Vilsmeier-Haack formylation of <font>Cu(II)</font> and <font>Ni(II)</font> porphyrin complexes under microwaves irradiation

Moura, Nuno M. M.; Faustino, Maria A. F.; Neves, Maria G. P. M. S.; Duarte, Armando C.; Cavaleiro, José A. S.

doi:10.1142/s1088424611003586

Cited by 21 publications

(12 citation statements)

References 14 publications

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“…2-Formyl-5,10,15,20-tetraphenylporphyrin ( 1 ) was prepared from 5,10,15,20-tetraphenylporphyrinatocopper(II), phosphorus oxychloride and DMF, according to a well established procedure [ 54 ].…”

Section: Methodsmentioning

confidence: 99%

Cationic Pyrrolidine/Pyrroline-Substituted Porphyrins as Efficient Photosensitizers against E. coli

et al. 2021

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New porphyrin–pyrrolidine/pyrroline conjugates were prepared by revisiting 1,3-dipolar cycloaddition reactions between a porphyrinic azomethine ylide and a series of dipolarophiles. Cationic conjugates obtained by alkylation of the pyrrolidine/pyrroline cycloadducts showed ability to generate singlet oxygen and to produce iodine in presence of KI when irradiated with visible light. Some of the cationic derivatives showed photobactericidal properties towards a Gram-negative bioluminescent E. coli. In all cases, these features were significantly improved using KI as coadjutant, allowing, under the tested conditions, the photoinactivation of the bacterium until the detection limit of the method with a drastic reduction of the required photosensitizer concentration and irradiation time. The obtained results showed a high correlation between the ability of the cationic porphyrin derivative to produce singlet oxygen and iodine and its E. coli photoinactivation profile.

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Section: Methodsmentioning

confidence: 99%

Cationic Pyrrolidine/Pyrroline-Substituted Porphyrins as Efficient Photosensitizers against E. coli

et al. 2021

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“…The access to the new neutral porphyrins 1b and 1c bearing the terpyridine units in the b-pyrrolic positions involved the Kröhnke type approach described previously for the synthesis of porphyrin 1a. 35 In this methodology the terpyridine moiety was built directly from the easy accessible 2-formyl-5,10,15,20-porphyrin (TPP-CHO) 36 by reaction with 2-acetylpyridine (5 equiv.) in the presence of ammonium acetate (8 equiv.…”

Section: Synthesis Of Neutral Derivativesmentioning

confidence: 99%

Synthesis, characterization and biological evaluation of cationic porphyrin–terpyridine derivatives

