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Barbatic acid

October 20, 2023

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.

Barbatic acid
Names
IUPAC name
2-Hydroxy-4-(2-hydroxy-4-methoxy-3,6-dimethylbenzoyl)oxy-3,6-dimethylbenzoic acid
Other names
Barbatinic acid
Identifiers
  • 17636-16-7
3D model (JSmol)
  • Interactive image
ChEBI
  • CHEBI:144123
  • 167666
  • DTXSID40170115
  • 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).

History Edit

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 Edit

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 Edit

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 Edit

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]

References Edit

  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. ^ a b c 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.

October 20, 2023
barbatic, acid, organic, compound, that, made, some, lichens, structural, class, known, depsides, particularly, common, genera, usnea, beard, lichens, cladonia, namesiupac, name, hydroxy, hydroxy, methoxy, dimethylbenzoyl, dimethylbenzoic, acidother, names, ba. 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 Barbatic acid NamesIUPAC name 2 Hydroxy 4 2 hydroxy 4 methoxy 3 6 dimethylbenzoyl oxy 3 6 dimethylbenzoic acidOther names Barbatinic acidIdentifiersCAS Number 17636 16 73D model JSmol Interactive imageChEBI CHEBI 144123PubChem CID 167666CompTox Dashboard EPA DTXSID40170115InChI 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 NSMILES CC1 CC C C C1C O OC2 C C C C C2 C C O O O C O C OCPropertiesChemical formula C 19H 20O 7Molar mass 360 362 g mol 1Melting 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 Infobox references Contents 1 History 2 Properties 3 Synthesis 4 Research 5 ReferencesHistory EditThe 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 EditBiosynthetically 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 EditA 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 lmax at 214 276 and 310 nm 10 Research EditSome 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 References Edit Stenhouse John Groves Charles E 1880 Beitrage 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 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 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 Asahina Yasuhiko Fuzikawa Fukuziro 1934 Untersuchungen uber Flechtenstoffe XLV Mitteil Uber die Identitat der Coccellsaure mit der Barbatinsaure Berichte der Deutschen Chemischen Gesellschaft A and B Series 67 11 1793 1795 doi 10 1002 cber 19340671103 Huneck Siegfried 1996 Identification of Lichen Substances Berlin Heidelberg Springer Berlin Heidelberg pp 48 117 239 ISBN 978 3 642 85245 9 OCLC 851387266 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 a b c 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 Elix John A Norfolk Susan 1975 Synthesis of para b orcinol depsides Australian Journal of Chemistry 28 5 1113 1124 doi 10 1071 ch9751113 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 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 Martins Monica Silva Monique Silva Hianna Silva Luanna Albuquerque Monica Aires Andre Falcao Emerson Pereira Eugenia de Melo Ana da Silva Nicacio 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 Silva H A M F Aires A L Soares C L R Sa 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 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 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 Vivas Mercedes Millanes Ana Maria Filho Neli K Lauro Xavier Honda Eugenia 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 Martins Monica Cristina Barroso Lima Marcio James Goncalves de Silva Flavia Pereira Azevedo Ximenes Eulalia Silva Nicacio Henrique da Pereira Eugenia 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 Retrieved from https en wikipedia org w index php title Barbatic acid amp oldid 1170232708, wikipedia, wiki, book, books, library,

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