Synthesis of 2,7,12,17-tetraphenylporphycene (TPPo). First aryl-substituted porphycene for the photodynamic therapy of tumors

Nonell, Santi; Bou, Núria; Borrell, José I.; Teixidó, Jordi; Villanueva, Ángeles; Juarranz, Ángeles; Cañete, Magdalena

doi:10.1016/0040-4039(95)00493-v

Cited by 64 publications

(44 citation statements)

References 12 publications

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“…Finally, dialdehyde 10 was converted to TPPo (2e) by using activated zinc, copper(I) chloride and titanium tetrachloride in tetrahydrofuran (THF) in 30% yield [7].…”

Section: Resultsmentioning

confidence: 99%

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A non-tetradecarboxylative synthesis of 2,7,12,17-tetraphenylporphycene

Gavalda

Borrell

Teixidó

et al. 2001

J. Porphyrins Phthalocyanines

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ABSTRACT:A new synthetic method for 2,7,12,17-tetraphenylporphycene (2e, TPPo) which avoids tetradecarboxylation by sublimation of the intermediate tetracarboxylic acid 8 is reported. Thus, the use of a pyrrol 13a bearing two orthogonal ester groups allows the synthesis of bipyrrol 12a, from which the benzyl ester groups are selectively removed to afford diester 11. The latter is transformed to dialdehyde 10 by using the McFayden-Stevens reaction, thus avoiding the unstable bipyrrol 9 formed during the tetradecarboxylation of 8.

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“…Finally, dialdehyde 10 was converted to TPPo (2e) by using activated zinc, copper(I) chloride and titanium tetrachloride in tetrahydrofuran (THF) in 30% yield [7].…”

Section: Resultsmentioning

confidence: 99%

“…Thus, in 1995, our group described the synthesis of TPPo [7] simultaneously to the presentation of a doctoral thesis by Hennig, Vogel's co-worker, in which the same compound was described [8]. The synthetic paths employed have several points in common, as can be seen in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

A non-tetradecarboxylative synthesis of 2,7,12,17-tetraphenylporphycene

Gavalda

Borrell

Teixidó

et al. 2001

J. Porphyrins Phthalocyanines

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“…Two main strategies (Scheme 1) have been devised to obtain the precursor 5,5'-diacyl substituted 2,2'-bipyrroles (2): acylation (Y=alkyl group) [85,123] (or formylation, Y=H) [62,66,124,125] of an adequately 4,4'-disubstituted or 3,3',4,4'-tetrasubstituted 2,2'-bipyrrole (3 or 4, respectively), in one side, or transformation of 2,2'-bypyrroles bearing two latent formyl groups to aldehydes 2 (Y=H), two ester groups in the case of 5 [126] or two 4,4,6-trimethyl-1,3-dioxan-2-yl groups in the case of 6 (G=C 7 H 13 O 2 ), on the other side [127].…”

Section: The Ideal Pdt Sensitizermentioning

confidence: 99%

“…The absence of a stabilizing carbonyl group in positions C5 and C5' of compounds 3 and 4 makes these compounds prone to oxidation by atmospheric oxygen. The subsequent acylation (Y=alkyl) [85,123] or formylation (Y=H) [62,66,124,125] of 3 and 4 using the Vilmeier-Hack protocol (YCONMe 2 /POCl 3 ) finally yields 5,5'-diacyl (Y=alkyl) and 5,5'-diformyl substituted (Y=H) 2,2'-bipyrroles (2), which are the immediate precursors of 2,7,12,17-tetrasubstituted porphycenes (1, Y=H, R 2 =H), 2,3,6,7,12,13,16,17-octasubstituted porphycenes (1, Y=H) and 9,10,19,20-tetrasubstituted porphycenes (1, R 1 =R 2 =H). This methodology has been claimed to be of general applicability, and several patents [129][130][131][132][133][134][135][136] have been filed covering a wide range of substituents R 1 , R 2 , and Y.…”

Section: The Ideal Pdt Sensitizermentioning

confidence: 99%

“…2), which results in 20-fold larger absorption coefficients in the red part of the spectrum. Several 2,7,12,17-tetraalkyl-substituted porphycenes (e.g., methyl, ethyl, n-propyl, methoxyethyl) [63][64][65], as well as the tetraphenyl derivative (TPPo) [66][67][68] and its palladium(II) complex (PdTPPo) [69][70][71] were found to be photoactive and to induce efficient cell damage in vitro and in vivo [64,[72][73][74][75]. This review aims to summarize the chemistry of porphycenes, and their photophysical and biological properties for PDT applications.…”

Section: Introductionmentioning

confidence: 99%

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Porphycenes: Facts and Prospects in Photodynamic Therapy of Cancer

Stockert¹,

Cañete²,

Juarranz³

et al. 2007

CMC

177

130

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The photodynamic process induces cell damage and death by the combined effect of a photosensitizer (PS), visible light, and molecular oxygen, which generate singlet oxygen ((1)O(2)) and other reactive oxygen species that are responsible for cytotoxicity. The most important application of this process with increasing biomedical interest is the photodynamic therapy (PDT) of cancer. In addition to hematoporphyrin-based drugs, 2nd generation PSs with better photochemical properties are now studied using cell cultures, experimental tumors and clinical trials. Porphycene is a structural isomer of porphyrin and constitutes an interesting new class of PS. Porphycene derivatives show higher absorption than porphyrins in the red spectral region (lambda > 600 nm, epsilon > 50000 M-(1)cm(-1)) owing to the lower molecular symmetry. Photophysical and photobiological properties of porphycenes make them excellent candidates as PSs, showing fast uptake and diverse subcellular localizations (mainly membranous organelles). Several tetraalkylporphycenes and the tetraphenyl derivative (TPPo) induce photodamage and cell death in vitro. Photodynamic treatments of cultured tumor cells with TPPo and its palladium(II) complex induce cytoskeletal changes, mitotic blockage, and dose-dependent apoptotic or necrotic cell death. Some pharmacokinetic and phototherapeutic studies on experimental tumors after intravenous or topical application of lipophilic alkyl-substituted porphycene derivatives are known. Taking into account all these features, porphycene PSs should be very useful for PDT of cancer and other biomedical applications.

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Cu,Ni, andPdMediated Homocoupling Reactions in Biaryl Syntheses: TheUllmann Reaction

Nelson

Crouch

2004

Organic Reactions

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The traditional Ullman reaction is the homocoupling of aromatic halides mediated by copper at elevated temperatures. Ullman first reported this reaction in 1901. Although the coupling conditions first reported are still widely used, a host of modifications have been made to these reactions. Some of these modifications include the use of activated and alternative metals, often resulting in much lower coupling temperatures. Nickel and palladium are the most utilized source of alternative metals, Periodic reviews have been published. This chapter covers the literature on copper, nickel, and palladium mediated homocoupling reactions in biaryl synthesis from 1901 to 2000. The focus of this chapter is the scope and limitation of these processes, preparation of the activated metal, and mechanism of the homocoupling process

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Synthesis of 2,7,12,17-tetraphenylporphycene (TPPo). First aryl-substituted porphycene for the photodynamic therapy of tumors

Cited by 64 publications

References 12 publications

A non-tetradecarboxylative synthesis of 2,7,12,17-tetraphenylporphycene

A non-tetradecarboxylative synthesis of 2,7,12,17-tetraphenylporphycene

Porphycenes: Facts and Prospects in Photodynamic Therapy of Cancer

Cu,Ni, andPdMediated Homocoupling Reactions in Biaryl Syntheses: TheUllmann Reaction

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