33909-86-3Relevant academic research and scientific papers
Synthesis and catalytic properties of a series of cobalt porphyrins as cytochrome P450 model: The effect of substituents on the catalytic activity
Hu, Bingcheng,Sun, Chengguo,Deng, Quanzhi,Liu, Zuliang
, p. 345 - 352 (2013/07/26)
A series of cobalt porphyrins derived from hemin was prepared as cytochrome P450 models. Effects of substituents at the cobalt deuteroporphyrin-propionate side chains are investigated in oxidation of toluene with air to benzaldehyde and benzyl alcohol without the use of solvent and sacrificial co-reductant. The catalytic activity of cobalt porphyrins depends on the type of substituents. When the electron-withdrawing groups like -Cl, -Br, were introduced into the double propionate side chains, they can increase the catalyst stability and selectivity to benzaldehyde. In comparison with these electron-withdrawing groups, the electron-donor groups, such as -CH3, -S-S- and -NH 2 groups, can improve their catalytic activities. Moreover, the electron-donor group containing an unpaired electron (such as -S-S-, -NH 2) is benefit for improving its catalytic efficiency and promoting the electron delivery. It can be concluded that the double propionate side chains in the deuteroporphyrin complex may participate in oxidation process and effect electron transfer from the high-valent metalloporphyrin species to the substrate.
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
scheme or table, p. 527 - 530 (2012/02/01)
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.
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 (2007/10/03)
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.
New Syntheses and Reactions of Some Halogenated Porphyrins
Minnetian, Ohannes M.,Morris, Ian K.,Snow, Kevin M.,Smith, Kevin M.
, p. 5567 - 5574 (2007/10/02)
Efficient syntheses of 2,4-dibromo- and 2,4-diiododeuteroporphyrin IX have been carried out by treating zinc(II) 2,4-bis(chloromercurio)deuteroporphyrin IX dimethyl ester (2) with bromine or iodine.Unavoidable mesochlorination occurs when 2 is treated with chlorine and with other free-radical chlorinating agents.Regioselective meso-chlorination and peripheral (β) bromination are shown to occur from brief treatment of copper(II) deuteroperphyrin IX or β-unsubstituted a,c-biladienes with the corresponding copper(II) halide in refluxing dimethylformamide.Protoporphyrin IX has been synthesized by vinylation of 2 via ethylene/LiPdCl3 (35percent yield), with vinyl bromide and Wilkinson's catalyst (63percent), or from 2,4-dibromodeuteroporphyrin IX with ethenyltributylstannane/(Ph3P)4Pd0 (85percent).
Manipulation of Vinyl Groups in Protoporphyrin IX: Introduction of Deuterium and Carbon-13 Labels for Spectroscopic Studies
Smith, Kevin M.,Fujinari, Eugene M.,Langry, Kevin C.,Parish, Daniel W.,Tabba, Hani D.
, p. 6638 - 6646 (2007/10/02)
Using commercially available hemin (5) as the starting material, routes for preparation of monovinyl deuterated (27), monovinyl carbon-13 enriched (41,42), and divinyl carbon-13 enriched (43,44) derivatives of protoporphyrin IX dimethyl ester (1) are described.The monovinyl carbon-13 enriched porphyrins 41 and 42 were obtained by way of a previously reported Wittig reaction on Spirographis and iso-Spirographis porphyrin dimethyl esters 28 and 39, respectively.A new efficient partial synthesis of Spirographis porphyrin dimethyl ester (28) from deuteroporphyrin IX dimethyl ester (7) is reported, and in this the key formyl group at the 2 position is inserted by way of a Vilsmeier reaction employing a hindered amide.
The Chemistry of Pyrrolic Compounds. LII. The Preferred Pathway of Electron Delocalization in Metalloporphyrins
Chakraborty, Swapna,Clezy, Peter S.,Sternhell, Sever,Thuc, Le van
, p. 2315 - 2323 (2007/10/02)
Measurement of the proton coupling constant in the allylic unit, CH3-C=C-H, of the zinc(II), nickel(II) and magnesium(II) chelates of the deuteroporphyrin isomer (3a) points in each case to the double bond of this system having a significantly diminished bond order.Similar data have been obtained for the dication derivative of (3a).These findings are in accord with the view that the ?-electron delocalization pathway in porphyrin dications and metalloporphyrins involves the periphery of the molecule as was previously shown for the metal-free porphyrin.New synthetic approaches to the porphyrin (3a) have been studied.
