15921-15-0

Usage

InChI:InChI=1/2C4H9O.Mg/c2*1-2-3-4-5;/h2*2-4H2,1H3;/q2*-1;+2

Upstream product

• 3739-64-8 allyl n-butyl ether 
• 71-36-3 butan-1-ol 
• 109-88-6 magnesium methanolate 
• 7439-95-4 magnesium 
• 36826-86-5 Mg⁽¹⁺⁾-tetrahydrofuran 
• 35754-82-6 Mg(n-PrOH)⁽¹⁺⁾ 
• 15571-48-9 Mg(i-PrOH)⁽¹⁺⁾ 
• 75-21-8 oxirane 
• 109-99-9 tetrahydrofuran 

Downstream Products

• 3739-64-8 allyl n-butyl ether 
• 35754-82-6 Mg(n-PrOH)⁽¹⁺⁾ 
• 71-36-3 butan-1-ol 
• 15571-48-9 Mg(i-PrOH)⁽¹⁺⁾ 
• 36826-86-5 Mg⁽¹⁺⁾-tetrahydrofuran 
• 588-67-0 benzyl 1-butyl ether 
• 1448239-43-7 [5,6,8,9,11,12-hexakis(4-tert-butylphenyl)[1,2,5]-selenadiazolo[3,4-b]porphyrazinato]magnesium 

Relevant academic research and scientific papers

Synthesis and photochemical properties of unsymmetrical phthalocyanine bearing two 1-adamantylsulfanyl groups at adjacent peripheral positions

A novel unsymmetrical magnesium(II) 2,3-bis(1-adamantylsulfanyl) phthalocyanine was prepared by mixed macrocyclization reaction of two phthalonitriles (phthalonitrile and 4,5-bis(1-adamantylsulfanyl)phthalonitrile) and characterized using UV-vis, MALDI MS and NMR methods. Precursor adamantyl disubstituted phthalonitrile was synthesized from 4,5-dichlorophthalonitrile. Absorption and emission properties of this novel phthalocyanine were investigated, including determination of fluorescence quantum yields, fluorescence lifetimes and solvatochromic effects. This newly synthesized phthalocyanine can be considered as a potential photosensitizer, as its singlet oxygen quantum yield (ΦΔ) of 0.49 was found in DMF and DMSO.

Tetra(3,4-pyrido)porphyrazines Caught in the Cationic Cage: Toward Nanomolar Active Photosensitizers

Investigation of a series of tetra(3,4-pyrido)porphyrazines (TPyPzs) substituted with hydrophilic substituents revealed important structure-activity relationships for their use in photodynamic therapy (PDT). Among them, a cationic TPyPz derivative with total of 12 cationic charges above, below and in the plane of the core featured a unique spatial arrangement that caught the hydrophobic core in a cage, thereby protecting it fully from aggregation in water. This derivative exhibited exceptionally effective photodynamic activity on a number of tumor cell lines (HeLa, SK-MEL-28, A549, MCF-7) with effective concentrations (EC50) typically below 5 nM, at least an order of magnitude better than the EC50 values obtained for the clinically approved photosensitizers verteporfin, temoporfin, protoporphyrin IX, and trisulfonated hydroxyaluminum phthalocyanine. Its very low dark toxicity (TC50 > 400 μM) and high ability to induce photodamage to endothelial cells (EA.hy926) without preincubation suggest the high potential of this cationic TPyPz derivative in vascular-targeted PDT.

Highly symmetrical polyfluorinated porphyrazines

By cyclotetramerization of 2,3-bis[2-fluoro-5-(trifluoromethyl)benzylthio] maleonitrile in the presence of magnesium butanolate, magnesium porphyrazinate carrying eight (2-fluoro-5-(trifluoromethyl)benzylthio) functional groups on the periphery positions

Synthesis and characterization of μ-nitrido, μ-carbido and μ-oxo dimers of iron octapropylporphyrazine

Three μ-X bridged diiron octapropylporphyrazine complexes having FeIII-O-FeIII, Fe+3.5-N=Fe+3.5 and FeIV=C=FeIV structural units have been prepared and characterized by UV-vis, EPR, X-ray absorption spectroscopy and electrochemical methods. Single crystals of all the complexes were obtained from benzene-acetonitrile and their structures were determined by X-ray diffraction. In contrast to μ-oxo complex (6), μ-nitrido (7) and μ-carbido (8) dimers crystallized with one benzene molecule per two binuclear complex molecules arranged cofacially to the porphyrazine planes at Fe-Cbenzene distances of 3.435-3.725 A and 3.352-3.669 A for 7 and 8, respectively. The short distances suggest an interaction between the iron sites and the benzene π-system which is stronger in the case of the FeIV=C=FeIV unit with a higher Lewis acidity. The Fe-X-Fe angle increases in the sequence 6-7-8 from 158.52° to 168.5° and 175.10°, respectively, in agreement with the Fe-X bond order. However, the lengths of the Fe-X bonds do not follow this trend: Fe-O = 1.75/1.76 A > Fe-C = 1.67/1.67 A > Fe-N = 1.65/1.66 A indicating unexpectedly long Fe-C bonds. This observation can be explained by back π-donation from the μ-carbido ligand to the Fe-C antibonding orbital thus decreasing the bond order which is confirmed by DFT calculations.

