- Isomers of β,β-Dinitro-5,10,15,20-tetraphenylporphy-rin Derivatives: Valuable starting materials for further transformations
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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.
- Mikus, Agnieszka,Rosa, Mariusz,Ostrowski, Stanis?aw
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- Expanding the light absorption of poly(3-hexylthiophene) by end-functionalization with π-extended porphyrins
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Poly(3-hexylthiophene)s end-functionalized with π-extended porphyrins have been synthesized in a one-pot procedure. The polymers show a broad absorption profile extending to 700 nm and a fibrillar microstructure, which can be tuned through judicious selection of the porphyrin molar ratio.
- Chevrier, Michèle,Richeter, Sébastien,Coulembier, Olivier,Surin, Mathieu,Mehdi, Ahmad,Lazzaroni, Roberto,Evans, Rachel C.,Dubois, Philippe,Clément, Sébastien
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supporting information
p. 171 - 174
(2015/12/26)
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- Selective formation of either Tr?ger's base or spiro Tr?ger's base derivatives from [2-aminoporphyrinato(2-)]nickel by choice of reaction conditions
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The article reports on the unique manipulation of the acid-catalyzed reaction of [2-aminoporphyrinato(2-)]nickel with formaldehyde to form selectively either the symmetric Tr?ger's base or the asymmetric spiro Tr?ger's base bis(metalloporphyrin) derivativ
- Tatar, Ameneh,Dolensky, Bohumil,Dvo?áková, Hana,Král, Vladimír
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supporting information
p. 6015 - 6017
(2013/01/13)
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- Diporphyrinylamines: Synthesis and electrochemistry
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The synthesis of three possible diporphyrinylamines is described. All compounds were obtained by using the Buchwald-Hartwig aromatic amination reaction. The electronic spectra of the three porphyrin dimers showed characteristic features found in highly de
- Pereira, Ana M. V. M.,Neves, Maria G. P. M. S.,Cavaleiro, Jose A. S.,Jeandon, Christophe,Gisselbrecht, Jean-Paul,Choua, Sylvie,Ruppert, Romain
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supporting information; experimental part
p. 4742 - 4745
(2011/10/18)
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- Unexpected hydroxylamine-induced ring-closure reactions of meso-tetraphenylsecochlorin bisaldehyde
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Reaction of meso-tetraphenylsecochlorin bisaldehyde with hydroxylamine results in the formation of the known meso-tetraphenyl-2-nitroporphyrin and the novel meso-tetraphenylimidazolophorphyrin. The products are the result of two diverging pathways of the presumed intermediate monooxime monoaldehyde that are unusual and surprising, but fully rationalized. The structures of both products were confirmed by spectroscopic techniques and single crystal X-ray diffractometry. This reaction represents the first reaction in which a pyrrole in a porphyrin was formally replaced by an imidazole moiety. The optical properties of the free base and metalloimidazoloporphyrin under neutral and acidic conditions are discussed. Further, an alternative synthesis of the imidazoloporphyrin Ni(ii) based on meso-tetraphenyl-1-formyl-chlorophin is presented.
- Akhigbe, Joshua,Peters, Gretchen,Zeller, Matthias,Brueckner, Christian
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p. 2306 - 2313
(2011/05/02)
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- Porphyrin anchoring on Si(100) using a β-pyrrolic position
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Nickel(ii) β-azido-meso-tetraphenylporphyrin was successfully anchored on silicon using a bifunctional linker that bears two terminal alkyne functions by the sequence (i) hydrosilylation of a CC triple bond of the linker by surface Si-H groups and (ii) 1,
- Liu, Hui,Duclairoir, Florence,Fleury, Benoit,Dubois, Lionel,Chenavier, Yves,Marchon, Jean-Claude
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scheme or table
p. 3793 - 3799
(2009/09/26)
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- Synthesis of New Porphyrins with Peripheral Conjugated Chelates and Their Use for the Preparation of Porphyrin Dimers Linked by Metal Ions
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This article describes the preparation of several new porphyrins bearing chelating peripheral groups fully conjugated with the macrocyclic π-system. Treatment of a 2-nitro-meso-tetraarylporphydn with phosphite gave a cyclic enamine, whose formylation gave an enaminoaldehyde. The thio analogue was obtained on treatment with Lawesson's reagent. The same reagent was also used to obtain the isomeric thioenaminoketone chelates. A enaminoketone ligand was prepared from a porphyrinic pyrrolone. All these ligands, as internal nickel complexes, could be metalated with palladium to yield porphyrinic dimers. The dimers obtained from enaminoketones and thioketones show a trans geometry, while in the enaminoaldehyde and -thioaldehyde series the cis isomer is thermodynamically favored. The bathochromic shifts of the electronic spectra of the aldehyde-derived dimers illustrate the strong electronic effect of peripheral metalation and dimerization. However, in the case of the pyrrolone-derived ligand, opposite effects were observed, due to partial reconstitution of the porphyrin chromophore on complexation. As with the dimers derived from enaminoketones, the dimers derived from the new ligands show typical splitting (up to 190 mV) of the electrochemical waves confirming large porphyrin-porphyrin interactions.
- Richeter, Sebastien,Jeandon, Christophe,Gisselbrecht, Jean-Paul,Graff, Roland,Ruppert, Romain,Callot, Henry J.
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p. 251 - 263
(2008/10/09)
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- Control of Reactivity at the Porphyrin Periphery by Metal Ion Co-ordination: a General Method for Specific Nitration at the β-Pyrrolic Position of 5,10,15,20-Tetraarylporphyrins
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The site of nitration by nitrogen dioxide on a range of metalloporphyrins has been found to be dependent on the co-ordinated metal; copper(II), nickel(II), and palladium(II) complexes are nitrated specifically on the porphyrin β-pyrrolic position while magnesium(II), zinc(II), chloroiron(III), and cobalt(II) complexes also give products which result from reaction at the meso-position.
- Catalano, Maria M.,Crossley, Maxwell J.,Harding, Margaret M.,King, Lionel G.
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p. 1535 - 1536
(2007/10/02)
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