22112-89-6

Usage

Uses

5,15-Diphenylporphyrin (cas# 22112-89-6) is a useful research chemical.

Biological Activity

5,15-diphenylporphyrin (5,15-dpp) is a selective stat3-sh2 antagonist [1].stat3 is constitutively activated in many human cancers. stat3 functions as a critical mediator of oncogenic signaling through transcriptional activation of genes encoding apoptosis inhibitors, cell-cycle regulators and inducers of angiogenesis [2]. aberrant stat3 activity has been associated with transforming mechanisms induced by oncogenic tyrosine kinases [1].

in vitro

5,15-dpp directly bound to stat3 and antagonized the function of stat3-sh2. 5,15-dpp selectively antagonized stat3-sh2 with an ic50 of 0.28 μm over the other sh2-containing proteins stat1 and grb2[1]. the estimated kd values for the 5,15-dpp binding to stat3 was 880 nm. treatment with 5,15-dpp suppressed the dna binding activity of stat3 in a concentration-dependent manner. 5,15-dpp poorly inhibited stat1 with an ic50 of 10 μm and showed no effect grb2 [1].

references

[1] uehara y, mochizuki m, matsuno k, et al. novel high-throughput screening system for identifying stat3–sh2 antagonists[j]. biochemical and biophysical research communications, 2009, 380(3): 627-631.[2] jing n, tweardy d j. targeting stat3 in cancer therapy[j]. anti-cancer drugs, 2005, 16(6): 601-607.

InChI:InChI=1/C32H22N4/c1-3-7-21(8-4-1)31-27-15-11-23(33-27)19-25-13-17-29(35-25)32(22-9-5-2-6-10-22)30-18-14-26(36-30)20-24-12-16-28(31)34-24/h1-20,33,36H/b23-19-,24-20-,25-19-,26-20-,31-27-,31-28-,32-29-,32-30-

Upstream product

• 118762-53-1 (Z)-2-(phenyl(2H-pyrrol-2-ylidene)methyl)-1H-pyrrole 
• 149-73-5 trimethyl orthoformate 
• 1003-29-8 2-pyrrole aldehyde 
• 21211-65-4 di(pyrrol-2-yl)methane 
• 100-52-7 benzaldehyde 
• 86447-66-7 2,5-anhydro-3-deoxy-4,6-di-O-toluoyl-D-ribohexose 
• 123-11-5 4-methoxy-benzaldehyde 
• 591-31-1 3-methoxy-benzaldehyde 
• 156821-61-3 (5,15-diphenylporphyrinato)zinc(II) 
• 108-98-5 thiophenol 
• 1449663-86-8 5-(3-methoxy-1,1-dimethyl-3-oxopropyl)-dipyrromethane 
• 72621-19-3 4-(4-bromobutoxy)benzaldehyde 
• 85754-58-1 4-(β,β-biscyanoethenyl)benzaldehyde 
• 52010-97-6 4-(hydroxylmethyl)benzaldehyde 

Downstream Products

• 1057140-05-2 5,15-dibromo-10,20-diphenylporphyrin 
• 917-23-7 5,15,10,20-tetraphenylporphyrin 

Relevant academic research and scientific papers

Synthesis of mono- And disubstituted porphyrins: A- and 5,10-A 2-type systems

General syntheses have been developed for meso-substituted porphyrins with one or two substituents in the 5,10-positions and no β substituents. 5-Substituted porphyrins with only one meso substituent are easily prepared by an acid-catalyzed condensation of dipyrromethane, pyrrole-2-carbaldehyde, and an appropriate aldehyde using a "[2+1+1]" approach. Similarly, 5,10-disubstituted porphyrins are accessible by simple condensation of unsubstituted tripyrrane with pyrrole and various aldehydes using a "[3+1]" approach. The yields for these reactions are low to moderate and additional formation of either di- or monosubstituted porphyrins due to scrambling of the intermediates is observed. However, the reactions can be performed quite easily and the desired target compounds are easily removed due to large differences in solubility. A complementary and more selective synthesis involves the use of organolithium reagents for SNAr reactions. Reaction of in situ generated porphyrin (porphine) with 1.1-8 equivalents of RLi gave the monosubstituted porphyrins, while reaction with 3-6 equivalents of RLi gave the 5,10-disubstituted porphyrins in yields ranging from 43 to 90%. These hitherto almost inaccessible compounds complete the series of different homologues of A-, 5,15-A2-, 5,10-A2-, A3-, and A4-type porphyrins and allow an investigation of the gradual influence of type, number, and regiochemical arrangement of substituents on the properties of meso-substituted porphyrins. They also present important starting materials for the synthesis of ABCD porphyrins and are potential synthons for supramolecular materials requiring specific substituent orientations.

