Aminolysis Reaction Research Articles

Novel uremic metabolite-based zwitterionic polyethersulfone (PES) hemodialysis membrane for improved hemocompatibility: Towards the fourth generation of hemodialysis modifiers

ESRD patients suffer from side effects of the dialysis process. Comprehension of different operational parameters’ effect on the hemocompatibility profiles of the separative membranes, i.e. dialyzers, could result in designing more compatible materials. This study includes a computational approach to assess the effect of pH by assessing different uremic metabolites' behavior. The pH effect was assessed by comparing the water interaction ability of different uremic metabolites (which appear at different bloodstream pH levels) using molecular dynamics (MD) simulations. Based on the findings of the studies, a new class of zwitterionic materials is introduced. The proposed modification, containing guanidine (GNDM) was experimentally implemented on poly ether sulfone (PES) membranes. Aminolysis and sultone-ring opening reactions were used to immobilize the zwitterionic structure. Attuned total reflectance-Furrier transmission infrared spectroscopy (ATR-FTIR) was used to characterize the functional groups of the modified membrane. Gravimetry was used to measure the amount of modification layer added to the membrane as well as the equilibrium water content (EWC). Atomic force microscopy (AFM) was used to measure the roughness patterns of the neat and modified membranes. Zeta potential analyzer was used to check the trend of surface charge variations. Differential scanning calorimetry (DSC) was used to assess the stable water content of the membranes. A filtration test was performed to check the stability of the immobilized materials on the membranes. The newly modified PES membranes were nearly 50 % smoother and negatively charged. DSC reflects a 16 % higher content of stable water for the modified membranes. Computational assessments also reflected that the modified structure created more hydrogen bonds and could keep the water molecules more stable on the surface of the membrane. As the new membrane owned a higher capability to keep the water more stable on its surface, it could be a perfect candidate for a hemocompatible dialysis membrane.

Surface modification of poly(methyl methacrylate)-sulphadiazine complexes as self photostabilizer against Ultraviolet (UV) Irradiation

ABSTRACT Surface functionalization of PMMA by Aminolysis reaction was utilised along with the addition of inorganic photo stabilisers (Zn(II), Ni(II), Cu(II) and Co(II)) to enhance the photostability of PMMA under exposure to UV light. The new polymers were characterised via different spectroscopic techniques. In order to assess the effectiveness of the PMMA films, Tinuvin 622, a commercial photo-stabiliser, was employed to assess the photostabilizing efficiency of our approach. The results have shown that Copper chloride was the most effective photostabilizer, followed by nickel, cobalt, and zinc chloride, in that order.

Acetylation of amines and alcohols catalyzed by acetylcholinesterase from Pseudomonas aeruginosa PAO1

Acetylcholinesterase (AChE) from Pseudomonas aeruginosa PAO1 has a catalytic Ser residue in its active site. In this study, we examined the aminolysis and alcoholysis reactions of AChE that occurred alongside its hydrolysis reaction. The recombinant AChE recognized ethyl acetate as a substrate. Therefore, we evaluated acetylation of the amine and hydroxyl group by AChE, using acetylcholine and ethyl acetate as the acetyl donor. AChE recognized diaminoalkanes with 4- to 12-carbon chains and aminoalcohols with 4- to 8-carbon chains as acetyl acceptors, resulting in their acetylated products. In the acetylation of 1,6-diaminohexane, AChE preferentially used ethyl acetate as the acetyl donor above pH 8.0 and the efficiency increased with increasing pH. In contrast, the acetylation of 6-amino-1-hexanol was efficient with acetylcholine as the acetyl donor in the pH range of 4–10. In addition, acetylated 6-amino-1-hexanol was decomposed by AChE. The kinetic study indicated that the acetyl donor and acceptor are competitively recognized by AChE as substrates.

