Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Fluorinated maleimide-substituted porphyrins and chlorins: synthesis and characterization.

ABSTRACT: Maleimide-containing fluorinated porphyrins and chlorins were prepared based on the reaction of Zn(II) or Ni(II) complexes of 5,10,15,20-tetrakis(4-amino-2,3,5,6-tetrafluorophenyl)porphyrin and chlorin with maleic anhydride. Porphyrin maleimide derivatives were also prepared by the reaction of 5,10,15,20-tetrakis(4-azido-2,3,5,6-tetrafluorophenyl)porphyrinato Zn(II) or Ni(II) with N-propargylmaleimide via the CuAAC click reaction to afford fluorinated porphyrin-triazole-maleimide conjugates. New maleimide derivatives were isolated in reasonable yields and identified by UV-vis, 1H NMR, 19F NMR spectroscopy and mass-spectrometry.

SUBMITTER: Ol'shevskaya VA

PROVIDER: S-EPMC6880841 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Fluorinated maleimide-substituted porphyrins and chlorins: synthesis and characterization.

Ol'shevskaya Valentina A VA Kononova Elena G EG Zaitsev Andrei V AV Zaitsev Andrei V AV

Beilstein journal of organic chemistry 20191113

Maleimide-containing fluorinated porphyrins and chlorins were prepared based on the reaction of Zn(II) or Ni(II) complexes of 5,10,15,20-tetrakis(4-amino-2,3,5,6-tetrafluorophenyl)porphyrin and chlorin with maleic anhydride. Porphyrin maleimide derivatives were also prepared by the reaction of 5,10,15,20-tetrakis(4-azido-2,3,5,6-tetrafluorophenyl)porphyrinato Zn(II) or Ni(II) with <i>N</i>-propargylmaleimide via the CuAAC click reaction to afford fluorinated porphyrin-triazole-maleimide conjugat ...[more]

PMID: 31807205

Similar Datasets

Rational routes to formyl-substituted chlorins.

Project description:Two distinct approaches have been developed for the synthesis of chlorins bearing formyl groups: (1) reaction of an acetal-substituted 1-acyldipyrromethane with 2,3,5,6-tetrahydro-1,3,3-trimethyldipyrrin to give upon hydrolysis a 5-formylchlorin and (2) Pd-mediated coupling of a bromochlorin with a one-carbon synthon (hydroxymethyl tributyltin or CO) to give a 13-, 15-, or 3,13-formylchlorin. The zinc chlorins exhibit long-wavelength peak absorption maxima ranging from 626 to 667 nm, indicating the wavelength tunability afforded by formyl substitution.

| S-EPMC2525510 | biostudies-literature

Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

Project description:Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H?TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H?TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

| S-EPMC6274165 | biostudies-literature

Synthesis of 4-substituted azopyridine-functionalized Ni(II)-porphyrins as molecular spin switches.

Project description:We present the synthesis and the spin switching efficiencies of Ni(II)-porphyrins substituted with azopyridines as covalently attached photoswitchable ligands. The molecules are designed in such a way that the azopyridines coordinate to the Ni ion if the azo unit is in cis configuration. For steric reasons no intramolecular coordination is possible if the azopyridine unit adopts the trans configuration. Photoisomerization of the azo unit between cis and trans is achieved upon irradiation with 505 nm (trans→cis) and 435 nm (cis→trans). Concurrently with the isomerization and coordination/decoordination, the spin state of the Ni ion switches between singlet (low-spin) and triplet (high-spin). Previous studies have shown that the spin switching efficiency is strongly dependent on the solvent and on the substituent at the 4-position of the pyridine unit. We now introduced thiol, disulfide, thioethers, nitrile and carboxylic acid groups and investigated their spin switching efficiency.

| S-EPMC7590622 | biostudies-literature

Toward a general synthesis of chlorins.

Project description:Recently, we described a new synthesis of C,D-ring symmetric chlorins 11, involving 2 + 2 condensation of bis-formyl-dihydrodipyrrins 9 with symmetrically substituted dipyrromethane diacids 10 (Method I). However, while versatile in many aspects, Method I was unsuited to the broader goal of synthesizing fully non-symmetric chlorins of general structure 15, which requires regioselective control over the reacting centers in the A,B- and C,D-ring components. In this paper, we describe four new 2 + 2 strategies that accomplish this differentiation (Methods II-V). Of these, Method V, which combines operational simplicity with moderate to high product yields, proved to be the most effective route, exploiting reactivity differences between the two formyl groups of A,B-rings 9 to impart excellent regioselectivity. Methods II-IV are also useful alternatives to Method V, although in some cases, the appropriately functionalized precursors are less readily available. All four approaches generate single regioisomers of diversely substituted chlorins, and in every case, the 2 + 2 condensation is accomplished in a simple, one-flask procedure without need for additives such as oxidizing agents or metals. Taken together, these methodologies provide expanded access to an array of chlorins for SAR studies that may advance the effectiveness of PDT and other applications.

| S-EPMC2443860 | biostudies-literature

Synthesis and structural characterization of fluorinated thiosemicarbazones.

