scholarly journals First Example of Unsaturated Poly(Ester Amide)s Derived From Itaconic Acid and Their Application as Bio-Based UV-Curing Polymers

2020 ◽  
Vol 10 (6) ◽  
pp. 2163 ◽  
Author(s):  
Rim Ouhichi ◽  
Sacha Pérocheau Arnaud ◽  
Abdelkader Bougarech ◽  
Souhir Abid ◽  
Majdi Abid ◽  
...  
Keyword(s):  
Double Bond ◽  
Itaconic Acid ◽  
Michael Addition ◽  
Addition Reaction ◽  
Ultra Violet ◽  
Uv Curing ◽  
Building Blocks ◽  
Amide Group ◽  
Polyester Resins ◽  
Printing Inks

Recently, itaconic acid has drawn considerable attention as a novel radical-curing building block for polyester resins. These bio-based materials have been used in thermal, as well as ultra violet (UV) curing applications, such as printing inks or coatings. Poly(ester amide)s from itaconic acid could be very interesting, as the amide group could alter the properties of the resins as well as cured materials. However, standard polycondensation reactions with diamines are not possible with itaconic acid as the amines preferably react via an aza-Michael addition at the α,β-unsaturated double bond. Therefore, alternative and more elaborate synthetic strategies have to be developed. Herein, we present two different synthetic strategies to poly(ester amide)s from itaconic acid that circumvent the addition reaction of the amines. This is in both cases done by a pre-reaction to form stable amide building blocks that are then reacted with itaconic acid or polyesters derived thereof. The structural composition and the properties of the resin are characterized, and the UV-curing reactivity is examined. All properties are compared to corresponding polyesters from itaconic acid.

scholarly journals Straightforward Synthetic Protocol to Bio-Based Unsaturated Poly(ester amide)s from Itaconic Acid with Thixotropic Behavior

Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 980 ◽  
Author(s):  
Lazaros Papadopoulos ◽  
Marcel Kluge ◽  
Dimitrios N. Bikiaris ◽  
Tobias Robert
Keyword(s):  
Itaconic Acid ◽  
Renewable Resources ◽  
Uv Curing ◽  
Building Blocks ◽  
Side Reactions ◽  
Addition Reactions ◽  
Polyester Resins ◽  
Amide Bonds ◽  
Before And After ◽  
Thixotropic Behavior

In the field of polymer chemistry, tremendous efforts have been made over the last decade to replace petrochemical monomers with building blocks from renewable resources. In this respect, itaconic acid has been used as an alternative to acrylic acid or maleic acid in unsaturated polyesters for thermal or UV-curing applications. However, examples of poly(ester amide)s from itaconic acid are scarce. Under standard polycondensation reactions, the presence of free amines leads to aza-Michael addition reactions at the α,β-unsaturated double bond of the itaconic acid and isomerization reactions to mesaconic acid. Both reactions make the resulting materials useless as UV-curing polymer resins. To avoid these undesired side reactions, we herein report the use of preformed, well-defined diols containing internal amide bonds. The resulting unsaturated poly(ester amide) resins were analyzed before and after UV-induced crosslinking. Viscosity measurements revealed a strong thixotropic behavior induced by the amide groups, which is usually not detected in structurally similar polyester resins.

Enaminones as Building Blocks In Heterocyclic Synthesis: A New One Pot Synthesis of Polyfunctional Substituted Pyridines

2001 ◽  
Vol 56 (10) ◽  
pp. 1074-1078 ◽  
Author(s):  
Samia Michel Agamy ◽  
Mervat Mohammed Abdel-Khalik ◽  
Mona Hassan Mohamed ◽  
Mohammed Hilmy Elnagdi
Keyword(s):  
Acetic Acid ◽  
Double Bond ◽  
Aromatic Aldehyde ◽  
Michael Addition ◽  
Ammonium Acetate ◽  
Building Blocks ◽  
Heterocyclic Synthesis ◽  
One Pot ◽  
Active Methyl ◽  
Substituted Pyridines

Enaminones react with a variety of active methyl and methylene reagents in presence of ammonium acetate to yield functionally substituted pyridines in good yields. The reaction proceeded via initial Michael addition across the double bond followed by cyclization. The reaction of enaminone with aromatic aldehyde in acetic acid/ammonium acetate afforded the dihydropyridine that was oxidized to the corresponding pyridine.