Detecting Mechanochemical Atropisomerization within an STM Break Junction

We have employed the scanning tunneling microscope break-junction technique to investigate the single-molecule conductance of a family of 5,15-diaryl porphyrins bearing thioacetyl (SAc) or methylsulfide (SMe) binding groups at the ortho position of the phenyl rings (S2 compounds). These ortho substituents lead to two atropisomers, cis and trans, for each compound, which do not interconvert in solution under ambient conditions; even at high temperatures, isomerization takes several hours (half-life 15 h at 140 °C for SAc in C2Cl4D2). All the S2 compounds exhibit two conductance groups, and comparison with a monothiolated (S1) compound shows the higher group arises from a direct Au-porphyrin interaction. The lower conductance group is associated with the S-to-S pathway. When the binding group is SMe, the difference in junction length distribution reflects the difference in S-S distance (0.3 nm) between the two isomers. In the case of SAc, there are no significant differences between the plateau length distributions of the two isomers, and both show maximal stretching distances well exceeding their calculated junction lengths. Contact deformation accounts for part of the extra length, but the results indicate that cis-to-trans conversion takes place in the junction for the cis isomer. The barrier to atropisomerization is lower than the strength of the thiolate Au-S and Au-Au bonds, but higher than that of the Au-SMe bond, which explains why the strain in the junction only induces isomerization in the SAc compound.

Core–shell poly-methyl methacrylate nanoparticles covalently functionalized with a non-symmetric porphyrin for anticancer photodynamic therapy

Photodynamic therapy (PDT) is an anticancer modality that exploits singlet oxygen and other reactive oxygen species, that are formed by selective irradiation of photosensitive molecules, to kill cancer cells. Most photosensitizers (PS) are hydrophobic and poorly soluble in water and several nanoplatforms have been established to achieve a more efficient delivery. Moreover, the covalent binding of the PS to nanoparticles could in principle reduce unwanted bleaching of the PS, while preserving its photodynamic activity. In this study we report the synthesis of a novel non-symmetrical diaryl-porphyrin suitably modified with a polymerizable pendant, that was used for the preparation of core-shell poly-methyl methacrylate nanoparticles covalently loaded with the diaryl-porphyrin (PMMA@PorVa). Particles, which were prepared with two different porphyrin loadings, are spherical in shape and with a narrow hydrodynamic diameter around 70 nm and a positive zeta potential. Their photo-toxicity was tested against the human colon carcinoma cell line HCT116 and the human ovarian adenocarcinoma cell line SKOV3. PMMA@PorVa were able to inhibit tumor cells proliferation similarly to the free porphyrin, thus confirming that the covalent attachment of the PS to PMMA nanoparticles allows to preserve PS photodynamic activity and in vitro efficacy. Flow cytometric analysis of apoptotic cells demonstrates that, especially in SKOV3 cells, the free diaryl-porphyrin is more effective in inducing apoptosis.

A Practical Synthesis of Meso-monosubstituted, β-Unsubstituted Porphyrins

(Matrix Presented) A simple straightforward synthesis for meso-monosubstituted, β-unsubstituted porphyrins is reported. Porphyrins of this type are easily prepared by condensation of dipyrromethane, pyrrole-2-carbaldehyde, and the desired aromatic or aliphatic aldehyde. The method can be used for a variety of functional groups with yields between 2 and 12%. In most cases, the 5,15-disubstituted porphyrin is obtained as a second product but can be removed easily.

