Über Rhodine und Verdine

Fischer, Herbert; Treibs, Alfred; Helberger, H.

doi:10.1002/jlac.19284660115

Cited by 34 publications

(5 citation statements)

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“…Now phylloerythrin is a porphyrin (22), on the grounds of its spectroscopic behavior. Thus for the first time a basis was obtained for the view that the chlorophyll molecule also stood in close relation to the porphyrins; a possibility further supported by synthetic studies through conversion of blood pigment porphyrins into chlorins and rhodins (55,17,12). By bacteriological methods (19,20) chlorophyll derivatives were likewise converted into porphyrins, again a confirmation of the relations stated above.…”

Section: H3cfi-cjh6supporting

confidence: 55%

Chlorophyll.

Fischer¹

1937

Chem. Rev.

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Section: H3cfi-cjh6supporting

confidence: 55%

Chlorophyll.

Fischer¹

1937

Chem. Rev.

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“…Indeed, a review on chlorin chemistry written 40 years ago would have included only a handful of pyrroline motifs (Scheme ). The history of chlorin synthetic chemistry now spans a saeculum, given Fischer’s work as a reasonable point of inception, ,, and the present review shows a remarkable and almost bewildering assortment of pyrroline motifs and synthetic approaches for installation of such motifs in a porphyrin substrate. Still, stepping back from this pointillist survey of the synthesis of >1000 chlorins, it is evident that much remains to be done.…”

Section: Outlook: Synthetic Chlorins As Surrogates For Chlorophyllsmentioning

confidence: 95%

“…Some 30 years ago, Clezy and co-workers commented, “The chemistry of the rhodins and verdins has largely remained untouched since Fischer discovered this class of compound over 50 years ago”. The work by Fischer , on the topic of rhodins and verdins has been reviewed to some extent. , The characteristic structures of a rhodin and a verdin are shown in Scheme , along with two other structures for comparison: the core skeleton of chlorophyll, the 13 1 -oxophorbine, and the porphyrin analogue thereof, the 17,18-didehydro-13 1 -oxophorbine. A verdin has been described as a porphyrin that contains an isocyclic ring but not a reduced ring, yet a rhodin also fits a quite similar description.…”

Section: Annulation By Side-chain Cyclization: Benzochlorinsmentioning

confidence: 99%

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

2016

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Chlorophylls make Earth green, are the central constituents in the engine of photosynthesis, and not surprisingly have garnered immense attention. A chlorin, the core chromophore of a chlorophyll, is a dihydroporphyrin macrocycle that contains one pyrroline ring and three pyrrole rings. The dominant method for the synthesis of chlorins has entailed the derivatization of porphyrins. The present review covers the ostensibly simple conversion of porphyrins, regardless of synthetic or biological origin, to chlorins. The period covered encompasses the entire history since the beginnings of chlorin synthetic chemistry in the early 20th century through 2015. Representative transformations include hydrogenation, cycloaddition, annulation, and diverse "breaking and mending" approaches. Altogether, the synthesis of >1000 chlorins or chlorin-like compounds (containing >50 distinct pyrroline motifs) is described. Such diversity animates the question "what structural features are essential for a chlorin to resemble chlorophyll?" To begin to address the structure-spectrum relationship, > 250 absorption spectra are provided for representative structures. The synthesis and spectral properties of the vast collection of compounds described herein are expected to illuminate the scope to which synthetic chlorins can serve as surrogates for chlorophylls and be exploited in diverse ways.

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“…The most interesting and widely known electrophilic substitution reaction is nitration. Nitration of compounds of the porphyrin series was reported for the first time in [2][3][4]. As a result, mesonitro derivatives were isolated even in reactions with porphyrins having no substituents in the β-positions.…”

mentioning

confidence: 96%

Phenyl-substituted porphyrins: III. Relative reactivity in the nitration reaction

et al. 2010

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Study on the nitration of phenyl-substituted porphyrins showed that protonation of the porphyrin macroring does not affect the relative reactivity of the meso-and β-positions and phenyl groups. * For communication II, see [1].Like other aromatic compounds possessing a closed conjugated π-electron system, porphyrins are capable of reacting with electrophiles to give the corresponding substitution products. The most interesting and widely known electrophilic substitution reaction is nitration. Nitration of compounds of the porphyrin series was reported for the first time in [2][3][4]. As a result, mesonitro derivatives were isolated even in reactions with porphyrins having no substituents in the β-positions. Treatment of porphyrin (I) with a nitrating mixture gives meso-nitroporphyrin (II), and further nitration of the latter yields 5,10-dinitroporphyrin (III) [5]. A mixture of meso-nitro derivatives V-VIII was obtained by nitration of octaethylporphyrin IV [6,7]. First attempts to perform electrophilic nitration of meso-tetraphenylporphyrin IX were unsuccessful. Treatment of IX with a nitrating mixture over a period of 9.5 h resulted in the formation of dihydroxyporphodimethene X, presumably through intermediate ipso-nitration product XI [8] (Scheme 1). Kruper et al. [9] succeeded in nitrating compound IX by treatment of its solution in methylene chloride or chloroform with fuming nitric acid (d = 1.53 g/cm 3 ). The nitration occurred at the para-position of one of phenyl substituents and afforded 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin (XII) (Scheme 2). Further nitration (by increasing the amount of nitrating agent) led to the formation of a 2 : 1 mixture of isomeric 5,10-and 5,15-bis(4-nitrophenyl)-porphyrins XIII and XIV. Prolonged nitration gave 5,10,15-tris(4-nitrophenyl)-20-phenylporphyrin (XV). The nitration of compound IX and its derivatives with various nitrating agents was studied in detail in [10][11][12]. On the basis of the obtained results it was concluded that meso-and β-positions in meso-phenylporphyrins are deactivated toward electrophilic substitution owing to protonation of the inner nitrogen atoms [12]. Compound XVI was not isolated.The goal of the present study was to compare the reactivity of the meso-and β-positions in the porphyrin

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Über Rhodine und Verdine

Abstract: Unter relativ milden Bedingungen hat M 7 i l l s t a t t e r 2 ) aus Phaophytin Rhodine und Chlorine erhalten. Die beiden wichtigsten Vertreter sind Phytochlorin e und Phytorhodin g von der Formel

Cited by 34 publications

References 2 publications

Chlorophyll.

Chlorophyll.

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

Phenyl-substituted porphyrins: III. Relative reactivity in the nitration reaction

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