Barbatic acid

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Barbatic acid
Barbatic acid.svg
Names
IUPAC name
2-Hydroxy-4-(2-hydroxy-4-methoxy-3,6-dimethylbenzoyl)oxy-3,6-dimethylbenzoic acid
Other names
Barbatinic acid
Identifiers
3D model (JSmol)
ChEBI
PubChem CID
  • InChI=1S/C19H20O7/c1-8-7-13(11(4)16(20)14(8)18(22)23)26-19(24)15-9(2)6-12(25-5)10(3)17(15)21/h6-7,20-21H,1-5H3,(H,22,23)
    Key: NMKBRSYSHBPUPY-UHFFFAOYSA-N
  • CC1=CC(=C(C(=C1C(=O)OC2=C(C(=C(C(=C2)C)C(=O)O)O)C)O)C)OC
Properties
C19H20O7
Molar mass 360.362 g·mol−1
Melting point 187 °C (369 °F; 460 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Barbatic acid is an organic compound that is made by some lichens. It is in the structural class known as depsides. It is particularly common in the genera Usnea (the beard lichens) and Cladonia .

Contents

History

The compound was first isolated in 1880 from the lichen Usnea barbata by chemists John Stenhouse and Charles Groves. [1] [2] [3] The compound coccellic acid, isolated from Cladonia coccifera , was later shown to be the same compound as barbatic acid. [4]

Properties

Biosynthetically, barbatic acid is made of two units of orsellinate derivatives that are created by an aromatic synthase enzyme. The repeated action of this enzyme produces an 8-carbon polyketide intermediate that is cyclized.

Barbatic acid's IUPAC name is 2-hydroxy-4-(2-hydroxy-4-methoxy-3,6-dimethylbenzoyl)oxy-3,6-dimethylbenzoic acid. Its chemical formula is C19H20O7; it has a molecular mass of 360.36  grams per mole. In its purified crystalline form, it exists as various forms: small rhombic prisms, long needles, or delicate thin sheets (lamellae). Its melting point is 187 °C (369 °F). [5]

The crystal structure of the methyl ester of barbatic acid (i.e., methyl 2-hydroxy-4-(2-hydrocy-4-methoxy-3,6-dimethylbenzoyloxy)-3,6-dimethylbenzoate, or barbatin) has been characterised. It is in the triclinic crystal system, in the space group called P1. In this crystal form, two highly substituted phenyl rings are bridged by an ester group and are inclined towards each other at 106.1°. There are two strong intramolecular hydrogen bonds between the hydroxyl substituents an the adjacent ester carbonyl groups. [6] The crystal structure of pure barbatic acid, determined using single crystal X-ray diffraction analysis, was reported in 2019. [7]

Synthesis

A synthesis for barbatic acid was reported in 1975 using trifluoroacetic acid as a condensing agent. [8] In 2022, a total synthesis was reported; the eight-step procedure starts with commercially available methyl atrarate, producing barbatic acid in a 22% total yield. [9]

A high-performance liquid chromatography (HPLC) technique has been adapted to couple the HPLC output with a photodiode array detector to screen for lichen products based on their specific ultraviolet–visible spectra. In this way, barbatic acid is detected by monitoring its retention time, and verifying the presence of three peaks representing wavelengths of maximum absorption (λmax) at 214, 276, and 310  nm. [10]

Research

Some preliminary research suggests that based on the in vitro molluscicidal activity of barbatic acid against the human parasite Schistosoma mansoni , it may have potential use in the large-scale control and/or eradication of schistosomiasis. [11] Other research has shown that it is non-toxic to human peripheral blood mononuclear cells at concentrations that are effective against the parasite. [12] Barbatic acid inhibits photosynthesis by irreversible binding to the proteins in the photosystem II complex. [13] [14]

Immobilised cells of the lichen Cladonia miniata var. parvipes have been used to synthesise barbatic acid. The cells were given sodium acetate or calcium acetate as a precursor for phenol biosynthesis. [15]

Laboratory experiments have demonstrated that barbatic acid has some antioxidant and antimicrobial activity. [16] It has cytotoxic and genotoxic activity against some tumour cell lines. [7] And in vitro and in vivo experiments using various cancer cell lines suggest that barbatic acid has antineoplastic and pro-apoptotic activities combined with a low toxicity. [7]

Related Research Articles

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<span class="mw-page-title-main">Depside</span> Class of chemical compounds

A depside is a type of polyphenolic compound composed of two or more monocyclic aromatic units linked by an ester group. Depsides are most often found in lichens, but have also been isolated from higher plants, including species of the Ericaceae, Lamiaceae, Papaveraceae and Myrtaceae.