Modification of Thermoresponsive Poly(<i>N</i>-Isopropylacrylamide) End-Group with Hydrophilic and/or Hydrophobic Compounds Tuned the LCST

Poly (N-isopropylacrylamide) (PNIPAAm) is one of the most well-known thermoresponsive polymers that exhibits a reversible coil-to-globule transition in aqueous solution at lower critical solution temperature (LCST) (32°C). PNIPAAm behave as an extended coil form in an aqueous solution below the LCST, meanwhile, above the LCST, it shrinks into a globule form. The LCST of PNIPAAm could be tune when it is chemically modified with hydrophilic and/or hydrophobic compound. In this study, modifications of PNIPAAm end-group with maleimide or phenyl maleimide compounds were prepared and their LCST behaviours were investigated. One end-group of synthesized poly (N-isopropylacrylamide)-chain transfer agent (PNIPAAm-CTA) was modified with maleimide or phenyl maleimide compound through aminolysis reaction to form PNIPAAm-Maleimide (PNIPAAm-M) and PNIPAAm-Phenyl maleimide (PNIPAAm-PhM). Maleimide is a hydrophilic compound, and phenyl maleimide is a slight hydrophobic compound were used in this study. The modification with hydrophilic compound will higher the LCST of PNIPAAm. The slight hydrophobic of phenyl maleimide compound will decrease the LCST. In this study, the successfulness of aminolysis process of PNIPAAm-CTA were determined through the fourier transform infrared (FTIR). Moreover, the LCST behavior of PNIPAAm-CTA, PNIPAAm-M and PNIPAAm-PhM were determined through light scattering intensity analysis. The results indicated that upon heating the solutions of PNIPAAm-CTA, PNIPAAm-M and PNIPAAm-PhM in 10 mM HEPES solution pH 7.4 at 25°C–40°C, PNIPAAm-CTA, and PNIPAAm-PhM solutions started to increase their light intensities at 35°C and PNIPAAm-M at 36°C, respectively. To conclude, modification of PNIPAAm end-group with hydrophobic and/or hydrophilic compound could tune their LCST.

Synthesis of amines: From a microwave batch reactor to a continuous milliflow reactor with heterogeneous feed and product

The aminolysis reaction is used to prepare amines or amides and is mainly performed in a batch reactor. Increased safety, product yield and quality are important drivers to convert batch to flow processes. However, handling of suspensions in flow reactors remains challenging due to sedimentation and clogging. This research investigates an aminolysis reaction with heterogeneous feed and product. Solvent screening is performed in a batch reactor to select the optimal non-hazardous solvent. Next, the influence of the reaction parameters are researched with 3–6 equivalents of aqueous ammonia, temperature of 180–240 °C and residence time (RT) of 5–15 min. Results show that polar aprotic solvents are most suitable and the highest obtained yield was 86.4%. Although, lowering of the RT to 5 min, lowers the amount of side product. Finally, the optimal reaction conditions are successfully applied in a pulsatile flow reactor. With 0.85 M starting material (solid content 22m%), feed and product are both heterogeneous, the reactor works without clogging. The obtained product yield is 97% at 210 °C and 5 min of RT, corresponding to a production of 6 g/min. In conclusion, by focusing on solid transport during reactor design, the aminolysis reaction is an excellent candidate for continuous synthesis.

Modified basicity from ZnO‐CaO synergy for the synthesis of oxamide

AbstractComposite ZnO‐CaO catalysts with different Zn/Ca molar ratios were investigated, and the ZnCa‐0.25 (Zn/Ca=0.25) catalyst showed excellent catalytic performance on the aminolysis reaction of dimethyl oxalate for oxamide (OA) synthesis. The physicochemical properties of the catalyst were investigated by XRD, Raman, SEM, STEM, XPS, CO2‐TPD, UV‐vis diffuse reflectance. The results indicated that strong basic sites created by ZnO‐CaO synergy could promote the aminolysis of dimethyl oxalate (DMO). Upper moved valence band top in the ZnCa‐0.25 suggested feasible electron transition in basic sites, which endowed catalyst stronger ability on the electron donor at the active site had a stronger effect on the activation of reactants at the ZnO‐CaO interface, thus led to a remarkable OA yield of 97.6 %.

