Fallacinal

Last updated
Fallacinal
Fallacinal.svg
Names
IUPAC name
4,5-Dihydroxy-7-methoxy-9,10-dioxoanthracene-2-carbaldehyde
Other names
  • 2-Anthracenecarboxaldehyde, 9,10-dihydro-4,5-dihydroxy-7-methoxy-9,10-dioxo- 1,8-Dihydroxy-6-methoxy-9,10-dioxo-9,10-dihydroanthracene-3-carbaldehyde
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
  • InChI=1S/C16H10O6/c1-22-8-4-10-14(12(19)5-8)16(21)13-9(15(10)20)2-7(6-17)3-11(13)18/h2-6,18-19H,1H3
    Key: MCPKJGRRWINKOH-UHFFFAOYSA-N
  • COC1=CC2=C(C(=C1)O)C(=O)C3=C(C2=O)C=C(C=C3O)C=O
Properties
C16H10O6
Molar mass 298.250 g·mol−1
Appearanceorange-red needles
Melting point 250–252 °C (482–486 °F; 523–525 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Fallacinal is an organic compound in the structural class of chemicals known as anthraquinones. It is found in many species of the lichen family Teloschistaceae.

Contents

History

In 1936, Japanese chemists Mitizo Asano and Sinobu Fuziwara reported on their investigations into the colour pigments of the lichen Xanthoria fallax (now known as Oxneria fallax ), found growing on the bark of mulberry trees. They isolated a pigment they named fallacin. [1] A few years later Asano and Yosio Arata further purified the crude material from this lichen, ultimately obtaining an orange-yellow compound with a molecular formula of C16H12O6. Using information from additional chemical tests, they proposed a tentative structural formula for fallacin. [2] In 1949, [3] T. R. Seshadri and S. Subramanian described their work with the Indian lichen Teloschistes flavicans , in which they isolated an orange substance they named teloschistin, and which had a structural formula identical to that of fallacin proposed by Asano and Arata years earlier. [4]

In 1956, Takao Murakami reported reexamining the crude pigment obtainable from Xanthoria fallax using Asano's original 1936 procedure. He separated out fallacin from parietin, a co-occurring substance, using several rounds of column chromatography, and showed that Asano's original pigment was actually a combination of two pigments with different melting points, which he designated as fallacin-A and fallacin-B. Murakami determined fallacin-A to have a melting point of 251–252 °C (484–486 °F) and a molecular formula of C16H10O6. He established the structure of the compound synthetically by oxidizing it with chromium trioxide, converting that into its acid chloride, and then performing catalytic reduction on this compound using the Rosenmund reduction followed by deacetylation. The resultant product was confirmed to be identical to fallacin-A, and so he designated this substance as fallacinal. He named fallacin-B as fallacinol, [4] a closely related substance that, because of Seshadri and Subramanian's work, is also known as "teloschistin" in the literature. [5]

Occurrence

Fallacinal was first chemically isolated from Oxneria fallax. Liquen Xanthoria fallax Enfoque 2012-1-21 SierraMadrona.jpg
Fallacinal was first chemically isolated from Oxneria fallax .

Fallacinal occurs in many species of the Teloschistaceae, a large family of mostly lichen-forming fungi. Historically, the substance was most associated with Caloplaca , Teloschistes , and Xanthoria , but these genera have since been subdivided into many smaller, monophyletic genera. [6] The cultivated mycobiont of Xanthoria fallax, grown in isolation with the green algal photobiont , still produces fallacinal. [7]

Yoshio Hirose and colleagues proposed a synthesis of fallacinal in 1982 involving the oxidation of fallacinol (a.k.a. teloschistin). [8]

In 1970, the Swedish chemist Johan Santesson proposed a possible biogenetic relationship between the anthraquinone compounds commonly found in the lichen genus Caloplaca . According to this scheme, emodin is methylated to give parietin, which then undergoes three successive oxidations, sequentially forming fallacinol, fallacinal, and then parietinic acid. [9] A chemosyndrome is a set of biosynthetically related compounds produced by a lichen. In 2002, Ulrik Søchting and Patrik Frödén identified chemosyndrome A, the most common chemosyndrome in the genus Teloschistes and in the entire family Teloschistaceae, which features parietin as the main substance and smaller proportions of fallacinol, fallacinal, parietinic acid, and emodin. [10]

Properties

In its purified form, fallacinal exists as orange-red needles with a melting point of 250–252 °C (482–486 °F). Its ultraviolet spectrum has five peaks of maximum absorption (λmax) at 244, 264, 280, 340, and 425  nm. Its infrared spectrum has three peaks at 1625, 1675, and 1720 cm−1; [5] the first two of these peaks corresponds to the chelated and non-chelated ketones, respectively, while the third peak indicates the aromatic aldehyde grouping. [4]

Related Research Articles

<span class="mw-page-title-main">Teloschistaceae</span> Family of lichen-forming fungi

The Teloschistaceae are a large family of mostly lichen-forming fungi belonging to the class Lecanoromycetes in the division Ascomycota. The family has a cosmopolitan distribution, although its members occur predominantly in temperate regions. Most members are lichens that either live on rock or on bark, but about 40 species are lichenicolous – meaning they are non-lichenised fungi that live on other lichens. Many members of the Teloschistaceae are readily identifiable by their vibrant orange to yellow hue, a result of their frequent anthraquinone content. The presence of these anthraquinone pigments, which confer protection from ultraviolet light, enabled this group to expand from shaded forest habitats to harsher environmental conditions of sunny and arid ecosystems during the Late Cretaceous.