<i>Cladia</i> Genus of fungi

Cladia is a genus of lichenized fungi in the family Cladoniaceae. Cladia species have a crustose primary thallus and a fruticose, secondary thallus, often referred to as pseudopodetium. The type species of the genus, Cladia aggregata, is widely distributed, occurring from South America, South Africa, Australasia and South-East Asia to southern Japan and India. Most of the other species are found in the Southern Hemisphere.

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<span class="mw-page-title-main">Roche ester</span> Chemical compound

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<span class="mw-page-title-main">Variegatic acid</span> Chemical compound

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<span class="mw-page-title-main">Lecanoric acid</span> Chemical compound

Lecanoric acid is a chemical produced by several species of lichen. Lecanoric acid is classified as a polyphenol and a didepside, and it functions as an antioxidant. The acid is named after the lichen Lecanora. The acid has also been isolated from Usnea subvacata, Parmotrema stuppuem, Parmotrema tinctorum,Parmotrema grayana, Xanthoparmelia arida and Xanthoparmelia lecanorica. A related compound, 5-chlorolecanoric acid, is found in some species of Punctelia.

<i>Stereocaulon ramulosum</i> Species of lichen

Stereocaulon ramulosum, commonly known as snow lichen, is a terricolous fruticose lichen belonging to the family Stereocaulaceae. It has cosmopolitan distribution. In the Australasian region, it is common in eastern Australia, New Zealand and has also been recorded at Lord Howe Island and Macquarie Island.

<i>Cladonia squamosa</i> Species of lichen

Cladonia squamosa or the dragon cup lichen is a species of cup lichen in the family Cladoniaceae.

<span class="mw-page-title-main">Atranorin</span> Chemical compound

Atranorin is a chemical substance produced by some species of lichen. It is a secondary metabolite belonging to a group of compounds known as depsides. Atranorin has analgesic, anti-inflammatory, antibacterial, antifungal, cytotoxic, antioxidant, antiviral, and immunomodulatory properties. In rare cases, people can have an allergic reaction to atranorin.

<span class="mw-page-title-main">Evernic acid</span> Chemical compound

Evernic acid is an organic compound with the molecular formula C17H16O7. Evernic acid was first isolated from the lichen Usnea longissima. Evernic acid is soluble in hot alcohol and bad soluble in water. Evernic acid is produced by the lichens Ramalina, Evernia, and Hypogymnia.

<span class="mw-page-title-main">Anziaic acid</span> Carboxylate ester

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<span class="mw-page-title-main">Strepsilin</span> Lichen that contains strepsilin

Strepsilin is a chemical found in lichens. It produces an emerald green colour in the C test. It is a dibenzofuran dimer, with hydroxy, oxy and methyl side groups. It is named after Cladonia strepsilis. Strepsilin was discovered by Wilhelm Zopf in 1903. The structure of strepsilin was determined by Shoji Shibata.

Cladonia inflata is a rare species of terricolous (ground-dwelling) lichen in the family Cladoniaceae. Found in Bahia, Brazil, it was formally described as a new species in 2018 by lichenologists André Aptroot and Marcela Eugenia da Silva Cáceres. The type specimen was collected by the authors from Palmeiras, on the Mount of Pai Inácio, at an altitude between 1,050 and 1,140 m ; here the lichen was found growing on siliceous sandstone rock in a transitional forest. Cladonia inflata is only known to occur at the type locality, and is only known from the type specimen. At this location the lichen is conspicuous but not abundant, and forms extensive mats with many other Cladonia species, such as C. bahiana, C. clathrata, C. dissecta, C. divaricata, C. friabilis, C. furfuracea, C. metaminiata, C. miniata, C. obscurata, C. parvipes, C. pityrophylla, C. polyscypha, C. salmonea, C. secundana, and C. substellata. The lichen has a fruticose (bushy), mineral-grey thallus that consists of upright hollow podetia measuring about 4 to 7 cm high, atop a cushion up to 10 cm (4 in) in diameter. It contains the secondary compound fumarprotocetraric acid. The specific epithet inflata refers to the inflated thallus of the lichen.