An Efficient Synthesis and Preliminary Investigation of Novel 1,3-Dihydro-2H-benzimidazol-2-one Nitro and Nitramino Derivatives.

The preparation and properties of a series of novel 1,3-dihydro-2H-benzimidazol-2-one nitro and nitramino derivatives are described. A detailed crystal structure of one of the obtained compounds, 4,5,6-trinitro-1,3-dihydro-2H-benzimidazol-2-one (TriNBO), was characterized using low temperature single crystal X-ray diffraction, namely an orthorhombic yellow prism, space group 'P 2 21 21', experimental crystal density 1.767 g/cm3 (at 173 K). Methyl analog, 5-Me-TriNBO-monoclinic red plates, space group, P 21/c, crystal density 1.82 g/cm3. TriNBO contains one activated nitro group at the fifth position, which was used for the nucleophilic substitution in the aminolysis reactions with three monoalkylamines (R=CH3, C2H5, (CH2)2CH3) and ethanolamine. The 5-R-aminoderivatives were further nitrated with N2O5/ HNO3 and resulted in a new group of appropriate nitramines: 1,3-dihydro-2H-5-R-N(NO2)-4,6-dinitrobenzimidazol-2-ones. Thermal analysis (TGA) of three selected representatives was performed. The new compounds possess a high melting point (200-315 °C) and thermal stability and can find a potential application as new thermostable energetic materials. Some calculated preliminary energetic characteristics show that TriNBO, 5-Me-TriNBO, 5-methylnitramino-1,3-dihydro-2H-4,6-dinitrobenzimidazol-2-one, and 5-nitratoethylnitramino-1,3-dihydro-2H-4,6-dinitrobenzimidazol-2-one possess increased energetic characteristics in comparison with TNT and tetryl. The proposed nitrocompounds may find potential applications as thermostable high-energy materials.

Semi-synthesis of biotin-bearing activity-based ubiquitin probes through sequential enzymatic ligation, N-S acyl transfer and aminolysis reaction

Activity-based Ubiquitin probes (Ub-ABPs) carrying a reporter group have emerged as effective tools for the investigation of deubiquitinating enzymes (DUBs), such as studying the molecular mechanism of DUBs, profiling new DUBs. But so far, the synthesis of commonly used biotin-bearing Ub-ABPs is a technical challenge. Here, we report a one-pot semi-synthetic strategy for the acquiring of Ub-ABPs carrying a biotin tag through sequential enzymatic ligation, N-S acyl transfer and aminolysis reaction without any purification steps. These probes enable to capture the different family of DUBs for enrichment and immunoblotting using the attached biotin tag.

Hydrolysis and aminolysis of aldehydes catalyzed by water and amines: Formation of diols/aminol and the implication to atmospheric particle formation

The hydrolysis and aminolysis reactions of aldehydes were proved to be associated with the secondary organic aerosols (SOA) in the atmosphere. However, these reactions are forbidden owing to the high energy barriers. To make these reactions feasible and assess the catalytic ability of water molecules and amines, the hydrolysis and aminolysis of glyoxal (GL) and glycolaldehyde (GA) were investigated using quantum chemical calculations. The results show that water molecules and amines can catalyze effectively the hydrolysis and aminolysis of aldehydes and the catalytic ability of water molecules is stronger than that of methylamine (MA) and dimethylamine (DMA). Glycine (Gly) can play a stronger role than water molecules in the GL/GA hydrolysis and aminolysis reactions owing to the carboxyl group. At low relative humidity and high pollution condition, the effective rate constants of Gly-catalyzed reactions can be comparable to that of water-catalyzed reactions. The results of MD simulations indicate that the products of GL/GA hydrolysis and aminolysis can participate in the new particle formation (NPF) involving sulfuric acid (SA).