<i>Gyalolechia</i> Genus of lichen-forming fungi

Gyalolechia is a genus of lichen-forming fungi belonging to the family Teloschistaceae. It contains 18 species of crustose lichens.

<i>Athallia</i> Genus of lichens

Athallia is a genus of lichen-forming fungi in the family Teloschistaceae. It was circumscribed in 2013 by Ulf Arup, Patrik Frödén, and Ulrik Søchting, and the type species is Athallia holocarpa. The genus name means "without a thallus".

<i>Igneoplaca</i> Lichen genus

Igneoplaca is a genus in the subfamily Xanthorioideae of the family Teloschistaceae. It contains a single species, the crustose lichen Igneoplaca ignea.

Parvoplaca nigroblastidiata is a species of corticolous (bark-dwelling), crustose lichen in the family Teloschistaceae. Found in Europe and Alaska, it was formally described as a new species in 2015 by Ulf Arup, Jan Vondrák, and Mehmet Halıcı. The type specimen was collected in the Nyhem Parish, Jämtland (Sweden), where it was growing on the bark of Populus tremula. In Turkey, it has been recorded at high altitudes on the bark of Juniperus excelsa and Abies cilicica, while in a single record from Alaska it is growing on Populus. In 2018 it was reported from the sacred groves of Epirus in Greece, and in 2020 from Norway.

Solitaria is a fungal genus in the family Teloschistaceae. It contains a single species, the corticolous (bark-dwelling), crustose lichen Solitaria chrysophthalma.

Usnochroma is a genus of lichen-forming fungi in the family Teloschistaceae. It has two species of crustose lichens. The genus was circumscribed in 2013 by lichenologists Ulrik Søchting, Ulf Arup, and Patrik Frödén, with Usnochroma carphineum assigned as the type species. The genus name refers to the yellowish-green colour of the thallus, which is caused by the substance usnic acid. Usnochroma species occur in Macaronesia, South Africa, the Mediterranean Basin, and Algeria.

Charcotiana is a single-species genus in the family Teloschistaceae. It contains the species Charcotiana antarctica, a crustose lichen found in Antarctica.

Sirenophila maccarthyi is a species of corticolous/lignicolous, crustose lichen in the family Teloschistaceae. It has a thallus that is whitish or greyish, often inconspicuous and not always continuous, which can appear darker or dirty grey near its numerous, clustered apothecia. Sirenophila maccarthyi is distributed across regions including Western Australia, New South Wales, Victoria, Tasmania, and New Zealand, in both coastal and inland habitats. It typically grows on the bark and dead wood of a wide range of trees and shrubs such as Acacia sophorae, Araucaria excelsa, and various Eucalyptus species.

<i>Polycauliona coralloides</i> Species of lichen

Polycauliona coralloides, the coral firedot lichen, is a species of small fruticose (bushy), saxicolous (rock-dwelling) lichen in the family Teloschistaceae. First formally described in 1866, it was later shuffled to a few different genera in its taxonomic history before ending up in Polycauliona, a genus resurrected from taxonomic obscurity in the molecular phylogenetics era. The lichen occurs on seaside rocks in the intertidal spray zone of California and northwestern Mexico. The species is readily recognized due to its distinctive coral-like form–its thallus grows as a tangle of orange, filamentous branches.

Flavoplaca kantvilasii is a species of saxicolous (rock-dwelling), crustose lichen in the family Teloschistaceae. Found in Australia, it was formally described as a new species in 2007.

<i>Kuettlingeria soralifera</i> Species of lichen

Kuettlingeria soralifera is a saxicolous (rock-dwelling), crustose lichen species in the family Teloschistaceae, first described in 2006. It is similar to Kuettlingeria xerica but distinguished by the presence of soredia on its thallus.

Hanstrassia lenae is a species of saxicolous (rock-dwelling) in the family Teloschistaceae. Described as a new species in 2007, the lichen is found in Russian Far East, Mongolia, and Siberia. It closely resembles Elenkiniana ehrenbergii but distinguished by the presence of soralia on its thallus. This species has a thick, effigurate thallus with weak marginal lobes and developed marginal, labriform (lip-shaped) soralia.

<i>Gallowayella weberi</i> Species of lichen

Gallowayella weberi is a species of corticolous and saxicolous, foliose lichen in the family Teloschistaceae. Found in the eastern United States, it is a small lichen with a smooth yellow to orange upper surface and a contrasting white lower surface.

Scutaria is a single-species fungal genus in the family Teloschistaceae. It contains the species Scutaria andina, found in South America. The thallus of this lichen has a form that is intermediate between crustose and foliose.

