Amidation Of Esters Research Articles

Research Progress in the Synthesis of N-Acyl Amino Acid Surfactants: A Review

This paper reviews the research progress in the synthesis of N-acyl amino acid surfactants, including chemical synthesis methods, enzymatic synthesis methods, chemo-enzymatic methods, and fermentation methods. Chemical synthesis is currently the main route for laboratory and industrial synthesis, including methods such as direct dehydration condensation of fatty acids, amidation of fatty acid anhydrides, carbonyl addition of fatty amides, amidation of fatty acid activated esters, amidation of fatty acid methyl esters, amidation of oils and fats, hydrolysis of fatty nitriles, and Schotten–Baumann condensation. Enzymatic synthesis has the advantages of mild reaction conditions and being green and pollution-free, but the yield is relatively low. The chemo-enzymatic method combines the advantages of enzymatic and chemical methods, but it has not been widely promoted. Fermentation methods have low production costs and are environmentally friendly but the technology is not yet mature. This paper elaborates on the principles, advantages, and disadvantages of each synthesis method and provides an outlook on future research directions.

Intramolecular Reductive Amidation of Unactivated Esters with Nitroarenes: A Telescoped Synthesis of Tetrahydropyrrolo/Pyrido[1,2-a]quinoxalinones.

A reductive amidation of unactivated esters with nitroarenes, a key step in the telescopic synthesis of tetrahydropyrrolo[1,2-a]quinoxalinones and tetrahydropyrido[1,2-a]quinoxalinones, is reported. The process involves an intermolecular base-mediated SNAr reaction, followed by intramolecular reductive amidation employing sodium dithionite. The substrate scope coupled with the demonstration of the synthesis of pharmaceuticals is reported. The key features include nitro reduction at room temperature, easy purification without chromatography, amidation of unactivated esters without any externally added activating agent, and a telescopic process.

Inverse Vulcanization of Activated Norbornenyl Esters – A Versatile Platform for Functional Sulfur Polymers

Elemental sulfur has shown to be a promising alternative feedstock for development of novel polymeric materials with high sulfur content. However, the utilization of inverse vulcanized polymers is restricted by the limitation of functional comonomers suitable for an inverse vulcanization. Control over properties and structure of inverse vulcanized polymers still poses a challenge to current research due to the dynamic nature of sulfur‐sulfur bonds and high temperature of inverse vulcanization reactions. In here, we report for the first time the inverse vulcanization of norbornenyl pentafluorophenyl ester (NB‐PFPE), allowing for post‐modification of inverse vulcanized polymers via amidation of reactive PFP esters to yield high sulfur content polymers under mild conditions. Amidation of the precursor material with three functional primary amines (α‐amino‐ω‐methoxy polyethylene glycol, aminopropyl trimethoxy silane, allylamine) was investigated. The resulting materials were applicable as sulfur containing poly(ethylene glycol) nanoparticles in aqueous environment. Cross‐linked mercury adsorbents, sulfur surface coatings, and high‐sulfur content networks with predictable thermal properties were achievable using aminopropyl trimethoxy silane and allylamine for post‐polymerization modification, respectively. With the broad range of different amines available and applicable for post‐polymerization modification, the versatility of poly(sulfur‐random‐NB‐PFPE) as a platform precursor polymer for novel specialized sulfur containing materials was showcased.

Inverse Vulcanization of Activated Norbornenyl Esters-A Versatile Platform for Functional Sulfur Polymers.

Elemental sulfur has shown to be a promising alternative feedstock for development of novel polymeric materials with high sulfur content. However, the utilization of inverse vulcanized polymers is restricted by the limitation of functional comonomers suitable for an inverse vulcanization. Control over properties and structure of inverse vulcanized polymers still poses a challenge to current research due to the dynamic nature of sulfur-sulfur bonds and high temperature of inverse vulcanization reactions. In here, we report for the first time the inverse vulcanization of norbornenyl pentafluorophenyl ester (NB-PFPE), allowing for post-modification of inverse vulcanized polymers via amidation of reactive PFP esters to yield high sulfur content polymers under mild conditions. Amidation of the precursor material with three functional primary amines (α-amino-ω-methoxy polyethylene glycol, aminopropyl trimethoxy silane, allylamine) was investigated. The resulting materials were applicable as sulfur containing poly(ethylene glycol) nanoparticles in aqueous environment. Cross-linked mercury adsorbents, sulfur surface coatings, and high-sulfur content networks with predictable thermal properties were achievable using aminopropyl trimethoxy silane and allylamine for post-polymerization modification, respectively. With the broad range of different amines available and applicable for post-polymerization modification, the versatility of poly(sulfur-random-NB-PFPE) as a platform precursor polymer for novel specialized sulfur containing materials was showcased.