Effect of Functionalization of the Polycaprolactone Film Surface on the Mechanical and Biological Properties of the Film Itself.

The lack of suitable functional groups for cell adhesion on the surface of Polycaprolactone (PCL) is one of the main limitations in order to use PCL for biomedical applications. The aim of this research is to modify the PCL film surface using arginine, via an aminolysis reaction. In this regard, after PCL films formation by casting method, they were immersed in arginine solutions of various concentration at room temperature or then heated to 40 °C and in the presence of isopropanol or without it. To assess the structure of the modified surface, its wettability, and mechanical properties, methods of measuring the contact angle and the strip tensile test were used, and to compare the degree of attachment and the rate of cell proliferation, the method of fluorescent staining of cultured cells was used. The change in protein synthesis by cells on the modified surface was assessed using Western blotting. The results obtained show that the treatment of PCL films with an aqueous solution of arginine at room temperature for 1 day increases the hydrophilicity of the surface. Wherein surface modification led to a two-fold decrease of mechanical strength and flow stress, but elongation increase by about 30% for PCL films after modification in 0.5 M aqueous arginine solution at room temperature. Moreover, cell attachment and proliferation, as well as collagen synthesis, were significantly enhanced after arginine modification. The proposed simple and effective method for modifying PCL films with arginine significantly expands the possibilities for developing biocompatible scaffolds for tissue engineering.

High-Temperature Performance Enhancement of Bitumen by Waste PET-Derived Polyurethane

Bitumen performance enhancement through modification by reactive polymers gained significant attention in the road construction industry. Polymeric bitumen additives, such as polyurethane, improve bitumen properties at low and high in-service temperatures. This research aimed to increase the polymer content (polyurethane) from 3% to 5%wt of bitumen by introducing cross-linking agent, sulfur. Synthesis of polyurethane was via in situ polymerization of bis (2-hydroxyethyl) terephthalamide (BHETA) in the presence of bitumen with sulfur as a cross-linking agent. BHETA was produced from polyethylene terephthalate (PET) by an aminolysis reaction. Penetration and softening point, frequency sweep test, performance grade (PG) and multiple stress creep recovery (MSCR) were evaluated to compare base and modified bitumen. Results show that the penetration and softening point of modified binders were reduced and increased, respectively, the frequency sweep test indicated improvement in viscoelastic properties of modified bitumen, PG of base bitumen was enhanced by two grades, i.e., from 58°C to 70°C, and the nonrecoverable creep compliance was increased by 81.82% at polymer content of 4% and sulfur content of 0.2%. The FTIR spectra of modified bitumen confirmed the formation of urethane linkages. Therefore, aminolysis of waste PET and in-situ polymerization to produce polyurethane can be applied to improve the performance of bitumen at high temperatures.

Reactive Extrusion Synthesis of Biobased Isocyanate-Free Hydrophobically Modified Ethoxylated Urethanes with Pendant Hydrophobic Groups.

Development of hydrophobically modified ethoxylated urethane (HEUR) rheology modifiers enabled the widespread application of waterborne paints and coatings, replacing their environmentally burdening solvent-based predecessors. However, the diisocyanates, required for the conventional synthesis of HEURs, pose severe eco-sustainability threats. In this paper, we demonstrate an innovative approach to avoiding toxic components in the preparation of rheology modifiers by obtaining a new class of water-soluble isocyanate-free hydrophobically modified ethoxylated poly(hydroxy-urethane)s (IFHEURs). The first step in the synthetic pathway was the preparation of CO2-based five-membered poly(ethylene glycol) bis(cyclic carbonate) and its subsequent aminolysis using 4,7,10-trioxa-1,13-tridecanediamine, yielding poly(hydroxy-urethane) (PHU) prepolymers terminated with cyclic carbonate groups. The PHU prepolymers were further extended in a reactive extrusion (REX) synthesis using biobased hydrophobic diamine PRIAMINE 1075. The REX technique made it possible to overcome the typical limitations of the aminolysis reaction and to reach the desired conversion within a moderate reaction time. IFHEURs have been structurally elucidated using FT-IR and NMR spectroscopy techniques, MALDI-ToF mass spectrometry, and SEC analysis and applied as rheology modifiers. The study of their associative behavior in aqueous solutions confirmed that the architectural flexibility of the obtained IFHEURs, containing terminal and pendant hydrophobic groups, opens a perspective for tuneable thickening performance.

