71147-55-2

Upstream product

• 14172-91-9 5,10,15,20-tetraphenylporphyrin Cu(II) complex 
• 14172-91-9 (tetraphenylporphyrin)copper(II) 
• 7697-37-2 nitric acid 
• 917-23-7 5,15,10,20-tetraphenylporphyrin 

Downstream Products

• 1257333-46-2 [Co(NC₄H₂)3(C(C₆H₅))4NC₄N₂C₁₂H₆N₂] 
• 1257333-47-3 [Ni(NC₄H₂)3(C(C₆H₅))4NC₄N₂C₁₂H₆N₂] 
• 1257333-49-5 [Zn(NC₄H₂)3(C(C₆H₅))4NC₄N₂C₁₂H₆N₂] 
• 1257333-50-8 [Cu(NC₄H₂)3(C(C₆H₅))4NC₄N₂C₁₂H₆N₂] 
• 869383-90-4 2-(1-acetyl-2-oxopropyl)-5,10,15,20-tetraphenylporphyrinatocopper(II) 
• 1415029-88-7 (2-amino-5,10,15,20-tetraphenylporphyrinato)zinc(II) 
• 82945-59-3 2-amino-5,10,15,20-tetraphenylporphyrin 
• 207236-03-1 2-nitro-7,8,12,13,17,18-hexabromo-meso-tetraphenylporphyrinato copper(II) 
• 1412456-47-3 [2-amino-3-nitro-5,10,15,20-tetraphenylporphyrinato]zinc(II) 

Relevant academic research and scientific papers

Isomers of β,β-Dinitro-5,10,15,20-tetraphenylporphy-rin Derivatives: Valuable starting materials for further transformations

The synthesis, chromatographic isolation, and structure elucidation of β,β-substituted isomers of dinitro-5,10,15,20-tetraphenylporphyrin complexes are described. meso-Tetraphenyl-porphyrin chelates (CuII, NiII, CoII) upon reaction wit e.g., itric acid (yellow HNO3, d = 1.52, diluted to 25–50%) in CHCl3 formed a mixture of nitro-derivatives with combined yields of ca 80%. This nitration (under optimized conditions: 25–30% HNO3, 30–40 min, r.t.) can be carried out selectively to give mainly β,β-dinitro-compounds in yields of up to 73%. From the above mixtures of five possible regioisomers that can be formed, usually two or three of them were isolated, for which the structures were assigned on the basis of 1H NMR spectra including COSY and NOESY measure-ments. These types of products are attractive starting materials for synthesis of potential anticancer PDT agents with unique structures, being practically unavailable by any other alternative method.

β-Maleimide substituted meso-arylporphyrins: Synthesis, transformations, physico-chemical and antitumor properties

The maleimide moiety is widely used in drug design. To explore the properties of maleimide containing photosensitizers we obtained a series of new β-maleimide functionalized meso-arylporphyrins through acylation of β-amino group in porphyrins with maleic anhydride followed by condensation of maleic acid monoamides. The selective reactivity of porphyrin maleimides toward thiols was demonstrated using mercaptocarboranes and cysteine. New derivatives retained the ability of tetrapyrrolic macrocyclic compounds to absorb light in visible spectral region and to generate triplet states and reactive oxygen species upon photoactivation. Importantly, illumination of cells loaded with a cell permeable 2-{3-[(o-carboran-1′-yl)thio]pyrrolidine-2,5-dione-1-yl}-5,10,15,20-tetraphenylporphyrin triggered rapid (within the initial minutes) generation of superoxide anion radical concomitantly with a decrease of mitochondrial membrane potential, and then the loss of the plasma membrane integrity and cell death. Thus, the maleimide-substituted porphyrins represent a new chemotype of polyfunctionalized compounds for an in-depth investigation as photosensitizers in cancer and beyond.

Synthetic access to new porphyrinoids from 2-nitro-5,10,15,20-tetraphenylporphyrin and an arylacetonitrile

Abstract: In this work, the reactivity of 2-nitro-5,10,15,20-tetraphenylporphyrin with 2-(4-nitrophenyl)acetonitrile in the presence of KOH as base was studied. Under these conditions, three new compounds were isolated: a β-di-substituted derivative, as the major compound, accompanied by two minor products, a π-extended and a β-isoxazoline-fused derivative, all in acceptable yields. A preliminary study was also performed in the presence of K2CO3. It allowed the isolation of a cyclopropyl-annulated chlorin in very good yield. All the obtained products were photochemically and photophysically characterized, some of them showing promising properties to be used as photosensitizers in photodynamic processes. Graphical abstract: [Figure not available: see fulltext.].

Exciton-Coupled Circular Dichroism Characterization of Monotopically Binding Guests in Host?Guest Complexes with a Bis(zinc porphyrin) Tweezer

A stiff-stilbene-linked bisporphyrin tweezer with inherent helicity was used for exciton-coupled circular dichroism (ECCD) characterization of a series of monotopically binding amine guest molecules. CD signals were observed for a variety of monoamines at relatively low tweezer/amine (host/guest) ratios between 1 : 10 to 1 : 70. For the amines producing the most intense CD signals, a binding stoichiometry of 1 : 2 was found. A likely explanation is the presence of guest-guest interactions in the complexes. This is supported by the correlation observed between CD signal intensity and magnitude of possible noncovalent binding between the guests, which can be divided into three groups showing no, moderate and strong response, respectively. Further support for this rationalization comes from molecular modelling.

