Nitrobenzene method: A keystone in <i>meso</i>-substituted halogenated porphyrin synthesis and applications

Pinto, Sara M. A.; Vinagreiro, Carolina S.; Tomé, Vanessa A.; Piccirillo, Giusi; Damas, Liliana; Pereira, Mariette M.

doi:10.1142/s1088424619300039

Cited by 11 publications

(6 citation statements)

References 120 publications

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“…In order to modify the Adler–Longo method and obtain a chlorin-free product, Rocha Gonsalves et al proposed a one-step nitrobenzene method for the synthesis of symmetrical meso -substituted porphyrins via condensation of pyrrole with aliphatic or aromatic aldehydes in acetic or propionic acid in the presence of nitrobenzene (30%) as an oxidant for intermediate tetraarylporphyrinogen [ 96 – 99 ] (Scheme 1 , Table 1 ). This procedure is advantageous due to its versatility and the possibility of obtaining porphyrins by direct condensation of pyrrole with aldehydes, regardless of their nature and type of substituents.…”

Section: Principal Methodologies Of the Synthesis Of Tetrapyrrole Mac...mentioning

confidence: 99%

Main Strategies for the Synthesis of meso-Arylporphyrins

Койфман

Агеева

2022

Russ J Org Chem

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meso -Arylporphyrins as most accessible tetrapyrrole macroheterocycles have always been the focus of attention from researchers concerned with practically useful properties of these compounds. The first syntheses of meso -arylporphyrins date back to about 90 years ago. Up to now, the yields of these compounds have been improved from 5 to 80%. The present review analyzes different ways and strategies for the synthesis of meso -aryl-substituted porphyrins. The most efficient methods that can be scaled up to an industrial level have been identified.

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Section: Principal Methodologies Of the Synthesis Of Tetrapyrrole Mac...mentioning

confidence: 99%

Main Strategies for the Synthesis of meso-Arylporphyrins

Койфман

Агеева

2022

Russ J Org Chem

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“…After work-up, all starting porphyrins were obtained in yields similar to those found in literature. [29,30] Then, in the case of porphyrin 1, nucleophilic substitution with the polyethylene glycol group was achieved by reacting the starting porphyrin with one equivalent of PEG500, DMF as solvent, and NaH as base, at 80ºC. The progress of the reaction was monitored via TLC and the reaction was stopped after 48 h. After purification using aluminium oxide column chromatography, porphyrin 1 was obtained in 48.5% yield (Scheme 1A, further details in supporting information).…”

Section: Synthesis Of the Porphyrin Ligands And Non-radioactive Mn-po...mentioning

confidence: 99%

“…Porphyrin 5 was purchased from Porphychem. Porphyrin 1, 2, 3 and 6 were obtained using previously described methodologies and characterization data in good agreement [28][29][30][31]. The following chemicals were purchased from Fisher Scientific:trifluoroacetic acid (TFA), acetonitrile (AcN), chloroform (CHCl3), ethyl acetate (EtOAc), ethanol (EtOH), dimethylformamide (DMF).…”

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confidence: 99%

Microwave-assisted radiolabelling of 52Mn-porphyrins: applications in cell and liposome radiolabelling