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

Lichexanthone is an organic compound in the structural class of chemicals known as xanthones. Lichexanthone was first isolated and identified by Japanese chemists from a species of leafy lichen in the 1940s. The compound is known to occur in many lichens, and it is important in the taxonomy of species in several genera, such as Pertusaria and Pyxine. More than a dozen lichen species have a variation of the word lichexanthone incorporated as part of their binomial name. The presence of lichexanthone in lichens causes them to fluoresce a greenish-yellow colour under long-wavelength UV light; this feature is used to help identify some species. Lichexanthone is also found in several plants, and some species of fungi that do not form lichens.

<i>Pulchrocladia retipora</i> Species of fruticose lichen

Pulchrocladia retipora, commonly known as the coral lichen, is a species of fruticose lichen in the family Cladoniaceae. Found predominantly in Australasia, its habitats range from the Australian Capital Territory to New Zealand's North and South Islands, and even the Pacific region of New Caledonia, where it grows in coastal and alpine heathlands. The lichen features coral-like branches and subbranches with numerous intricate, netlike perforations. It is known by multiple names, with some sources referring to it by its synonym Cladia retipora, or the common name lace lichen.

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

Sekikaic acid is an organic compound in the structural class of chemicals known as depsides. It is found in some lichens. First isolated from Ramalina sekika, it is a fairly common lichen product in the genera Ramalina and Cladonia. The species epithet of the powdery lichen Lepraria sekikaica refers to the presence of this substance—a rarity in genus Lepraria.

