Über die Lactonringbildung des Cumarins

1960 ◽  
Vol 15 (12) ◽  
pp. 768-769 ◽  
Author(s):  
Stewart A. Brown
Keyword(s):  
Cinnamic Acid ◽  
Higher Plants ◽  
Lactone Ring ◽  
Coumaric Acid ◽  
Reaction Sequence ◽  
Enzyme Systems ◽  
Common Precursor ◽  
Hierochloe Odorata ◽  
Tracer Experiments

Tracer experiments with 14C have shown that p-coumaric acid is over 70 times less efficient than cinnamic acid as a precursor of coumarin in Hierochloe odorata, and that tyrosine is over 60 times less efficient than phenylalanine. The results show that in this species the reaction sequence postulated by HAWORTH, in which coumarins are formed from p-coumaric acid, is not significantly involved in the biosynthesis of coumarin itself. It is suggested that, in higher plants, cinnamic acid (or an “activated“ form of it) is a common precursor of all coumarins, and that ortho- or para-hydroxylation of this compound leads subsequently to the formation of coumarin and the 7-hydroxycoumarins, respectively. Different enzyme systems may be required for the formation of the lactone ring of coumarin and the 7-hydroxycoumarins.

BIOSYNTHESIS OF THE COUMARINS. TRACER STUDIES ON COUMARIN FORMATION IN HIEROCHLOË ODORATA AND MELILOTUS OFFICINALIS

1960 ◽  
Vol 38 (2) ◽  
pp. 143-156 ◽  
Author(s):  
Stewart A. Brown ◽  
G. H. N. Towers ◽  
D. Wright
Keyword(s):  
Cinnamic Acid ◽  
Shikimic Acid ◽  
Perennial Grass ◽  
Coumaric Acid ◽  
Sweet Clover ◽  
Tracer Studies ◽  
Melilotus Officinalis ◽  
Specific Activities ◽  
Acid Pathway ◽  
Hierochloe Odorata

Coumarin formation has been studied with C14in the perennial grass, Hierochloë odorata, and in yellow sweet clover, Melilotus officinalis. In general the latter species yielded inconsistent data. In Hierochloë, o-coumaric, cinnamic, and shikimic acids and L-phenylalanine were the best of 10 compounds tested as coumarin precursors, the first two at least being incorporated with little randomization of C14. Acetate was more poorly utilized. It was concluded that the aromatic ring of coumarin arises via the shikimic acid pathway in preference to acetate condensation. When the time of metabolism was varied, o-coumaryl glucoside and free o-coumaric acid rapidly acquired high specific activities from cinnamic acid-C14, but coumarin and melilotic acid became active much more slowly. A lag in the acquisition of C14by coumarin for the first 6 to 8 hours was followed by a rectilinear increase until at least 24 hours. Much the greatest accumulation of C14was found in o-coumaryl glucoside during this entire period. Furthermore, this compound when fed to Hierochloë is comparable to cinnamic acid as a coumarin precursor. These findings suggest a possible function for o-coumaryl glucoside or a derivative in coumarin biosynthesis.

Biosynthesis of Daphnetin in Daphne mezereum L.

1986 ◽  
Vol 41 (3) ◽  
pp. 247-252 ◽  
Author(s):  
Stewart A. Brown
Keyword(s):  
Caffeic Acid ◽  
Aromatic Ring ◽  
Lactone Ring ◽  
Ring Formation ◽  
Coumaric Acid ◽  
Tracer Experiments

Shoots of Daphne mezereum synthesized daphnetin (7,8-dihydroxycoumarin) more efficiently from [2-14C]umbelliferone (7-hydroxycoumarin) than from [2-14C]p-coumaric acid, and [2-14C]caffeic acid was more poorly utilized still. These findings do not support the idea of derivation of daphnetin via hydroxylation of the caffeic acid ring at the 2 position, followed by lactone ring formation; instead they are consistent with the concept of daphnetin formation by an additional hydroxylation of umbelliferone at C-8. Umbelliferone was recovered with little l4C dilution from emulsin-hydrolysed extracts of shoots fed labelled umbelliferone, and TLC of extracts from untreated shoots revealed two substances yielding umbelliferone on hydrolysis. Evidence is presented from TLC and HP LC analysis that one of these is skimmin (7-O-β-ᴅ -glucosylumbelliferone), not previously reported from Daphne. The tracer experiments further support the theory that umbelliferone is the general precursor of coumarins bearing two or more hydroxyl functions on the aromatic ring.