Cesium Carbonate Promoted Direct Amidation of Unactivated Esters with Amino Alcohol Derivatives.

Cesium carbonate promoted direct amidation of unactivated esters with amino alcohols was developed without the use of transition-metal catalysts and coupling reagents. This method enabled the synthesis of several serine-containing oligopeptides and benzamide derivatives with yields up to 90%. The methodology proceeds under mild reaction conditions and exhibits no racemization for most naturally occurring amino acid substrates. The reaction demonstrates good compatibility with primary alkyl and benzyl esters and broad tolerance for a range of amino acid substrates with nonpolar and protected side chains. The hydroxy group on the amine nucleophile was found to be critical for the reaction to be successful. A likely mechanism involving cesium coordination to the substrates enabling the subsequent proximity-driven acyl transfer was proposed. The practicality of this approach was demonstrated in the preparation of a biologically active nicotinamide derivative in a reasonable yield.

Transamidation of secondary carboxamides and amidation of esters are facilitated by magnetic Co@NC nanoparticles, as a highly efficient and recyclable catalyst under neat conditions

Magnetic Co@NC nanoparticles catalysed transamidation of N-Boc-activated secondary amides and direct amidation of esters with amines has been developed. This technique exhibits excellent tolerance towards various functional groups.

Iron-Mediated Reductive Amidation of Triazine Esters with Nitroarenes.

A reductive amidation of triazine esters with nitroarenes by using cheap iron as a reducing metal in the presence of TMSCl in DMF was developed. The reactions proceeded efficiently under transition metal-free conditions to give the corresponding amides in moderate to good yields with good functional group compatibility. Preliminary mechanistic investigations indicated that nitrosobenzene, N-phenyl hydroxylamine, azoxybenzene, azobenzene, aniline, and N-arylformamide possibly served as the intermediates of the reaction.

LaCoO3 nanorod immobilized waste egg shell: a nanocatalytic system for the reduction of water pollutants and direct amidation of esters

LaCoO3 nanorod immobilized waste egg shell: a nanocatalytic system for the reduction of water pollutants and direct amidation of esters

Tin(II) Chloride-Catalyzed Direct Esterification and Amidation of tert-Butyl Esters Using α,α-Dichlorodiphenylmethane Under Mild Conditions.

A practical one-pot synthesis of esters and amides from tert-butyl esters via acid chloride was developed. Reactions of tert-butyl esters with α,α-dichlorodiphenylmethane as the chlorinating agent and SnCl2 as catalyst-generated acid chloride intermediates in situ were subsequently used in reactions with a variety of alcohols and amines to afford the corresponding esters and amides in high yields under mild reaction conditions. This catalytic synthetic procedure offers an effective strategy for the facile esterification and amidation of tert-butyl esters.

Streamlining the synthesis of amides using Nickel-based nanocatalysts

The synthesis of amides is a key technology for the preparation of fine and bulk chemicals in industry, as well as the manufacture of a plethora of daily life products. Furthermore, it constitutes a central bond-forming methodology for organic synthesis and provides the basis for the preparation of numerous biomolecules. Here, we present a robust methodology for amide synthesis compared to traditional amidation reactions: the reductive amidation of esters with nitro compounds under additives-free conditions. In the presence of a specific heterogeneous nickel-based catalyst a wide range of amides bearing different functional groups can be selectively prepared in a more step-economy way compared to previous syntheses. The potential value of this protocol is highlighted by the synthesis of drugs, as well as late-stage modifications of bioactive compounds. Based on control experiments, material characterizations, and DFT computations, we suggest metallic nickel and low-valent Ti-species to be crucial factors that makes this direct amide synthesis possible.