Exploiting the Carbon and Oxa Michael Addition Reaction for the Synthesis of Yne Monomers: Towards the Conversion of Acrylates to Biocompatible Building Blocks

ChemPhotoChem ◽  
2020 ◽  
Vol 4 (7) ◽  
pp. 476-480
Author(s):  
Daniel Hennen ◽  
Delara Hartmann ◽  
Paul H. Rieger ◽  
Andreas Oesterreicher ◽  
Johannes Wiener ◽  
...  
Keyword(s):  
Michael Addition ◽  
Addition Reaction ◽  
Building Blocks ◽  
Michael Addition Reaction

Cupin Variants as Macromolecular Ligand Library for Stereoselective Michael Addition of Nitroalkanes

2019 ◽  
Author(s):  
Nobutaka Fujieda ◽  
Miho Yuasa ◽  
Yosuke Nishikawa ◽  
Genji Kurisu ◽  
Shinobu Itoh ◽  
...  
Keyword(s):  
Michael Addition ◽  
In Silico ◽  
Addition Reaction ◽  
Single Point ◽  
Point Mutations ◽  
Unsaturated Ketone ◽  
Michael Addition Reaction ◽  
Beta Barrel ◽  
Cupin Superfamily ◽  
Single Point Mutations

Cupin superfamily proteins (TM1459) work as a macromolecular ligand framework with a double-stranded beta-barrel structure ligating to a Cu ion through histidine side chains. Variegating the first coordination sphere of TM1459 revealed that H52A and H54A/H58A mutants effectively catalyzed the diastereo- and enantio-selective Michael addition reaction of nitroalkanes to an α,β-unsaturated ketone. Moreover, in silico substrate docking signified C106N and F104W single-point mutations, which inverted the diastereoselectivity of H52A and further improved the stereoselectivity of H54A/H58A, respectively.

Recent Synthetic Approaches and Biological Evaluations of Amino Hexahydroquinolines and Their Spirocyclic Structures

2019 ◽  
Vol 19 (7) ◽  
pp. 875-915 ◽  
Author(s):  
Amr M. Abdelmoniem ◽  
Magda F. Mohamed ◽  
Doaa M. Abdelmoniem ◽  
Said A.S. Ghozlan ◽  
Ismail A. Abdelhamid
Keyword(s):  
Double Bond ◽  
Calcium Channel ◽  
Michael Addition ◽  
Antitubercular Agents ◽  
Sar Studies ◽  
Two Component ◽  
Synthetic Routes ◽  
Synthetic Approaches ◽  
Three Components

In this review, the recent synthetic approaches of amino hexahydroquinolines and their spirocyclic structures were highlighted. The synthetic routes include, two-components, three-components or fourcomponents reactions. The two-component [3+3] atom combination reaction represents the simplest method. It involves Michael addition of the electron rich β-carbon of β-enaminones to the activated double bond of cinnamonitriles followed by cyclization to yield hexahydroquinoline compounds. The bioactivity profiles and SAR studies of these compounds were also reviewed with emphasis to the utility of these substances as antimicrobial, anticancer and antitubercular agents, as well as calcium channel modulators.

scholarly journals Recoverable Phospha-Michael Additions Catalyzed by a 4-N,N-Dimethylaminopyridinium Saccharinate Salt or a Fluorous Long-Chained Pyridine: Two Types of Reusable Base Catalysts

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1159
Author(s):  
Eskedar Tessema ◽  
Vijayanath Elakkat ◽  
Chiao-Fan Chiu ◽  
Jing-Hung Zheng ◽  
Ka Long Chan ◽  
...  
Keyword(s):  
Michael Addition ◽  
Polar Solvent ◽  
Addition Reaction ◽  
High Yield ◽  
Addition Reactions ◽  
Polar Solvents ◽  
Unsaturated Bond ◽  
Base Catalysts ◽  
Michael Additions