scholarly journals Cinnamic acid and p-coumaric acid, precursors of ubiquinone in higher plants, green algae and fungi

1970 ◽  
Vol 118 (3) ◽  
pp. 55P-55P ◽  
Author(s):  
D R Threlfall ◽  
A Law ◽  
G R Whistance
Keyword(s):  
Green Algae ◽  
Cinnamic Acid ◽  
Higher Plants ◽  
Coumaric Acid

BIOSYNTHESIS OF THE COUMARINS. TRACER STUDIES ON COUMARIN FORMATION IN HIEROCHLOË ODORATA AND MELILOTUS OFFICINALIS

1960 ◽  
Vol 38 (1) ◽  
pp. 143-156 ◽  
Author(s):  
Stewart A. Brown ◽  
G. H. N. Towers ◽  
D. Wright
Keyword(s):  
Cinnamic Acid ◽  
Shikimic Acid ◽  
Perennial Grass ◽  
Coumaric Acid ◽  
Sweet Clover ◽  
Tracer Studies ◽  
Melilotus Officinalis ◽  
Specific Activities ◽  
Acid Pathway ◽  
Hierochloe Odorata

Coumarin formation has been studied with C14in the perennial grass, Hierochloë odorata, and in yellow sweet clover, Melilotus officinalis. In general the latter species yielded inconsistent data. In Hierochloë, o-coumaric, cinnamic, and shikimic acids and L-phenylalanine were the best of 10 compounds tested as coumarin precursors, the first two at least being incorporated with little randomization of C14. Acetate was more poorly utilized. It was concluded that the aromatic ring of coumarin arises via the shikimic acid pathway in preference to acetate condensation. When the time of metabolism was varied, o-coumaryl glucoside and free o-coumaric acid rapidly acquired high specific activities from cinnamic acid-C14, but coumarin and melilotic acid became active much more slowly. A lag in the acquisition of C14by coumarin for the first 6 to 8 hours was followed by a rectilinear increase until at least 24 hours. Much the greatest accumulation of C14was found in o-coumaryl glucoside during this entire period. Furthermore, this compound when fed to Hierochloë is comparable to cinnamic acid as a coumarin precursor. These findings suggest a possible function for o-coumaryl glucoside or a derivative in coumarin biosynthesis.

METABOLISM OF PHENYLPROPANOID COMPOUNDS IN SALVIA: II. BIOSYNTHESIS OF PHENOLIC CINNAMIC ACIDS

1959 ◽  
Vol 37 (1) ◽  
pp. 537-547 ◽  
Author(s):  
D. R. McCalla ◽  
A. C. Neish
Keyword(s):  
Caffeic Acid ◽  
Phenolic Acids ◽  
Cinnamic Acid ◽  
Shikimic Acid ◽  
Sinapic Acid ◽  
Coumaric Acid ◽  
Cinnamic Acids ◽  
Phenyllactic Acid ◽  
Salvia Splendens ◽  
Specific Activities

p-Coumaric, caffeic, ferulic, and sinapic acids were found to occur in Salvia splendens Sello in alkali-labile compounds of unknown constitution. A number of C14-labelled compounds were administered to leafy cuttings of salvia and these phenolic acids were isolated after a metabolic period of several hours and their specific activities measured. Cinnamic acid, dihydrocinnamic acid, L-phenylalanine, and (−)-phenyllactic acid were found to be good precursors of the phenolic acids. D-Phenylalanine, L-tyrosine, and (+)-phenyllactic acid were poor precursors. A kinetic study of the formation of the phenolic acids from L-phenylalanine-C14 gave data consistent with the view that p-coumaric acid → caffeic acid → ferulic acid → sinapic acid, and that these compounds can act as intermediates in lignification. Feeding of C14-labelled members of this series showed that salvia could convert any one to a more complex member of the series but not so readily to a simpler member. Caffeic acid-β-C14 was obtained from salvia after the feeding of L-phenylalanine-β-C14 or cinnamic acid-β-C14, and caffeic acid labelled only in the ring was obtained after feeding generally labelled shikimic acid.

scholarly journals Identification of the Tyrosine- and Phenylalanine-Derived Soluble Metabolomes of Sorghum

2021 ◽  
Vol 12 ◽  
Author(s):  
Jeffrey P. Simpson ◽  
Jacob Olson ◽  
Brian Dilkes ◽  
Clint Chapple
Keyword(s):  
Amino Acids ◽  
Cinnamic Acid ◽  
Aromatic Amino Acids ◽  
Flavonoid Glycosides ◽  
Coumaric Acid ◽  
Biotic And Abiotic Stress ◽  
Proportional Contribution ◽  
Negative Ionization ◽  
Derivatives Of