Gawne

Pinto

Nielsen

et al. 2022

Preprint

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Manganese porphyrins have several therapeutic/imaging applications, including their use as radioprotectants (in clinical trials) and as paramagnetic MRI contrast agents. The affinity of porphyrins for lipid bilayers also makes them candidates for cell/liposome labelling. We hypothesised that metalation with the positron emission tomography (PET) radionuclide 52Mn (t1/2 = 5.6 d) would allow long-term in vivo biodistribution studies of Mn-porphyrins as well as a method to label and track cells/liposomes, but methods for fast and efficient radiolabelling are lacking. Several porphyrins were produced and radiolabelled by addition to neutralised [52Mn]MnCl2 and heated using a microwave (MW) synthesiser and compared with non-MW heating. MW radiosynthesis allowed >95 % radiochemical yields (RCY) in just 1 h. Conversely, non-MW heating at 70 oC for 1 h resulted in low RCY (0 – 25 % RCY) and most porphyrins did not reach radiolabelling completion after 24 h. Formation of the 52Mn-complexes were confirmed with radio-HPLC by comparison with their non-radioactive 55Mn counterparts. Following this, several 52Mn-porphyrins were used to radiolabel liposomes resulting in 75 – 86 % labelling efficiency (LE). Two lead 52Mn-porphyrins were taken forward to label MDA-MB-231 cancer cells in vitro, achieving ca. 11 % LE. After 24 h, 32 – 45 % of the 52Mn-porphyrin was retained in cells. In contrast to standard methods, MW heating allows the fast synthesis of 52Mn-porphyrins with >95% radiochemical yields that avoid purification. 52Mn-porphyrins also show promising cell/liposome labelling properties. Our reported technique can potentially be exploited for the in vivo imaging of Mn-porphyrin therapeutics, as well as for the accurate in vivo quantification of Mn-porphyrin MRI agents.

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“…After work-up, all starting porphyrins were obtained in yields similar to those found in literature. 27,28 Then, in the case of porphyrin 1, nucleophilic substitution with polyethylene glycol group was achieved by reacting the starting porphyrin with one equivalent of PEG500, DMF as solvent, NaH as base at 80ºC. The progress of the reaction was performed via TLC and the reaction was stopped after 48 h. After purification using aluminium oxide column chromatography, porphyrin 1 was obtained in 48.5% yield (Scheme 1A, further details in supporting information).…”

Section: Synthesis Of the Porphyrin Ligands And Non-radioactive Mn-porphyrinsmentioning

confidence: 99%

Microwave-assisted radiolabelling of 52Mn-porphyrins

Gawne

Pinto

Nielsen

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

Manganese porphyrins have several therapeutic/imaging applications; including their use as radioprotectants (in clinical trials), and as paramagnetic MRI contrast agents. The affinity of porphyrins for lipid bilayers also makes them candidates for cell/liposome labelling. We hypothesised that metalation with the positron emission tomography (PET) radionuclide 52Mn (t1/2 = 5.6 d) would allow long-term in vivo biodistribution studies of Mn-porphyrins as well as a method to label and track cells/liposomes, but methods for fast and efficient radiolabelling are lacking. Several porphyrins were produced and radiolabelled by addition to neutralised [52Mn]MnCl2 and heated at 165 oC for 1 h using a microwave (MW) synthesiser at a ligand concentration of 0.6 – 0.7 mM. These conditions were compared with non-MW heating at 70oC. MW radiosynthesis allowed >95 % radiochemical yields (RCY) in just 1 h. Conversely, non-MW heating at 70 oC for 1 h resulted in low RCY (0 – 25 % RCY) and most porphyrins did not reach completion after 24h. Formation of the 52Mn-complexes were confirmed with radio-HPLC by comparison with their non-radioactive 55Mn counterparts. Following this, several 52Mn-porphyrins were used to radiolabel liposomes by incubation at 50 oC for 30 min resulting in 75 – 86 % labelling efficiency (LE). Two lead 52Mn-porphyrins were taken forward to label MDA-MB-231 cancer cells in vitro, achieving ca. 11 % LE. After 24 h, 32 – 45 % of the 52Mn-porphyrin was retained in cells. In contrast to standard methods, MW heating allows fast synthesis of 52Mn-porphyrins with >95% radiochemical yields that avoid purification. 52Mn-porphyrins also show promising cell/liposome labelling properties. This technique can potentially be exploited for the in vivo imaging of Mn-porphyrin therapeutics, as well as for the accurate in vivo quantification of Mn-porphyrin MRI agents.

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Nitrobenzene method: A keystone in meso-substituted halogenated porphyrin synthesis and applications

Cited by 11 publications

References 120 publications

Main Strategies for the Synthesis of meso-Arylporphyrins

Main Strategies for the Synthesis of meso-Arylporphyrins

Microwave-assisted radiolabelling of 52Mn-porphyrins: applications in cell and liposome radiolabelling

Microwave-assisted radiolabelling of 52Mn-porphyrins

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