et al. 2016

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in the beta-pyrrolic positions; the results already obtained show that this type of PSs is also very promising.This fact, and our nding of an easy synthesis for porphyrin 1a (see Fig. 1) bearing a terpyridine unit in the beta pyrrolic position, 35 prompted us to expand the studies to the syntheses of the analogues 1b and 1c in order to use them as templates for further cationization. So, herein, we report the synthesis and the characterization of a series of neutral and cationic porphyrins bearing terpyridine units in one of their beta-pyrrolic positions. In the course of the characterization of these compounds we found that isomer differentiation of the cationic compounds could be easily achieved by ESI-MS (electrospray mass spectrometry).Additionally, their efficacy on the photoinactivation of bioluminescent E. coli was evaluated. The bioluminescent genetically transformed E. coli was selected as a model of Gramnegative bacteria to monitor in real-time photodynamic inactivation through bioluminescence measurement, thus avoiding the laborious and time-consuming conventional method of counting colony-forming units. Results and discussion Synthesis of neutral derivativesThe synthetic strategy to obtain the new b-pyrrolic cationic derivatives 6 and 7 (see Scheme 2) required the previous preparation of the corresponding neutral derivatives according with experimental work summarized in Scheme 1. The access to the new neutral porphyrins 1b and 1c bearing the terpyridine units in the b-pyrrolic positions involved the Kröhnke type approach described previously for the synthesis of porphyrin 1a. 35 In this methodology the terpyridine moiety was built directly from the easy accessible 2-formyl-5,10,15,20-porphyrin (TPP-CHO) 36 by reaction with 2-acetylpyridine (5 equiv.) in the presence of ammonium acetate (8 equiv.) and La(OTf) 3 (20 mol%).35 The procedure led to compound 1a in good yield (45%) affording as minor compounds the benzoporphyrin 2a (29%) and the porphyrin-chalcone 3a (10%) ( Table 1, entry 1).Based on that synthetic strategy we envisaged, just by changing the 2-acetylpyridine by the adequate 3-and 4-acetylpyridine the syntheses of the new neutral terpyridine derivatives 1b and 1c.In order to force the formation of the desired terpyridine 1a, the reaction was repeated in the presence of 2-acetylpyridine during 4 h. The results summarized in Table 1 (entry 2) show that the expected derivatives 1a, 2a and 3a were isolated in yields similar to our previously used conditions. However, a careful analysis of TLC data allowed us to detect a minor and more polar red product. Aer purication, the structure of this product, obtained in 4% yield, was established based on spectroscopic data (see infra and also ESI †) as the new 2-(2,4-diarylpyridin-6-yl)-5,10,15,20-tetraphenylporphyrin 4 (Fig. 2).Attempts to improve compound 4 yield by increasing the reaction time were not successful. The formation of the new derivative 4 can be explained in a similar manner as the one proposed for derivative 1a, 35 using as template...

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“…Synthetic methods for the chemical modification of porphyrins are well established in the literature and enable access to a wide variety of derivatives which can be utilized for biological and material applications. − Of recent special interest is the synthesis of “push–pull” porphyrins − with multiple electrophilic substituents at the β-pyrrole positions which have been examined for use in nonlinear optics, photodynamic therapy (PDT), , and dye-sensitized solar cells (DSSC). , …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Electrochemical Characterization of Acetylacetone (acac) and Ethyl Acetate (EA) Appended β-Trisubstituted Push–Pull Porphyrins: Formation of Electronically Communicating Porphyrin Dimers

et al. 2018

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Two new families of “push–pull” tetraphenylporphyrins with one acetylacetone (acac) or ethyl acetate (EA) moiety at a β-pyrrole position of the macrocycle and two Br or Ph substituents at the antipodal β-positions were synthesized and structurally, spectroscopically, and electrochemically characterized. The examined porphyrins are represented as MTPP(R)2acac and MTPP(R)2EA (where R = Br or Ph and M = H2, Co, Ni, Cu, or Zn). NiTPP(Br)2acac exhibits an extremely nonplanar conformation (Δ24 = 0.44 Å, ΔCβ = 0.82 Å), while H2TPP(Br)2EA and ZnTPP(Ph)2EA exhibit a quasi-planar conformation. All of the synthesized acac-appended porphyrins show a keto–enol tautomerism in solution, which results in formation of hydrogen bonded dimers as evidenced by 1H NMR and mass spectrometry. Dimers were also detected under the electrochemical conditions for the dibromo derivatives but not the diphenyl substituted porphyrins. A facile stepwise and reversible electrogeneration of the electronically communicating porphyrin dimers is observed for MTPP(Br)2acac where M = CuII, NiII, or ZnII.

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Vilsmeier-Haack formylation of Cu(II) and Ni(II) porphyrin complexes under microwaves irradiation

Cited by 21 publications

References 14 publications

Cationic Pyrrolidine/Pyrroline-Substituted Porphyrins as Efficient Photosensitizers against E. coli

Cationic Pyrrolidine/Pyrroline-Substituted Porphyrins as Efficient Photosensitizers against E. coli

Synthesis, characterization and biological evaluation of cationic porphyrin–terpyridine derivatives

Synthesis and Electrochemical Characterization of Acetylacetone (acac) and Ethyl Acetate (EA) Appended β-Trisubstituted Push–Pull Porphyrins: Formation of Electronically Communicating Porphyrin Dimers

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