The synthesis of small organic molecules, known as specialized or secondary metabolites, is one mechanism by which plants resist and tolerate biotic and abiotic stress. Many specialized metabolites are derived from the aromatic amino acids phenylalanine (Phe) and tyrosine (Tyr). In addition, the improved characterization of compounds derived from these amino acids could inform strategies for developing crops with greater resilience and improved traits for the biorefinery. Sorghum and other grasses possess phenylalanine ammonia-lyase (PAL) enzymes that generate cinnamic acid from Phe and bifunctional phenylalanine/tyrosine ammonia-lyase (PTAL) enzymes that generate cinnamic acid and p-coumaric acid from Phe and Tyr, respectively. Cinnamic acid can, in turn, be converted into p-coumaric acid by cinnamate 4-hydroxylase. Thus, Phe and Tyr are both precursors of common downstream products. Not all derivatives of Phe and Tyr are shared, however, and each can act as a precursor for unique metabolites. In this study, 13C isotopic-labeled precursors and the recently developed Precursor of Origin Determination in Untargeted Metabolomics (PODIUM) mass spectrometry (MS) analytical pipeline were used to identify over 600 MS features derived from Phe and Tyr in sorghum. These features comprised 20% of the MS signal collected by reverse-phase chromatography and detected through negative-ionization. Ninety percent of the labeled mass features were derived from both Phe and Tyr, although the proportional contribution of each precursor varied. In addition, the relative incorporation of Phe and Tyr varied between metabolites and tissues, suggesting the existence of multiple pools of p-coumaric acid that are fed by the two amino acids. Furthermore, Phe incorporation was greater for many known hydroxycinnamate esters and flavonoid glycosides. In contrast, mass features derived exclusively from Tyr were the most abundant in every tissue. The Phe- and Tyr-derived metabolite library was also utilized to retrospectively annotate soluble MS features in two brown midrib mutants (bmr6 and bmr12) identifying several MS features that change significantly in each mutant.

Studies on the Biosynthesis of Pseudoisoeugenols in Tissue Cultures of Pimpinella anisum

1988 ◽  
Vol 43 (5-6) ◽  
pp. 328-336 ◽  
Author(s):  
Rainer Martin ◽  
Gerhard Schilling ◽  
Jürgen Reichling
Keyword(s):  
Tissue Culture ◽  
Cinnamic Acid ◽  
Tissue Cultures ◽  
Coumaric Acid ◽  
Pimpinella Anisum

A leaf-differentiating tissue culture which produced substantial amounts of pseudoisoeugenol- (2-methylbutyrate) has been used to examine the origin of the pseudoisoeugenol skeleton. 14Cand 13C-labelling revealed ʟ-phenylalanine, trans-cinnamic acid and p-coumaric acid as precursors. 13C-labelled precursors proved to be especially useful.

Biosynthese von p-Hydroxybenzoesäure und anderer Benzoesäuren in höheren Pflanzen

1964 ◽  
Vol 19 (5) ◽  
pp. 398-405 ◽  
Author(s):  
M. H. Zenk ◽  
G. Müller
Keyword(s):  
Benzoic Acid ◽  
Protocatechuic Acid ◽  
Higher Plants ◽  
Side Chain ◽  
Hydroxybenzoic Acid ◽  
Benzoic Acids ◽  
Coumaric Acid ◽  
Cinnamic Acids ◽  
Feeding Experiments ◽  
Catalpa Ovata

Feeding experiments with glucose- (2-14C), phenylalanine- (3-14C), tyrosine- (3-14C) and p-coumaric acid- (3-14C) showed that the latter three substances are incorporated in good yields into p-hydroxybenzoic acid in leaves of Catalpa ovata. Kinetic experiments showed that p-hydroxybenzoic acid is formed from phenylalanine via p-coumaric acid and the subsequent β-oxidation of the side chain. p-Hydroxybenzoic acid can also be synthetised by hydroxylation of benzoic acid, but this does not seem to be the biosynthetic route in Catalpa.Phenylalanine- (3-14C) is also incorporated into benzoic acid, protocatechuic acid, and vanillic acid by different plants; the radioactivity of the β-C atom of the amino acid was found in each case to be located in the carboxyl group of the C6 — C1 acid. This suggests that in higher plants the benzoic acids are formed from the corresponding cinnamic acids via β-oxidation.

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