Accelerated Amidation of a Glycine Propargyl Ester on a Polymer and the Two-Way Use of One-Pot Double Postpolymerization Modification with Click Chemistry

Abstract The glycine propargyl (GP) ester moiety, as a newly activated ester, is a candidate for amidation in modification reactions and can be combined with click chemistry. Here, the amidation of GP esters on a polymer side chain was investigated using various amino-group-containing compounds. The amidation on the GP ester proceeded well when n-alkyl, cycloalkyl, and aromatic-group-containing primary amines were used without a catalyst under neutral conditions. Hydrophilic amines containing hydroxy and carboxy groups provided no amidation products. The amidation on the polymer was accelerated by the neighboring group effect on the polymer side chain. One-pot double postpolymerization modification was achieved using a GP ester-bearing polymer by combining amidation with the Huisgen cycloaddition.

Thiourea-Catalyzed Amidation of Esters: A New Method for the Preparation of Amides

Abstract: Although amides are one of the most abundant bonds in biology and medicinal chemistry, methods to prepare them are still limited. To expand on current methods for the formation of amides bonds, organocatalysts (thiourea-based) were developed to mediate the conversion of esters to amides. The reactions proceed in good to moderate yields and tolerate a variety of functional groups. 1 H NMR titration and computational studies show a strong hydrogen-bonding interaction between the thiourea catalyst and the ester moiety. This hydrogen-bonding interaction is proposed to be the driving force for the amidation of esters.

A sustainable metal and base-free direct amidation of esters using water as a green solvent.

Herein, we report a simple and efficient synthetic approach for direct amidation of esters via C(acyl)-O bond cleavage without any additional reagents or catalysts, using only water as a green solvent. Subsequently, the reaction byproduct is recovered and utilized for the next phase of ester synthesis. This method emphasized metal-free, additive-free, and base-free characteristics making it a new, sustainable, and eco-friendly way to realize direct amide bond formation. In addition, the synthesis of the drug molecule diethyltoluamide and the Gram-scale synthesis of a representative amide are demonstrated.

Mechanistic Understanding of KOt Bu-Mediated Direct Amidation of Esters with Anilines: An Experimental Study and Computational Approach.

A sustainable and cost-effective protocol has been reported for the synthesis of amide bonds from unactivated esters and non-nucleophilic amines promoted by potassium tert-butoxide under aerobic conditions. The reaction proceeds under relatively mild conditions, encompassing wide substrate scope. A combined experimental and quantum chemical study has been performed to shed light on the mechanism, which implied that a radical pathway is operating for the present protocol.

Magnetic Hyperbranched Molecular Materials for Treatment of Oily Sewage Containing Polymer in Oilfield Compound Flooding.

With the continuous improvement in oilfield development and the application of tertiary oil recovery technology, the water content of oilfield-produced fluids has gradually increased, and a large number of oilfield sewage with complex components has also been produced after oil–water separation, and effective treatment is urgently needed. ASP flooding sewage contains alkali, various surfactants, polymers, microemulsion oil droplets, and solid impurities, which are difficult to be effectively treated by traditional water treatment agents and methods. In this study, aminopropyl triethoxysilane (APTES) was used to modify the nano-Fe3O4 coated with tetraethyl silicate (TEOS). The product was used as the ferromagnetic nano-core for the iterative reaction of Michael addition and ester amidation to synthesize a magnetic hyperbranched polyamide amine, and its performance in the treatment of ASP flooding wastewater was evaluated experimentally. For the preparation of APTES-modified Fe3O4@SiO2 (FOSN) product, TEOS was coated over Fe3O4 in an ethanol aqueous solution environment and then APTES was added dropwise. The first-generation branched product (1-FSMN) was obtained by the reaction of FOSN and methyl acrylate graft product (FOSN-M) with ethylenediamine, and the highest yield was 93.7%. The highest yield of the second-generation branched product (2-FSMN) was 91.6%. In this study, a composite flooding wastewater sample from a block in the Bohai oilfield was taken. The suspended solids content was 143 mg/L, the oil content was 921.09 mg/L, the turbidity was 135 NTU, and the zeta potential was −47 mV. The third-generation hyperbranched polymer (3-FSMN) and its quaternary ammonium salt (3-FSMN-Q) performed best in the appropriate dosage range, with the highest oil removal rate of 97%, suspended solid removal rate of 90.3%, turbidity reduction rate of 86.6% and zeta potential reduction rate of 88%. For 3-FSMN and its quaternary ammonium salt, the gravity/magnetic PAC compound treatment experiment was carried out. In the settlement time of only 5 min, 3-FSMN/PAC and 3-FSMN-Q/PAC can achieve the maximum oil removal rate of 87.1% and suspended solids removal rate of 87.3% for polymer containing wastewater from ASP flooding, and 86.3 and 86.0% for 120 mg/L. Its treatment capacity was much better than that of common treatment agent combination (CPAM/PAC).