Austroplaca soropelta is a species of saxicolous and muscicolous, crustose lichen in the family Teloschistaceae. It has a bipolar distribution, meaning it occurs in polar areas of both the Northern and Southern Hemispheres.

<span class="mw-page-title-main">Parietinic acid</span> Chemical compound found in some lichens

Parietinic acid is an organic compound in the structural class of chemicals known as anthraquinones. It is found in many species of the lichen family Teloschistaceae. The substance was first reported in the literature by the German chemist Walter Eschrich in 1958.

<i>Gallowayella borealis</i> Species of lichen

Gallowayella borealis is a species of saxicolous and muscicolous, lichen in the family Teloschistaceae. The lichen is characterized by a foliose (leafy) thallus that forms small, cushion-like clusters, with lobes that are often convex and have a distinctive orange colour with a reddish tint, occasionally covered in pruina. It reproduces vegetatively through abundant soralia producing rounded, granule-like soredia. Chemically, it contains high levels of parietin among other lichen products. Gallowayella borealis thrives on both horizontal and vertical rock surfaces, often enriched by guano, and is particularly abundant in continental Antarctica, co-existing with Polycauliona candelaria near penguin rookeries. It has a bipolar distribution, found in the Arctic and boreal forests of the Northern Hemisphere as well as in ice-free zones of continental Antarctica.

Fominiella is a genus of lichen-forming fungi in the family Teloschistaceae. It contains two species with a thin, film like and inconspicuous thallus.

<span class="mw-page-title-main">Fallacinol</span> Chemical compound found in some lichens

Fallacinol (teloschistin) is an organic compound in the structural class of chemicals known as anthraquinones. It is found in some lichens, particularly in the family Teloschistaceae, as well as a couple of plants and non lichen-forming fungi. In 1936, Japanese chemists isolated a pigment named fallacin from the lichen Oxneria fallax, which was later refined and assigned a tentative structural formula; by 1949, Indian chemists had isolated a substance from Teloschistes flavicans with an identical structural formula to fallacin. Later research further separated fallacin into two distinct pigments, fallacin-A and fallacin-B (fallacinol). The latter compound is also known as teloschistin due to its structural match with the substance isolated earlier.

References

  1. ↑ Asano, Mitizo; Fuziwara, Sinobu (1936). "Über das Farbstoff von Xanthoria fallax (Hepp.) Arn. (Vorläufige Mitteil.)". Journal of the Pharmaceutical Society of Japan. 56 (12): 1007–1010. doi: 10.1248/yakushi1881.56.12_1007 .
  2. ↑ Asano, M.; Arata, Y. (1941). "Über die Bestandteile von Xanthoria fallax (Hepp.) Arn". Journal of the Pharmaceutical Society of Japan. 60 (10): 521–525. doi: 10.1248/yakushi1881.60.10_521 .
  3. ↑ Seshadri, T.R.; Subramanian, S. Sankara (1949). "Chemical investigation of Indian lichens - Part VIII. Some lichens growing on sandal trees (Ramalina tayloriana and Roccella montagnei)". Proceedings of the Indian Academy of Sciences. A. 30: 67.
  4. 1 2 3 Muramaki, Takao (1956). "The coloring matters of Xanthoria fallax (Hepp.) Arn. Fallacinal and fallacinol". Pharmaceutical Bulletin. 4 (4): 298–302.
  5. 1 2 Huneck, Siegfried (1996). Identification of Lichen Substances. Berlin, Heidelberg: Springer Berlin Heidelberg. pp. 173–174. ISBN   978-3-642-85245-9. OCLC   851387266.
  6. ↑ Arup, Ulf; Søchting, Ulrik; Frödén, Patrik (2013). "A new taxonomy of the family Teloschistaceae". Nordic Journal of Botany. 31 (1): 16–83. doi:10.1111/j.1756-1051.2013.00062.x.
  7. ↑ Nakano, H.; Komiya, T.; Shibata, S. (1972). "Anthraquinones of the lichens of Xanthoria and Caloplaca and their cultivated mycobionts". Phytochemistry. 11 (12): 3505–3508. doi:10.1016/s0031-9422(00)89847-7.
  8. ↑ Hirose, Yoshio; Suehiro, Yoshihisa; Furukawa, Yumiko; Murakami, Takao (1982). "Chemische Studien ueber natuerliche Anthrachinone. II. Synthese von Citreoroseine, Fallacinol und Fallacinal" [Chemical Studies on Natural Anthraquinones. II. Synthesis of Citreorosein, Fallacinol, and Fallacinal]. Chemical and Pharmaceutical Bulletin (in German). 30 (11): 4186–4188. doi:10.1248/cpb.30.4186.
  9. ↑ Santesson, Johan (1970). "Anthraquinones in Caloplaca". Phytochemistry. 9 (10): 2149–2166. doi:10.1016/S0031-9422(00)85380-7.
  10. ↑ Søchting, Ulrik; Frödén, Patrik (2002). "Chemosyndromes in the lichen genus Teloschistes (Teloschistaceae, Lecanorales)". Mycological Progress. 1 (3): 257–266.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.