Orsellic acid
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| Surname | Orsellic acid | ||||||||||||||||||
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| Molecular formula | C 8 H 8 O 4 | ||||||||||||||||||
| Brief description |
colorless needles |
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| Molar mass | 168.15 g mol −1 | ||||||||||||||||||
| Physical state |
firmly |
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| As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . | |||||||||||||||||||
The orsellinic acid is an organic acid and is derived from the benzoic acid from by two hydroxy groups and a methyl group as a substituent are added. It belongs to u. a. to the group of phenolic acids . It is also close to the subgroup of dihydroxybenzoic acids and differs specifically from β-resorcylic acid (2,4-dihydroxybenzoic acid) through an added methyl group. It plays a role in the biochemistry of lichens and the Aspergillus and Penicillium strains from which it can be isolated. The biosynthesis in these organisms takes place via the polyketide route .
Occurrence and biosynthesis
Orsellic acid is formed u. a. as a secondary metabolite in Aspergillus nidulans . The formation of orsellic acid can be specifically triggered by close physical contact with neighboring bacteria or a mutation in the signalosome complex. Orsellic acid, orcin and penicillic acid are found in cultures of Penicillium fennelliae . It plays a role in the biochemistry of the lichens , from which it can be isolated.
The biosynthesis proceeds via the polyketide route , in which a tetraketide is built up from simple, coenzyme A -activated acyl groups (mostly acetyl-CoA ) and then cyclized.
For A. nidulans the gene for an orsellic acid synthase (OAS) was identified, which is similar to a typical, non- reducing polyketide synthase . The sequence information gives clues to various domains that play a role in the biosynthetic pathway. Sequence motifs of a starting acyltransferase, a keto synthase, an acyltransferase, a product template domain, an acyl carrier protein and a thioesterase have been identified. This suggests that one molecule of orsellic acid can be formed from three molecules of malonyl-CoA and one enzyme-bound acetyl-CoA. Acetyl-CoA serves as the starting molecule for the synthesis; all further steps are enzyme-linked.
presentation
The synthesis is achieved by Michael addition of acetoacetate to ethyl crotonate with subsequent intramolecular Dieckmann condensation . In the process, ethyl dihydroorsellinate is formed . Dehydration and ester cleavage lead to orsellic acid.
Orsellic acid can also be produced by the oxidation of orcylaldehyde .
It can also be shown if evernic acid (CAS number: 570-10-5) and ramalic acid (CAS number: 500-37-8) are heated with barium hydroxide and thus the ester bond is broken.
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- Structural formulas of evernic acid (left) and ramalic acid (right)
Another synthesis is based on orcin , which is carboxylated with magnesium methyl carbonate in DMF .
properties
Orsellic acid forms colorless crystals in the form of needles. It decomposes when heated rapidly at 176 ° C and decarboxylates to orcine .
literature
- Adolf Sonn: "A new synthesis of orsellic acid (5th communication on lichen substances.)", In: Reports of the German Chemical Society , 1928 , 61 (5), pp. 926-927 ( doi : 10.1002 / cber.19280610508 ).
Individual evidence
- ↑ a b c d David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Physical Constants of Organic Compounds, pp. 3-182.
- ↑ a b data sheet orsellic acid from AlfaAesar, accessed on April 30, 2017 ( PDF )(JavaScript required) .
- ↑ Volker Schroeckh, Kirstin Scherlach, Hans-Wilhelm Vorteilmann, Ekaterina Shelest, Wolfgang Schmidt-Heck, Julia Schuemann, Karin Martin, Christian Hertweck, Axel A. Brakhage: "Intimate bacterial-fungal interaction triggers biosynthesis of archetypal polyketides in Aspergillus nidulans", in: Proceedings of the National Academy of Sciences of the United States of America , 2009 , 106 (34), pp. 14558-14563 ( doi : 10.1073 / pnas.0901870106 ; PDF ).