Synthesis and characterization of dendritic compounds containing nitrogen: monomer precursors in the construction of biomimetic membranes

In this article, we synthesized a novel dendritic 2-oxazoline, 2-(3,4,5-tris(4-dodecyloxybenzyloxy)phenyl)-4,5-dihydro-1,3-oxazole), and its amide precursor N-(2-hydroxyethyl)-3,4,5-tris(4-dodecyloxybenzyloxy)benzamide. Of the distinct synthetic routes explored, it was established that the direct amidation of esters with sodium methoxide followed by the dehydrative cyclisation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as oxidizing agent and triphenylphosphine was the most efficient route to synthesize the dendritic 2-oxazoline. Besides, N-(2-hydroxyethyl)-3,4,5-tris(4-dodecyloxybenzyloxy)benzamide exhibited a monotropic columnar mesophase, whilst the dendritic 2-oxazoline does not exhibited a liquid crystalline mesophase. At the end, the first attempts to polymerize the 2-oxazoline monomer via cationic ring opening polymerization showed promising results. Therefore, the dendritic 2-oxazoline could be used as a mesogenic monomer in the synthesis of side-chain liquid-crystalline polyoxazolines that might self-assembly into columnar structures.

Iridium-Catalyzed Amidation of In Situ Prepared Silyl Ketene Acetals to Access α-Amino Esters.

Disclosed herein is a convenient Ir-catalyzed amidation of esters to access α-amido esters. Initially prepared silyl ketene acetals are directly employed, without separate purification, for subsequent amidation with an oxycarbonylnitrenoid precursor using the Cp*(LX)Ir(III) catalyst. The α-amidation was facile for both α-aryl and α-alkyl esters. Density functional theory studies revealed that the generation of a putative Ir-nitrenoid is facilitated by the chelation of the countercation additive during the N-O bond cleavage of the nitrene precursor.

Base-promoted direct amidation of esters: beyond the current scope and practical applications.

The base-promoted direct amidation of unactivated esters is among the most useful reactions for amide bond formation in contemporary organic chemistry. The intensive research in this area has led to the development of a number of new methods to achive this transformation. However, to date, the existing literature is more methodological and in many instances lacks practical directions. Therefore, the full potential of this transformation is yet to be revealed by broadening the substrate scope. In a search for new practical applications of the amidation reaction, herein we present a comprehensive study of a number of base-promoted direct amidations that encompass a wide range of amines and esters. Furthermore, we applied our findings in the synthesis of phosphoramidates and several industrially relevant products.

Investigation of Co3O4 Activity and Stability in Amidation of Fatty Acid Methyl Esters

AbstractCo3O4 activity in amidation reaction between fatty acid methyl esters and 3‐(Dimethylamino)‐1‐propylamine was investigated for the first time. The catalytic effect was approved by comparison of non‐catalyzed and catalyzed reactions activation energies and connected with the unique structure of Co3O4. Using of Co3O4 allows decreasing of activation energy of amidation reaction up to 1.5 times (from 90 to 59 kJ/mol). During the recycling test no significant decrease in reaction rate and product yield was detected even after 5 cycles. Using various analysis methods (XRD, FTIR, EDS‐SEM) of fresh and spent catalyst it was fixed that Co3O4 has no transformation throughout the synthesis.

Efficient synthesis of primary and secondary amides via reacting esters with alkali metal amidoboranes

Amides are one of the most important organic compounds that are widely applied in medicine, biochemistry, and materials science. To find an efficient synthetic method of amides is a challenge for organic chemistry. We report here a facile synthesis method of primary and secondary amides through a direct amidation of esters with sodium amidoboranes (NaNHRBH3, R = H, Me), at room temperature without using catalysts and other reagents. This process is rapid and chemoselective, and features quantitative conversion and wide applicability for esters tolerating different functional groups. The experimental and theoretical studies reveal a reaction mechanism with nucleophilic addition followed by a swift proton transfer-induced elimination reaction.