Structure and dynamics processes in free-base chlorins controlled by chemical modifications of macroring and aryl groups in: Meso -positions

In this work we present the synthesis, detailed structural characterization and analysis of molecular motion for unsymmetrical pyrrolidine-fused chlorins employing NMR, UV spectroscopy and DFT theoretical calculations. In samples, the meso-rings were modified by substitution of hydrogen by fluorine in ortho1 and meta positions 2. The sample with perfluorinated ring 3 and phenyl derivative 4 were used as reference species. The assignment of signals was performed employing 2D NMR techniques. The rotational dynamics was examined by means of 1H and 19F variable-temperature (VT) 1D NMR spectroscopy and 2D EXSY experiments. The synergism of steric effect between pyrrolidine ring and meso-rings is unambiguously proved. Models 1 and 3 behave very similar, aromatic rings are rigid in temperature range 233-373 K. For sample 2 and 4 the distinct molecular dynamics was revealed. The barrier of rotation depends on localization of ring in the chlorin structure. Those which are bonded in the neighborhood of pyrrolidine ring are more rigid compared to those localized on the opposite site. The temperature is a trigger which sequentially releases the rotation of aromatic group in the desired localization. Introduction of fluorine in labeled position has influence on static geometry defined by saddling angles.

Beta-(2,3-dihydro-naphthyl[1,2,e]-m-oxazinyl) tetraphenylporphyrin, and preparation method and application thereof

The invention discloses beta-(2,3-dihydro-naphthyl[1,2,e]-m-oxazinyl)tetraphenylporphyrin of which the structural general formula is disclosed as Formula (I) or Formula (II), and a preparation method and application thereof. The preparation method comprises the following steps: 1) preparing 5,10,15,20-tetraphenyl porphyrin from pyrrole and benzaldehyde, carrying out coordination with copper to obtain 5,10,15,20-tetraphenyl copper porphyrins, carrying out regioselective nitration to obtain beta-nitro-substituted-5,10,15,20-tetraphenyl copper porphyrins, carrying out decoppering and reduction to obtain beta-amino-substituted-5,10,15,20-tetraphenyl porphyrins, and reacting with acetate to obtain beta-amino-substituted-tetraphenyl metalloporphyrins (beta-NH2-MTPP); 2) carrying out condensation reaction on the beta-NH2-MTPP, formaldehyde and 2-naphthol, separating the product by column chromatography to obtain a beta-(2,3-dihydro-1H-naphthyl[1,2,e]-m-oxazinyl)-substituted tetraphenyl porphyrin metal complex; and decoppering to obtain the beta-(2,3-dihydro-naphthyl[1,2,e]-m-oxazinyl)tetraphenylporphyrin. The compounds can be used for preparing photodynamic-therapy photosensitizers and antineoplastic drugs with small toxic and side effects and high activity.

Synthesis and properties of bis-porphyrin molecular tweezers: Effects of spacer flexibility on binding and supramolecular chirogenesis

Ditopic binding of various dinitrogen compounds to three bisporphyrin molecular tweezers with spacers of varying conformational rigidity, incorporating the planar enediyne (1), the helical stiff stilbene (2), or the semi-rigid glycoluril motif fused to the porphyrins (3), are compared. Binding constants Ka = 104-106 M-1 reveal subtle differences between these tweezers, that are discussed in terms of porphyrin dislocation modes. Exciton coupled circular dichroism (ECCD) of complexes with chiral dinitrogen guests provides experimental evidence for the conformational properties of the tweezers. The results are further supported and rationalized by conformational analysis.

Synthesis, photophysical properties and biological evaluation of β-alkylaminoporphyrin for photodynamic therapy

A series of β-alkylaminoporphyrins conjugated with different amines at β position (D1–D3) or with electron-donating and electron-withdrawing substituents at phenyl position (D4–D6) were synthesized. Their photophysical and photochemical properties, intracellular localization, photocytotoxicities in vitro and vivo were also investigated. All target compounds exhibited no cytotoxicities in the dark and excellent photocytotoxicities against HeLa cells. Among them, D6 showed the highest phototoxicity and the lowest dark toxicity, which was more phototoxic than Hematoporphyrin monomethyl ether (HMME). In addition, D6 exhibited best photodynamic antitumor efficacy on BALB/c nude mice bearing HeLa tumor. Therefore, D6 is a powerful and promising antitumor photosensitizer for photodynamic therapy.

β-Pyrazino-fused tetrarylporphyrins

A novel method for the preparation of β-fused porphyrin dyads was developed that exploits a one-pot reaction of 2,3-diaminoporphyrins with diethyl oxalate. This approach provides good yields of the zinc β-fused dyad and the corresponding free-base, openin

2-(1-acetyl-2-oxopropyl)-5,10,15,20-tetraphenylporphyrin and its transition-metal complexes

The 2-(1-acetyl-2-oxopropyl)-5,10,15,20-tetraphenylporphyrin free base (H2TPP-AOP) and its transition-metal complexes (MTPP-AOP, M = Cu 2+, Zn2+) have been synthesized. Single-crystal X-ray diffraction analysis revealed th