Phospha-Michael addition, which is the addition reaction of a phosphorus-based nucleophile to an acceptor-substituted unsaturated bond, certainly represents one of the most versatile and powerful tools for the formation of P-C bonds, since many different electrophiles and P nucleophiles can be combined with each other. This offers the possibility to access many diversely functionalized products. In this work, two kinds of basic pyridine-based organo-catalysts were used to efficiently catalyze phospha-Michael addition reactions, the 4-N,N-dimethylaminopyridinium saccharinate (DMAP·Hsac) salt and a fluorous long-chained pyridine (4-Rf-CH2OCH2-py, where Rf = C11F23). These catalysts have been synthesized and characterized by Lu’s group. The phospha-Michael addition of diisopropyl, dimethyl or triethyl phosphites to α, β-unsaturated malonates in the presence of those catalysts showed very good reactivity with high yield at 80–100 °C in 1–4.5 h with high catalytic recovery and reusability. With regard to significant catalytic recovery, sometimes more than eight cycles were observed for DMAP·Hsac adduct by using non-polar solvents (e.g., ether) to precipitate out the catalyst. In the case of the fluorous long-chained pyridine, the thermomorphic method was used to efficiently recover the catalyst for eight cycles in all the reactions. Thus, the easy separation of the catalysts from the products revealed the outstanding efficacy of our systems. To our knowledge, these are good examples of the application of recoverable organo-catalysts to the DMAP·Hsac adduct by using non-polar solvent and a fluorous long-chained pyridine under the thermomorphic mode in phospha-Michael addition reactions.

Synthesis of sp3-Enriched β-Fluoro Sulfonyl Chlorides

Synthesis ◽  
2020 ◽  
Author(s):  
Oleksandr O. Grygorenko ◽  
Rustam Gurbanov ◽  
Andriy Sokolov ◽  
Sergey Golovach ◽  
Kostiantyn Melnykov ◽  
...  
Keyword(s):  
Drug Discovery ◽  
Double Bond ◽  
Building Blocks ◽  
Protecting Groups ◽  
Sulfonyl Chlorides ◽  
Wide Range ◽  
Cyclic Compounds

AbstractA three-step approach to the synthesis of sp3-enriched β-fluoro sulfonyl chlorides starting from alkenes is reported. The method was successfully applied to a wide range of acyclic and cyclic substrates, bearing either an exocyclic or an endocyclic double bond. The procedure worked with a wide range of substrates and tolerated a number of functional and protecting groups. Moreover, the target cyclic compounds were obtained as single cis diastereomers on a multigram scale. The title compounds are promising building blocks for drug discovery that can be used to obtain sp3-enriched β-fluoro and α,β-unsaturated sulfonamides.

Tandem Alkylation/Michael Addition Reaction of Dithiocarbamic Acids with Alkyl γ-Bromocrotonates: Access to Functionalized 1,3-Thiazolidine-2-thiones

Synthesis ◽  
2021 ◽  
Author(s):  
Azim Ziyaei Halimehjani ◽  
Petr Beier ◽  
Maryam Khalili Foumeshi ◽  
Ali Alaei ◽  
Blanka Klepetářová
Keyword(s):  
Amino Acids ◽  
Carbon Disulfide ◽  
Multicomponent Reaction ◽  
Michael Addition ◽  
Addition Reaction ◽  
Primary Amines ◽  
Oxidation Reactions ◽  
Michael Addition Reaction ◽  
Synthetic Utility ◽  
Reaction Proceeds

AbstractThiazolidine-2-thiones were prepared via a novel multicomponent reaction of primary amines (amino acids), carbon disulfide, and γ-bromocrotonates. The reaction proceeds via a domino alkylation/intramolecular Michael addition to provide the corresponding thiazolidine-2-thiones in high to excellent yields. By using diamines in this protocol, bis(thiazolidine-2-thiones) derivatives were synthesized. The synthetic utility of the adducts was demonstrated by hydrolysis, amidation, and oxidation reactions.

Bisphosphine catalyzed sequential [3 + 2] cycloaddition and Michael addition of ynones with benzylidenepyrazolones via dual α′,α′-C(sp3)–H bifunctionalization to construct cyclopentanone-fused spiro-pyrazolones

2018 ◽  
Vol 16 (48) ◽  
pp. 9461-9471 ◽  
Author(s):  
Jiayong Zhang ◽  
Zhiwei Miao
Keyword(s):  
Michael Addition ◽  
Addition Reaction ◽  
Michael Addition Reaction

A sequential [3 + 2] cycloaddition and Michael addition reaction of ynones with benzylidenepyrazolones afforded cyclopentanone-fused spiro-pyrazolones catalyzed by DPPB via dual α′,α′-C(sp3)–H bifunctionalization.

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