References

  1. ↑ Stenhouse, John; Groves, Charles E. (1880). "Beiträge zur Geschichte der Orcine: Betorcinol und einige seiner Derivate". Justus Liebig's Annalen der Chemie (in German). 203 (3): 285–305. doi:10.1002/jlac.18802030304.
  2. ↑ Stenhouse, John; Groves, Charles E. (1880). "XXII.—Contributions to the history of the orcins. Betorcinol and some of its derivatives". Journal of the Chemical Society, Transactions. 37: 395–407. doi:10.1039/ct8803700395.
  3. ↑ Robertson, Alexander; Stephenson, Richard John (1932). "222. Lichen acids. Part III. The constitution of barbatic acid and the syntheses of isorhizonic acid and methyl barbatate". Journal of the Chemical Society (Resumed): 1675. doi:10.1039/jr9320001675.
  4. ↑ Asahina, Yasuhiko; Fuzikawa, Fukuziro (1934). "Untersuchungen über Flechtenstoffe, XLV. Mitteil.: Über die Identität der Coccellsäure mit der Barbatinsäure". Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 67 (11): 1793–1795. doi:10.1002/cber.19340671103.
  5. ↑ Huneck, Siegfried (1996). Identification of Lichen Substances. Berlin, Heidelberg: Springer Berlin Heidelberg. pp. 48, 117, 239. ISBN   978-3-642-85245-9. OCLC   851387266.
  6. ↑ Stoeckli-Evans, H.; Blaser, D. (1991). "Structure of the methyl esters of barbatic and evernic acids: natural para-depsides". Acta Crystallographica Section C Crystal Structure Communications. 47 (12): 2620–2624. doi:10.1107/s0108270191006340.
  7. 1 2 3 Reddy, S. Divya; Siva, Bandi; Kumar, Katragunta; Babu, V.S. Phani; Sravanthi, Vemireddy; Boustie, Joel; Nayak, V. Lakshma; Tiwari, Ashok K.; Rao, CH. V.; Sridhar, B.; Shashikala, P.; Babu, K. Suresh (2019). "Comprehensive analysis of secondary metabolites in Usnea longissima (lichenized ascomycetes, Parmeliaceae) using UPLC-ESI-QTOF-MS/MS and pro-apoptotic activity of barbatic acid". Molecules. 24 (12): e2270. doi: 10.3390/molecules24122270 . PMC   6630668 . PMID   31216770.
  8. ↑ Elix, John A.; Norfolk, Susan (1975). "Synthesis of para-β-orcinol depsides". Australian Journal of Chemistry. 28 (5): 1113–1124. doi:10.1071/ch9751113.
  9. ↑ Yu, Xiang; Xi, Yin-Kai; Luo, Guo-Yong; Long, Yi; Yang, Wu-De (3 January 2022). "Synthesis of barbatic acid". Journal of Asian Natural Products Research. 24 (12): 1150–1156. doi:10.1080/10286020.2021.2023506. PMID   34978467. S2CID   245651506.
  10. ↑ Yoshimura, Isao; Kinoshita, Yasuhiro; Yamamoto, Yoshikazu; Huneck, Siegfried; Yamada, Yasuyuki (1994). "Analysis of secondary metabolites from lichen by high-performance liquid chromatography with a photodiode array detector". Phytochemical Analysis. 5 (4): 197–205. doi:10.1002/PCA.2800050405.
  11. ↑ Martins, Mônica; Silva, Monique; Silva, Hianna; Silva, Luanna; Albuquerque, Mônica; Aires, André; Falcão, Emerson; Pereira, Eugênia; de Melo, Ana; da Silva, Nicácio (2017). "Barbatic acid offers a new possibility for control of Biomphalaria glabrata and schistosomiasis". Molecules. 22 (4): 568. doi: 10.3390/molecules22040568 . PMC   6154637 . PMID   28362351.
  12. ↑ Silva, H.A.M.F.; Aires, A.L.; Soares, C.L.R.; Sá, J.L.F.; Martins, M.C.B.; Albuquerque, M.C.P.A.; Silva, T.G.; Brayner, F.A.; Alves, L.C.; Melo, A.M.M.A.; Silva, N.H. (2020). "Barbatic acid from Cladia aggregata (lichen): Cytotoxicity and in vitro schistosomicidal evaluation and ultrastructural analysis against adult worms of Schistosoma mansoni". Toxicology in Vitro. 65: 104771. doi:10.1016/j.tiv.2020.104771. PMID   31935486. S2CID   210827117.
  13. ↑ Endo, Tsuyoshi; Takahagi, Toshikazu; Kinoshita, Yasuhiro; Yamamoto, Yoshikazu; Sato, Fumihiko (1998). "Inhibition of photosystem II of spinach by lichen-derived Depsides". Bioscience, Biotechnology, and Biochemistry. 62 (10): 2023–2027. doi: 10.1271/bbb.62.2023 . PMID   27385453.
  14. ↑ Takahagi, Toshikazu; Ikezawa, Nobuhiro; Endo, Tsuyoshi; Ifuku, Kentaro; Yamamoto, Yoshikazu; Kinoshita, Yasuhiro; Takeshita, Shunji; Sato, Fumihiko (2006). "Inhibition of PSII in atrazine-tolerant tobacco cells by barbatic acid, a lichen-derived depside". Bioscience, Biotechnology, and Biochemistry. 70 (1): 266–268. doi: 10.1271/bbb.70.266 . PMID   16428846. S2CID   13291222.
  15. ↑ Vivas, Mercedes; Millanes, Ana Maria; Filho Neli K., Lauro Xavier; Honda, Eugênia C.; Pereira, Carlos Vicente; Legaz, Maria-Estrella (2006). "Production of barbatic acid by immobilized cells of Cladonia miniata var. parvipes in calcium alginate". Journal of the Hattori Botanical Laboratory. 100: 855–863.
  16. ↑ Martins, Mônica Cristina Barroso; Lima, Marcio James Gonçalves de; Silva, Flávia Pereira; Azevedo-Ximenes, Eulália; Silva, Nicácio Henrique da; Pereira, Eugênia Cristina (2010). "Cladia aggregata (lichen) from Brazilian northeast: chemical characterization and antimicrobial activity". Brazilian Archives of Biology and Technology. 53 (1): 115–122. doi: 10.1590/s1516-89132010000100015 .
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