheng Guo,Hu, Bing Cheng,Zhou, Wei You,Xu, Shi Chao,Deng, Quan Zhi,Liu, Zu Liang
, p. 527 - 530 (2011)
A novel thiol-derivative porphyrin [2,7,12,18-tetramethyl-13,17-di(3- disulfidepropyl)porphyrin] bearing the symmetrical disulphide bond and its metal complexes have been successfully prepared by means of modification on naturally easily derived heme. The results are described by MS-MS and UV-vis spectroscopy.
Sanders et al.
, p. 49,50, 51, 52 (1978)
Dynamic docking and electron transfer between Zn-myoglobin and cytochrome b5
Liang, Zhao-Xun,Nocek, Judith M.,Huang, Kai,Hayes, Ryan T.,Kurnikov, Igor V.,Beratan, David N.,Hoffman, Brian M.
, p. 6849 - 6859 (2002)
We present a broad study of the effect of neutralizing the two negative charges of the Mb propionates on the interaction and electron transfer (ET) between horse Mb and bovine cyt b5, through use of Zn-substituted Mb (ZnMb, 1) to study the phot
Benzoylation at the meso position of a zinc(II) deuteroporphyrin
Vazquez, Jordi,Gonzalez, Maria M.,Marti, Cristina,Nonell, Santi,Trull, Francesc R.
, p. 69 - 79 (1998)
By short treatment of zinc(II) deuteroporphyrin-IX dimethyl ester with benzoic anhydride/SnCl4, a mixture of benzoylated derivatives was obtained from which a tribenzoyl derivative with benzoyl groups at the 2, 4, and γ-meso positions could be isolated in low yield. Except for the known Vilsmeier formylation, this constitutes the first example of a Friedel-Crafts acylation taking place at the meso position of a porphyrin chelate. The expected lack of regioselectivity of this reaction, even at low conversion rates, and the difficulty to separate the products limit, of course, its synthetic value for the preparation of the particular benzoyl derivatives. This limitation cannot be overcome by starting with a completely β-substituted porphyrin or with a symmetrically substituted porphyrin, since attempts to benzoylate Zn(II) mesoporphyrin-IX dimethyl ester lead exclusively to demetallation. However, these findings add to the knowledge of the fundamental properties of porphyrin reactivity. A rationalization based on calculations at a semiempirical level, which are in acceptable agreement with the experimental results, is presented.
On further knowledge of chlorophyll and hemin. VII. On meso-oxo-porphinogens
Inhoffen,Fuhrhop,von der Haar
, p. 92 - 105 (1966)
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Protonation-deprotonation equilibria in tetrapyrroles Part 4: Mono- and diprotonations of deutero-, hemato-, meso-, and protoporphyrin IX dimethyl esters in methanolic hydrochloric acid
Hynninen, Paavo H.
, p. 385 - 395 (2015/05/20)
The N-protonations in the deutero, hemato, meso and protoporphyrin IX dimethyl esters (DME) were investigated by spectrophotometric titrations using HCl as the acid and methanol as the solvent. Two spectroscopically different protonated species were observed for each porphyrin DME in addition to the neutral form. These were assigned to the N-protonated monocation and dication. There were no difficulties encountered in observing the monocation formation in the HCl-MeOH system. Very sharp isosbestic points were characteristic of each protonation stage. The pK3 values for the porphyrins in the above order were 3.23, 4.70, 2.93 and 3.37; the pK4 values were 2.48, 2.62, 2.41 and 2.64, respectively. For all porphyrins studied, no further spectral changes were observed after the dication was completely formed. This was interpreted as indicating that the formation of more highly protonated species is not possible in fullydelocalized porphyrins possessing the 18 π-electron [18]diazaannulene delocalization pathway. When the titration was performed on the free dicarboxylic acid porphyrins, aggregation obscured the first protonation step and no clear monocation spectrum could be distinguished. However, also in that case the titration ended up to a UVvis spectrum typical of the dication and the effect of aggregation on the pK4 values was negligible. The UVvis spectrometric parameters are given for the neutral forms and for the protonated species of the porphyrin DMEs. The results are discussed in terms of the NH tautomerization connected to the π-electron delocalization pathway (aromaticity), which tends to hinder outofplane distortions in the porphyrin plane, and in terms of solvation and counterion stabilization of the protonated forms.
Rapid aerobic oxidation of alcohols to carbonyl compounds with dioxygen using metallodeuteroporphyrin dimethyl esters as catalysts in the presence of isobutylaldehyde
Sun, Chengguo,Hu, Bingcheng,Liu, Zuliang
experimental part, p. 295 - 303 (2012/07/28)
A facile biomimetic method for rapid oxidation of alcohols to carbonyl compounds using dioxygen as the primary oxidant catalyzed by metallodeuteroporphyrin dimethyl ester [M(DPDME)] in acetonitrile as the reaction solvent and isobutylaldehyde as cocatalyst has been investigated. Among the M(DPDME) catalysts, where M = Fe(III), Co(II), Mn(III), Ni(II), Cu(II), and Zn(II), cobalt porphyrin was found to be the most active and effective catalyst. The catalytic system was widely used in the oxidation of various alcohols and especially exhibited excellent activity for oxidation of aromatic alcohols under mild conditions. Moreover, M(DPDME) was prepared from an improved facile method by chemical modification of natural hemin and an alternative mechanism for the aerobic oxidation of alcohols has been proposed and discussed.