Exploration of meso-substituted formylporphyrins and their Grignard and Wittig reactions

Formylporphyrins were prepared by using either the 1,3-dithian-2-yl residue as a precursor for the CHO group or by the Vilsmeier reaction. Two synthetic routes for the introduction of the 1,2-dithian-2-yl group were explored. Furthermore, reactions of the

A Porphyrin C-Nucleoside Incorporated into DNA

(Matrix Presented) A free porphyrin coupled on 2-deoxy-D-ribose was synthesized and incorporated into DNA via phosphoramidite chemistry. Substitution at the ends of a 5′-modified self-complementary duplex was found to be thermally and thermodynamically st

METHOD FOR PREPARING PORPHYRIN DERIVATE

The present invention relates to a method for manufacturing porphyrin derivatives, comprising a step of oxidizing porphyrinogen by oxygen bubbling under a metal catalyst to synthesize porphyrin derivatives. Therefore, since the method for manufacturing porphyrin derivatives of the present introduced a method of oxidization using oxygen bubbling under the metal catalyst without using a quinone-based oxidizing agent, it is possible to increase the yield of porphyrin derivatives and have an effect that a refining process is very easy.COPYRIGHT KIPO 2019

A novel porphyrin derivative, composition for detecting cyanide ion comprising the same and method for detecting cyanide ion using the same

The present invention provides a novel dicyanovinyl porphyrin compound, a composition for detecting cyanide ion containing the same, and a method for detecting cyanide ion using the same. The dicyanovinyl porphyrin compound, the composition for detecting cyanide ion containing the same and the method for detecting cyanide ion using the same of the present invention can be usefully used as a cyanide ion specific detection technique in a field of cyanide ion detection.COPYRIGHT KIPO 2019

Synthesis of functionalized, sterically congested calix[4]phyrin macrocycles using donor-acceptor-substituted cyclopropanes-first example of a mono-meso-spirolactone incorporated into a calix[4]phyrin

Calix[4]phyrins are an important class of hybrid macrocyclic systems at the interface between porphyrins and calixpyrroles (porphyrinogens). A new stepwise synthesis of oxidation-resistant meso-hydrogenated calix[4]phyrins is reported, which allows variable substitution in the residues of their sp 2-meso-centers without the need for a porphyrin intermediate. It relies on the acid-catalyzed condensation of a sterically hindered donor-acceptor-substituted cyclopropane precursor with pyrrole to form a sterically congested dipyrromethane. This was subsequently condensed with a wide range of alkyl and aryl aldehydes bearing electron-donating or electron-withdrawing substituents followed by an oxidation step to form stable calix[4]phyrin(1.1.1.1)s with bridging meso-CH hydrogen atoms through an acid-promoted dehydrative condensation. The methodology avoids any need for premetallation of the macrocycle and/or the use of organometallic catalysts or reagents and allows the incorporation of the bulky cyclopropane-derived substituents specifically into the 5,15-meso-like positions. The resulting regioisomerically pure products display conformational features that reflect their mixed nature between porphyrins and calixpyrroles and they were assessed by X-ray diffraction analysis, NMR techniques and UV/Vis spectroscopy. The possibility to introduce key functional groups enables subsequent modification of these calix[4]phyrins and allows their connection to other groups such as biologically active moieties. Of special interest is an unprecedented example of an acid-driven lactonization that results in the incorporation of a mono-meso-spirolactone into a calix[4]phyrin(1.1.1.1). Moreover, it is demonstrated that this approach to calix[4]phyrins is also applicable to other sterically congested dipyrromethanes.

Palladium-catalyzed kumada coupling reaction of bromoporphyrins with silylmethyl grignard reagents: Preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems

We have developed an efficient method for preparing silylmethyl-substituted porphyrins via the palladium-catalyzed Kumada cross-coupling reaction of bromoporphyrins with silylmethyl Grignard reagents. We demonstrated the synthetic utility of these silylmethylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives through a variety of transformations of the silylmethyl groups, including the DDQ-promoted oxidative conversion to CHO, CH2OH, CH2OMe, and CH2F functionalities and the fluoride ion-mediated desilylative introduction of carbona-carbon single and double bonds.