Flavan derivatives. XVII. Epimerization of the benzylic 4-hydroxyl group in flavan-3,4-diols and the formation of 4-alkyl ethers by solvolysis

1967 ◽  
Vol 20 (10) ◽  
pp. 2151
Author(s):  
JW Clark-Lewis ◽  
LR Williams
Keyword(s):  
Aqueous Media ◽  
Cyclic Ether ◽  
Hydroxyl Group ◽  
Mechanism Of Formation ◽  
Enol Ether ◽  
Mild Conditions ◽  
Ethoxyl Group ◽  
Alkyl Ethers ◽  
By Products ◽  
Thermodynamic Factors

Epimerization and solvolysis of the benzylic 4-hydroxyl group is shown to be a general property of flavan-3,4-diols, and the diols give 4- ethoxyflavan-3-ols with ethanolic hydrochloric acid (1%). The diols are first converted into epimeric mixtures of 3,4-cis- and 3,4-trans-diols and in aqueous media cis-cis-flavan-3,4-diols yield mainly 2,3-cis-3,4- trans-diols. These 2,3-cis-3,4-diols undergo solvolysis to yield 2,3- cis-3,4-trans-4-ethoxyflavan-3-ols in which the 3,4-trans- stereochemistry is controlled by participation of the neighbouring 3ax- hydroxyl group. 2,3-trans-Flavan-3,4-diols give mixtures of trans- trans-diols and 2,3-trans-3,4-cis-diols and solvolysis first yields 2.3-trans-3,4-cis-4-ethoxyflavan-3-ols and then mixtures of the 3,4- cis- and 3,4-trans-ethers; the final proportion of these two ethers is controlled by thermodynamic factors. Solvolysis under mild conditions gives minor products considered to be 3-oxoflavans (or their enols) because of their immediate conversion into antho-cyanidins by cold acids in the presence of air, and from the formation of an enol-ether on prolonged solvolysis under more vigorous conditions. The relevance of these observations to the mechanism of formation of anthocyanidins from flavan-3,4-diols is discussed. Other by-products of solvolysis reactions include a dimeric cyclic ether (dioxan derivative) of 2,3- trans-3,4-cis-7,8,4?-trimethoxyflavan-3,4-diol. The structure and stereochemistry of solvolysis products were established by N.M.R. data; the 4-ethoxyl group in the ethers generally gave rise to an ABX3 multiplet.

scholarly journals Aloe Vera-Mediated Te Nanostructures: Highly Potent Antibacterial Agents and Moderated Anticancer Effects

Nanomaterials ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 514
Author(s):  
David Medina-Cruz ◽  
Ada Vernet-Crua ◽  
Ebrahim Mostafavi ◽  
María Ujué González ◽  
Lidia Martínez ◽  
...  
Keyword(s):  
Biomedical Applications ◽  
Aqueous Media ◽  
Aloe Vera ◽  
Multidrug Resistant ◽  
Dermal Fibroblasts ◽  
Anticancer Properties ◽  
Green Approach ◽  
Anticancer Effects ◽  
Synthesis Of Nanomaterials ◽  
By Products

Cancer and antimicrobial resistance to antibiotics are two of the most worrying healthcare concerns that humanity is facing nowadays. Some of the most promising solutions for these healthcare problems may come from nanomedicine. While the traditional synthesis of nanomaterials is often accompanied by drawbacks such as high cost or the production of toxic by-products, green nanotechnology has been presented as a suitable solution to overcome such challenges. In this work, an approach for the synthesis of tellurium (Te) nanostructures in aqueous media has been developed using aloe vera (AV) extracts as a unique reducing and capping agent. Te-based nanoparticles (AV-TeNPs), with sizes between 20 and 60 nm, were characterized in terms of physicochemical properties and tested for potential biomedical applications. A significant decay in bacterial growth after 24 h was achieved for both Methicillin-resistant Staphylococcus aureus and multidrug-resistant Escherichia coli at a relative low concentration of 5 µg/mL, while there was no cytotoxicity towards human dermal fibroblasts after 3 days of treatment. AV-TeNPs also showed anticancer properties up to 72 h within a range of concentrations between 5 and 100 µg/mL. Consequently, here, we present a novel and green approach to produce Te-based nanostructures with potential biomedical applications, especially for antibacterial and anticancer applications.

scholarly journals Nitrile Synthesis with Aldoxime Dehydratases: A Biocatalytic Platform with Applications in Asymmetric Synthesis, Bulk Chemicals, and Biorefineries

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4466
Author(s):  
Pablo Domínguez de María
Keyword(s):  
Asymmetric Synthesis ◽  
Organic Solvents ◽  
Raw Materials ◽  
Aqueous Media ◽  
Industrial Processes ◽  
Polymer Chemistry ◽  
Fine Chemicals ◽  
Mild Conditions ◽  
Bulk Chemicals ◽  
Recent Developments

Nitriles comprise a broad group of chemicals that are currently being industrially produced and used in fine chemicals and pharmaceuticals, as well as in bulk applications, polymer chemistry, solvents, etc. Aldoxime dehydratases catalyze the cyanide-free synthesis of nitriles starting from aldoximes under mild conditions, holding potential to become sustainable alternatives for industrial processes. Different aldoxime dehydratases accept a broad range of aldoximes with impressive high substrate loadings of up to >1 Kg L−1 and can efficiently catalyze the reaction in aqueous media as well as in non-aqueous systems, such as organic solvents and solvent-free (neat substrates). This paper provides an overview of the recent developments in this field with emphasis on strategies that may be of relevance for industry and sustainability. When possible, potential links to biorefineries and to the use of biogenic raw materials are discussed.

