Synthesis and Structure Determination of Gibberellin-Derived Antheridiogens From Fern Gametophytes of the Lygodium Genus

1995 ◽  
Vol 48 (2) ◽  
pp. 427 ◽  
Author(s):  
M Furber ◽  
P Kraftklaunzer ◽  
LN Mander ◽  
M Pour ◽  
T Yamauchi ◽  
...  
Keyword(s):  
Free Radical ◽  
Methyl Ester ◽  
Hydroxy Derivative ◽  
Radical Bromination ◽  
Step Procedure ◽  
Efficient Route ◽  
Lygodium Japonicum ◽  
Synthetic Routes ◽  
Fern Gametophytes

Two successful and two unsuccessful synthetic routes are described for the conversion of commercially available fungal gibberellins to the antheridiogen GA73 methyl ester (5), originally isolated from gametophytes of the fern Lygodium japonicum. The more efficient route began with the Birch reduction of either the GA7 derivative (31) or methyl gibberellate 3,13-dimesylate (32) to give the ∆1(10),16-diene acid (33), which was converted into the ∆1,9-diene acid (40) by means of a four step procedure. This intermediate could be selectively hydrogenated to the ∆9-ene derivative which underwent iodolactonization and then elimination of HI to afford enone (29), Wittig methylenation of which furnished the target antheridiogen (5). In addition, (29) was functionalized at C12 by free radical bromination to give access to the 12β-hydroxy derivative of (5), i.e. (6), a new antheridiogen isolated from Lygodium circinnatum.

Temperature Dependent Green Synthesis of 3-Carboxycoumarins and 3,4-unsubstituted Coumarins

2019 ◽  
Vol 16 (1) ◽  
pp. 130-135 ◽  
Author(s):  
Jack van Schijndel ◽  
Dennis Molendijk ◽  
Luiz Alberto Canalle ◽  
Erik Theodorus Rump ◽  
Jan Meuldijk
Keyword(s):  
Knoevenagel Condensation ◽  
Ammonium Bicarbonate ◽  
Solvent Free ◽  
Temperature Dependent ◽  
Step Procedure ◽  
Synthetic Routes ◽  
High Yields ◽  
Temperature Optima ◽  
Solvent Free Synthesis ◽  
Full Conversion

Aim and Objective: Because of the low abundance of 3,4-unsubstituted coumarins in plants combined with the complex purification process required, synthetic routes towards 3,4-unsubstituted coumarins are especially valuable. In the present work, we explore the possibilities of a solvent-free Green Knoevenagel condensation on various 2-hydroxybenzaldehyde derivatives and malonic acid without the use of toxic organocatalysts like pyridine and piperidine but only use ammonium bicarbonate as the catalyst. Materials and Methods: To investigate the scope of the Green Knoevenagel condensation for the synthesis of 3,4-unsubstituted coumarins, various 2-hydroxybenzaldehyde derivatives were screened as starting material in the optimized two-step procedure developed for 2-hydroxybenzaldehyde. </P><P> Results: This study shows that the intramolecular esterification and the decarboxylation are in competition, but show different temperature optima. In order to suppress premature decarboxylation and maximize the yield of coumarin, a two-step procedure was adopted. The reaction mixture containing ammonium bicarbonate is initially kept at 90ºC for 1 hour. After completion of the cyclization, the temperature of the reaction mixture is increased to 140ºC for 2 hours. Following this protocol, coumarin could be isolated with a yield of 95%. Conclusion: A two-step procedure for the solvent-free synthesis of several 3,4-unsubstituted coumarins was developed using ammonium bicarbonate, resulting in high yields of the desired products. Moreover, this procedure has a low E-factor and is, therefore an environmental friendly reaction in line with the principles of Green Chemistry. It was shown that by initially capping the temperature at 90ºC, premature decarboxylation can be suppressed. After full conversion to the intermediate 3-carboxycoumarin, the temperature can be increased to 140ºC finalizing the reaction. Ammonium bicarbonate was shown to catalyze both the Green Knoevenagel condensation and the decarboxylation step.

scholarly journals Managing pH of Organic Matrices and New Commercial Substrates for Ornamental Plant Production: A Methodological Approach

Agronomy ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 851
Author(s):  
Sonia Cacini ◽  
Sara Di Lonardo ◽  
Simone Orsenigo ◽  
Daniele Massa
Keyword(s):  
Methodological Approach ◽  
Buffering Capacity ◽  
Ornamental Plant ◽  
Plant Production ◽  
Climatic Chamber ◽  
Step Procedure ◽  
Coir Dust ◽  
Organic Matrices ◽  
Substrate Mixtures