- ↑ Michael Ramm: Bacteria induce the synthesis of active substances in fungi. Leibniz Institute for Natural Product Research and Infection Biology - Hans Knöll Institute (HKI), press release from August 21, 2009 from Informationsdienst Wissenschaft (idw-online.de), accessed on August 24, 2015 .; www.organische-chemie.ch: August 25, 2009 .
- ↑ James F. Sanchez, Yi-Ming Chiang, Edyta Szewczyk, Ashley D. Davidson, Manmeet Ahuja, C. Elizabeth Oakley, Jin Woo Bok, Nancy Keller, Berl R. Oakley, Clay CC Wang: "Molecular genetic analysis of the orsellinic acid / F9775 gene cluster of Aspergillus nidulans ", in: Mol Biosyst. , 2010 , 6 (3), pp. 587-593 ( doi : 10.1039 / B904541D ; PMID 20174687 ; PMC 2903553 (free full text)).
- ↑ Krystyna Nahlik, Marc Dumkow, Özgür Bayram, Kerstin Helmstaedt, Silke Busch, Oliver Valerius, Jennifer Gerke, Michael Hoppert, Elke Schwier, Lennart Opitz, Mieke Westermann, Stephanie Grond, Kirstin Feussner, Cornelia Goebel, Alexander Kaever, Peter Meinecke, Ivo Feussner, Gerhard H. Braus: "The COP9 signalosome mediates transcriptional and metabolic response for hormones, oxidative stress protection and cell wall rearrangement during fungal development", in: Molecular Microbiology , 2010 , 78 (4), pp. 964-979 ( doi : 10.1111 / j.1365-2958.2010.07384.x ).
- ↑ GW Eijk: "Isolation and identification of orsellinic acid and penicillic acid produced by Penicillium fennelliae Stolk", in: Antonie van Leeuwenhoek , 1969 , 35 (1), pp. 497-504 ( doi : 10.1007 / BF02219167 ).
- ^ TJ Nolan, J. Keane, VE Davidson: "Chemical constituents of the lichen Parmelia latissima Fee", in: Scientific Proceedings of the Royal Dublin Society, Series A , 1940 , 22 , pp. 237-239.
- ↑ Klaus Mosbach: "The biosynthesis of orsellic acid and penicillic acid (I)", in: Acta Chem. Scand. , 1960 , 14 , pp. 457-464 ( PDF ).
- ↑ Klaus Mosbach: "The role of malonic acid in the biosynthesis of orsellic acid", in: Naturwissenschaften , 1961 , 48 (15), pp. 525-525 ( doi : 10.1007 / BF00595346 ).
- ↑ Kurt Hoesch: "Synthesis of Orsellic acid and Evernic acid", in: Reports of the German Chemical Society , 1913 , 46 (1), pp. 886-892 ( doi : 10.1002 / cber.191304601116 ).
- ↑ Ying Kang, Yan Mei, Yuguo Du, Zhendong Jin: "Total Synthesis of the Highly Potent Anti-HIV Natural Product Daurichromenic Acid along with Its Two Chromane Derivatives, Rhododaurichromanic Acids A and B", in: Organic Letters , 2003 , 5 ( 23), pp. 4481-4484 ( PMID 14602030 ; ( doi : 10.1021 / ol030109m ).
- ^ A b R. Russell, C. Kemmelmeier: "Neutral, alkaline and difference ultraviolet spectra of secondary metabolites from Penicillium and other fungi, and comparisons to published maxima from gradient high-performance liquid chromatography with diode-array detection", in: Journal of Chromatography A , 1990 , 511 , pp. 195-221 ( doi : 10.1016 / S0021-9673 (01) 93285-6 ; PMID 2211911 ).
- ↑ J. Santesson: "Syntheses of Orsellinic Acid and Related Compounds", in: Acta Chem. Scand. , 1970 , 24 , pp. 3373-3378 ( PDF ).
- ^ R. Hegnauer: Chemotaxonomy of Plants , Volume 1: Thallophyten, Bryophyten; Pteridophytes and gymnosperms, Birkhäuser Verlag, Basel 1962, p. 160 ( limited preview in Google book search).