Amorphous Polymeric Dithiazine apDTZ Solid Fouling: Critical Review, Analysis and Solution of an Ongoing Challenge in Triazine-Based Hydrogen Sulphide Mitigation

2021 ◽  
Author(s):  
Grahame Taylor ◽  
Jonathan Wylde ◽  
Walter Samaniego ◽  
Ken Sorbie
Keyword(s):  
Hydrogen Sulphide ◽  
Reaction Pathway ◽  
Theoretical Calculations ◽  
Mechanism Of Formation ◽  
Review Analysis ◽  
Operational Problem ◽  
Depth Study ◽  
The Common ◽  
By Products ◽  
A Current

Abstract Despite attempts to inhibit or avoid the formation of fouling deposits (polymeric amorphous dithiazine or apDTZ for short) from the use of MEA triazine, this remains a major operational problem and limits the use of this most popular and ubiquitous hydrogen sulphide (H2S) scavenger. This paper (a) reviews and summarizes previous work, (b) provides fresh insights into the reaction product and mechanism of formation, (c) proposes an effective method of removal, and (d) proposes some mechanisms of apDTZ digestion. The mechanism of apDTZ formation is discussed and reasoning is provided from a variety of perspectives as to the mechanism of MEA-triazine reaction with H2S. These include basicity and nucleophilic substitution considerations, steric properties and theoretical calculations for electron density. Novel procedures to chemically react with and destroy this solid fouling are presented with an in-depth study and experimental verification of the underlying chemistry of this digestion process. A review of agents to chemically destroy apDTZ is undertaken and a very effective solution has been found in peroxyacetic acid, which is much more powerful and effective than previously suggested peroxides. The structure of amorphous polymeric dithiazine is emphasized and the reason why this fouling cannot be 1,3,5-trithiane is stressed. This work therefore overcomes a current industry misconception by providing insight on two major paradoxes in the reaction pathway; namely i) why the thiadiazine reaction product from tris hydroxyethyl triazine (MEA triazine) is never observed and ii) why does the dithiazine in all cases never progress to the trithiane (3rd sulphur molecule substitution)? The latter issue is probably the biggest misconception in the industry and literature regarding triazine and H2S reactions. Many reasons for this are put forward and the common misconception of "overspent" triazine is refuted. A very effective chemical reaction that results in soluble by-products, counteracting the problems produced by this intractable polymer is found and their composition is proposed and experimentally verified.

Facile construction of leaf-like WO3 nanoflakes decorated on g-C3N4 towards efficient oxidation of alcohols under mild conditions

2018 ◽  
Vol 42 (20) ◽  
pp. 16523-16532 ◽  
Author(s):  
Cai Xu ◽  
Xiaozhong Wang ◽  
Gang Xu ◽  
Yingqi Chen ◽  
Liyan Dai
Keyword(s):  
Selective Oxidation ◽  
Aqueous Media ◽  
Mild Conditions ◽  
Oxidation Of Alcohols

Selective oxidation of aryl and alkyl alcohols with H2O2 in aqueous media catalyzed by a well-defined WO3/g-C3N4 composite.

Oxydation des alcènes par l'ion thallique. I. Stéréochimie et mécanisme de l'oxydation des cyclohexènes

1971 ◽  
Vol 49 (15) ◽  
pp. 2586-2589 ◽  
Author(s):  
C. Freppel ◽  
R. Favier ◽  
J.-C. Richer ◽  
M. Zador
Keyword(s):  
Aqueous Media ◽  
Hydroxyl Group ◽  
Step Method ◽  
One Step ◽  
Rigid Conformation

The stereochemistry of the diols obtained by oxidation of 3-t-butylcyclohexene by thallic sulfate indicates that the α hydroxyl group participates in the breaking of the C—T1 bond of the intermediate organothallous compound. The fact that only the trans diols are obtained indicates that an SN2 substitution of the thallium can be excluded. We suggest that the thallic oxidation in aqueous media of olefin of rigid conformation is an excellent one-step method of preparing trans diols. The formation of the trans diaxial diol upon oxidation of 4-t-butylcyclohexene tends to confirm that hypothesis.

scholarly journals Synthesis and functionalization of dextran-based single-chain nanoparticles in aqueous media

2017 ◽  
Vol 5 (6) ◽  
pp. 1143-1147 ◽  
Author(s):  
R. Gracia ◽  
M. Marradi ◽  
U. Cossío ◽  
A. Benito ◽  
A. Pérez-San Vicente ◽  
...  
Keyword(s):  
Aqueous Media ◽  
Polymer Nanoparticles ◽  
Single Chain ◽  
Chain Polymer ◽  
Water Dispersible ◽  
Mild Conditions

Water-dispersible dextran-based single-chain polymer nanoparticles (SCPNs) were prepared in aqueous media and under mild conditions.

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