Professional peat-free substrates for ornamental plant production are increasingly required by nursery growers. Most promising materials are green compost, coconut coir dust, and woody fibre, used alone or in mixtures. One of the major concerns is pH, usually higher than optimal. In this work, a method based on a three-step procedure was adopted to acidify three organic matrices alone or in mixtures and to individuate the most suitable product, between iron(II) sulphate 7-hydrate and elemental sulphur chips. Firstly, the determination of the buffering capacity by dilution with sulphuric acid was carried out to determine dosages. Afterwards, an incubation trial of 84 (iron(II) sulphate) or 120 days (sulphur chips) was conducted on matrices and substrate mixtures with calculated doses in a climatic chamber maintained at 21 °C. Iron(II) sulphate resulted not suitable because it caused a rapid, but not lasting, pH lowering and an excessive electrical conductivity (EC) increase. Sulphur chips could instead guarantee an adequate and lasting pH lowering. These results were then validated in the open field trial on matrices and substrates. The proposed acidification methodology could be considered in developing new substrates, but the rapidity of pH acidification and EC increase on plant and mineral nutrition should be further investigated.

scholarly journals In Vitro and In Vivo Antioxidant Properties of Taraxacum officinale in Nω-Nitro-l-Arginine Methyl Ester (L-NAME)-Induced Hypertensive Rats

Antioxidants ◽  
2019 ◽  
Vol 8 (8) ◽  
pp. 309
Author(s):  
Olukayode O. Aremu ◽  
Adebola O. Oyedeji ◽  
Opeoluwa O. Oyedeji ◽  
Benedicta N. Nkeh-Chungag ◽  
Constance R. Sewani Rusike
Keyword(s):  
Oxidative Stress ◽  
Free Radical ◽  
Methyl Ester ◽  
Leaf Extract ◽  
Radical Scavenging ◽  
Free Radical Scavenging ◽  
Hypertensive Rats ◽  
Total Antioxidant

Oxidative stress has gained attention as one of the fundamental mechanisms responsible for the development of hypertension. The present study investigated in vitro and in vivo antioxidant effects of 70% ethanol-water (v/v) leaf and root extracts of T. officinale (TOL and TOR, respectively). Total phenolic and flavonoid content of plant extracts were assessed using Folin Ciocalteau and aluminium chloride colorimetric methods; while, 2,2-diphenyl-1-picrlhydrazyl (DPPH), 2,2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and ferric reducing antioxidant power (FRAP) protocols were used to determine the free radical scavenging and total antioxidant capacities (TAC), respectively. The in vivo total antioxidant capacity and malondialdehyde acid (MDA) levels for lipid peroxidation tests were performed on organ homogenate samples from Nω-nitro-L-arginine methyl ester (L-NAME)-induced hypertensive rats treated with leaf extract, TOL (500 mg/kg/day) and TOR (500 mg/kg/day) for 21 days. Results showed that compared to TOR, TOL possessed significantly higher (p < 0.01) polyphenol (4.35 ± 0.15 compared to 1.14 ± 0.01) and flavonoid (23.17 ± 0.14 compared to 3 ± 0.05) content; free radical scavenging activity (EC50 0.37 compared to 1.34 mg/mL) and total antioxidant capacities (82.56% compared to 61.54% ABTS, and 156 ± 5.28 compared to 40 ± 0.31 FRAP) and both extracts showed no toxicity (LD50 > 5000 mg/kg). TOL and TOR significantly (p < 0.01) elevated TAC and reduced MDA levels in targets organs. In conclusion, T. officinale leaf extract possesses significant anti-oxidant effects which conferred significant in vivo antioxidant protection against free radical-mediated oxidative stress in L-NAME-induced hypertensive rats.

Directing Bromination of Piperazine-2,5-diones

1995 ◽  
Vol 48 (7) ◽  
pp. 1379 ◽  
Author(s):  
TW Badran ◽  
CLL Chai ◽  
CJ Easton ◽  
JB Harper ◽  
DM Page
Keyword(s):  
Free Radical ◽  
Methyl Substituent ◽  
Radical Bromination ◽  
Acetyl Group

From intermolecular and intramolecular competition experiments, it has been established that, by comparison with an N-methyl substituent, an N-acetyl group deactivates glycine residues in piperazine-2,5-diones towards free-radical bromination. Combined with the ease of introduction and removal of N-acetyl substituents, the deactivating effect provides a method for regiocontrolled functionalization of these compounds.

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