Project description:Six new fluorinated thiosemicarbazones R‑C(R')=N-NH-C(S)NH(2) (R = 2,4-C(6)H(3)F(2), R' = H (1); R = 2,5-C(6)H(3)F(2), R' = H (2); R = 2,6-C(6)H(3)F(2), R' = H (3); R = 3,4-C(6)H(3)F(2), R' = H (4); R = 3,5-C(6)H(3)F(2), R' = H (5) and R = 4-C(6)H(4)F, R' = C(6)H(5), (6)) have been prepared. The molecular structures of compounds 1 to 6 have been determined.

| S-EPMC6270490 | biostudies-literature

Novel fluorinated ring-fused chlorins as promising PDT agents against melanoma and esophagus cancer.

Project description:Investigation of novel 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused chlorins, derived from 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, as PDT agents against melanoma and esophagus cancer is disclosed. Diol and diester fluorinated ring-fused chlorins, including derivatives with 2-(2-hydroxyethoxy)ethanamino groups at the phenyl rings, were obtained via a two-step methodology, combining SNAr and [8π + 2π] cycloaddition reactions. The short-chain PEG groups at the para-position of the phenyl rings together with the diol moiety at the fused pyrazole ring promote a red-shift of the Soret band, a decrease of the fluorescence quantum yield and an increase of the singlet oxygen formation quantum yield, improving the photophysical characteristics required to act as a photosensitizer. Introduction of these hydrophilic groups also improves the incorporation of the sensitizers by the cells reaching cellular uptake values of nearly 50% of the initial dose. The rational design led to a photosensitizer with impressive IC50 values, 13 and 27 nM against human melanoma and esophageal carcinoma cell lines, respectively.

| S-EPMC8128062 | biostudies-literature

Atropisomers of meso Tetra(N-Mesyl Pyrrol-2-yl) Porphyrins: Synthesis, Isolation and Characterization of All-Pyrrolic Porphyrins.

Project description:Atropisomerism has been observed in a variety of biaryl compounds and meso-aryl substituted porphyrins. However, in porphyrins, this phenomenon had been shown only with o-substituted 6-membered aromatic groups at the meso-position. We show herein that a 5-membered heteroaromatic (N-mesyl-pyrrol-2-yl) group at the meso-position leads to atropisomerism. In addition, we report a 'one-pot' synthetic route for the synthesis of 'all-pyrrolic' porphyrin (APP) with several N-protection groups (Boc, Cbz, Ms and Ts). Among these groups, we found that only the Ms group gave four individually separable atropisomers of meso-tetra(N-Ms-pyrrol-2-yl) porphyrin. Furthermore, the reductive removal of Cbz- was achieved to obtain meso-tetra(pyrrol-2-yl) porphyrin. Thus, our synthetic procedure provides an easy access to a group of APPs and stable atropisomers, which is expected to expand the application of novel APP-based materials.

| S-EPMC7187276 | biostudies-literature

Rational design of substituted maleimide dyes with tunable fluorescence and solvafluorochromism.

Project description:A series of maleimide derivatives were systematically designed and synthesized with tunable fluorescent properties. The facile modifications herein provide a simple methodology to expand the scope of maleimide-based dyes and also provide insight into the relationship between substitution pattern and optical properties.

| S-EPMC5885783 | biostudies-literature

Copolymerization of Phenylselenide-Substituted Maleimide with Styrene and Its Oxidative Elimination Behavior.

Project description:Selenium-containing monomer monophenyl maleimide selenide (MSM) was synthesized and copolymerized with styrene (St) using reversible addition-fragmentation chain transfer (RAFT) polymerization. Copolymers with controlled molecular weight and narrow molecular weight distribution were obtained. The structure of the copolymer was characterized by nuclear magnetic resonance, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrum, Fourier transform infrared spectroscopy (FT-IR) and Ultraviolet⁻visible spectroscopy (UV-vis) spectroscopy. The copolymer can be oxidized by H₂O₂ to form carbon-carbon double bonds within the main chain due to the unique sensitivity of selenide groups in the presence of oxidants. Such structure changing resulted in an interesting concentration-related photoluminescence emission enhancement.

| S-EPMC6415178 | biostudies-literature

Multicomponent Molecular Systems Based on Porphyrins, 1,3,5-Triazine and Carboranes: Synthesis and Characterization.

Project description:2,4,6-Trichloro-1,3,5-triazine (cyanuric chloride) is an excellent coupling reagent for the preparation of highly structured multifunctional molecules. Three component systems based on porphyrin, cyanuric chloride and carborane clusters were prepared by a one-pot stepwise amination of cyanuric chloride with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, followed by replacement of the remaining chlorine atoms with carborane S- or N-nucleophiles. Some variants of 1,3,5-triazine derivatives containing porphyrin, carborane and residues of biologically active compounds such as maleimide, glycine methyl ester as well as thioglycolic acid, mercaptoethanol and hexafluoroisopropanol were also prepared. A careful control of the reaction temperature during the substitution reactions will allow the synthesis of desired compounds in a good to high yields. The structures of synthesized compounds were determined with UV-vis, IR, 1H NMR, 11B NMR, MALDI-TOF or LC-MS spectroscopic data. The dark and photocytotoxicity as well as intracellular localization and photoinduced cell death for compounds 8, 9, 17, 18 and 24 were evaluated.

| S-EPMC9572311 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data