New soluble porphyrazine derivatives containing electron-rich substituents

Hydroxypropylsulfanyl groups of metal-free and metallo-porphyrazines (M=2H, Mg, Cu, Zn, or Co) have been prepared by the esterification with a carboxylate such as 1-naphthoic acid. The symmetrically functionalized porphyrazines with eight ester units were soluble in common organic solvents such as CHCl 3, CH2Cl2, tetrahydrofuran, acetone, and toluene and insoluble in water and n-hexane. The compounds have been characterized by FT-IR, UV-Vis, mass, 1H, 13C NMR, and elemental analysis.

First example of an octa-glycoconjugated magnesium(II)porphyrazine

Treatment of disodium maleonitriledithiolate with 1,2:3,4-di-O-isopropylidene-6-O-trifluoromethanesulfonyl-α-d-galactopyranose gives 2,3-bis(6-deoxy-1,2:3,4-di-O-isopropylidene-6-thio-α-d-galactopyranos-6-yl)maleonitrile in 87% yield. Heating of the latter with magnesium bis(butan-1-olate) in butan-1-ol affords [2,3,7,8,12,13,17,18-octakis(6-deoxy-1,2:3,4-di-O-isopropylidene-6-thio-α-d-galactopyranos-6-yl)porphyrazinato]magnesium(II) in 53% yield. The glycoconjugated porphyrazine has an absorbance maximum at 673 nm and is a candidate as photosensitizer for photodynamic therapy.

Synthesis and characterization of a β-fused tetraporphyrin-phthalocyanine star-shaped array

A star-shaped array, consisting in four tetraphenylporphyrin fused to a phthalocyanine central unit by pyrazine groups, is constructed via the condensation reaction of a dicyanoquinoxaline annulated to a porphyrin ring. The nature of the annulated group is critical for the success of the reaction; in the case of smaller linkers, such as a dicyanopyrazine unit, a nucleophilic substitution occurred, giving the corresponding alcoxy derivative in alcoholic solvents. The visible spectrum of the array shows the typical absorptions of the macrocyclic sub units. The synthetic pathway here presented opens the way to the preparation of β-fused porphyrin-phthalocyanine arrays.

Synthesis, structural and spectral properties of novel octakis(3,5-bis- trifluoromethyl-benzylthio) substituted porphyrazine derivatives

[Octakis(3,5-bis-trifluoromethyl-benzylthio)porphyrazinato] magnesium carrying eight (3,5-bis-trifluoromethyl-benzylthio) groups on the peripheral positions have been synthesized by cyclotetramerization of 1,2-bis(3,5-bis- trifluoromethyl-benzylthio)maleonitrile in the presence of magnesium butanolate. Its demetalation by the treatment with trifluoroacetic acid resulted in the metal-free derivative. Further reaction of this product with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate have led to the metallo derivatives M = Cu(II), Zn(II), Co(II). These novel complexes were characterized by elemental analysis, together with FT-IR, 1H NMR, 13C NMR, 19F NMR, UV-vis and mass spectral data.

1,2,5-chalcogenadiazole-annulated tripyrazinoporphyrazines: Synthesis, spectral characteristics, and influence of the heavy atom effect on their photophysical properties

A series of low-symmetry ZnII, MgII, and metal-free porphyrazine derivatives with one 1,2,5-chalcogenadiazole ring (with S, Se or Te) and three pyrazines bearing tert-butylsulfanyls were synthesized. The absorption maxima of ZnII complexes lay at 660, 674, and 707 nm for S, Se, and Te, respectively, indicating increasing contribution of the 1,2,5-chalcogenadiazole rings to the π-electronic system. Photophysical studies revealed that introduction of Se as a chalcogen and ZnII as a central metal causes an increase in the singlet oxygen quantum yield, reaching a value of 0.81, whereas the combination of S and MgII gives only 0.39. This takes place on the account of the fluorescence quantum yields that differ significantly from 0.072 (ZnII+Se) to 0.51 (MgII+S). These results demonstrated the two-dimensional heavy atom effect combining the role of the chalcogen (first dimension) as well as the central metal (second dimension). Attempts to prepare oxygen-containing isologues led to the formation of an unexpected side product.

Sulfanyl porphyrazines with morpholinylethyl periphery—synthesis, electrochemistry, and photocatalytic studies after deposition on titanium(Iv) oxide p25 nanoparticles

The syntheses, spectral UV–Vis, NMR, and electrochemical as well as photocatalytic properties of novel magnesium(II) and zinc(II) symmetrical sulfanyl porphyrazines with 2-(morpholin-4-yl)ethylsulfanyl peripheral substituents are presented. Both porphyrazine derivatives were synthe-sized in cyclotetramerization reactions and subsequently embedded on the surface of commercially available P25 titanium(IV) oxide nanoparticles. The obtained macrocyclic compounds were broadly characterized by ESI MS spectrometry, 1D and 2D NMR techniques, UV–Vis spectroscopy, and subjected to electrochemical studies. Both hybrid materials, consisting of porphyrazine derivatives embedded on the titanium(IV) oxide nanoparticles’ surface, were characterized in terms of particle size and distribution. Next, they were subjected to photocatalytic studies with 1,3-diphenylisobenzofuran, a known singlet oxygen quencher. The applicability of the obtained hybrid material consisting of titanium(IV) oxide P25 nanoparticles and magnesium(II) porphyrazine derivative was assessed in photocatalytic studies with selected active pharmaceutical ingredients, such as diclofenac sodium salt and ibuprofen.