Mechanistic Investigation of Lysine-Targeted Covalent Inhibition of PI3Kδ via ONIOM QM:QM Computations.

Phosphoinositide 3-kinase (PI3K) enzymes are important drug targets, especially in oncology, and several inhibitors are currently under investigation in clinical trials for the treatment of lymphocytic leukemia, follicular lymphoma, breast, thyroid, colorectal, and lung cancer. Targeted covalent inhibitors hold significant promise for drug discovery research especially for kinases. Targeting the lysine residues attracts attention as a new strategy in designing targeted covalent inhibitors, since the lysine residue provides several advantages over the traditional cysteine residue. Recently, new highly selective covalent inhibitors of PI3Kδ with activated ester warheads, targeting the conserved Lys779 residue, were reported. Based on the observed kinetics, a covalent inhibition mechanism was proposed, but the atomistic details of the reaction are still not understood. Therefore, in the present work, we have conducted quantum chemical ONIOM M06-2X/6-31+G(d,p):PM6 calculations on the active site cluster structure of PI3Kδ to elucidate the microscopic details of the mechanism of the aminolysis reaction between Lys779 and the ester inhibitors. Our calculations clearly discriminate the noncovalent methyl ester inhibitor and the covalent inhibitors with activated phenolic esters. For the representative p-NO2, p-F, p-H, and p-OCH3 phenolic esters, the Gibbs free energy profiles of alternative mechanistic paths through either Asp782 or Asp911 demonstrate the modulatory role of active site aspartate residues. The most plausible path alters depending on the electron-withdrawing/donating nature of the p-substituted phenolate leaving group. Inhibitors with sufficiently strong electron-withdrawing group prefer direct dissociation of the leaving group from the tetrahedral zwitterion intermediate, while the ones with electron-donating group favor the formation of a neutral tetrahedral intermediate prior to the dissociation. The relative Gibbs free energy barriers of p-NO2 < p-F < p-H < p-OCH3 substituted phenyl esters display the same qualitative trend as the experimentally measured kinact/KI values. Our results provide in depth insight into the mechanism, which can pave the way for optimizing the inhibitor efficiency.

Multifunctional Porous Films Based on Polylactic Acid/Polycaprolactone Blend and Graphite Nanoplateles

The aim of this work was to develop polylactic acid (PLA) based porous films with suitable properties to be used as sensors and absorbers. The formulation was designed to make the films porous, ductile, and conductive and characterized by surface functionalization. The phase inversion method was used to impart porosity to the polymer film. Polycaprolactone (PCL) and graphite, in the form of graphite nanoplatelets (GNP), were added to increase the elongation at break of the polymer matrix and to make the systems conductive, respectively. To optimize the formulation, the effect of polymer concentration in the initial solution on the viscosity, porosity, and morphology was investigated. FE-SEM measurements showed that the phase inversion method allowed limiting the aggregation of both PCL domains and GNP, whose flakes were found to adhere well to the polymer matrix and to have a nucleating effect, as evidenced by DSC measurements. A simple aminolysis reaction was performed using a diamine, i.e., ethylenediamine, to generate surface amino functionalities. In particular, the extent of functionalization as a function of reaction time was investigated by using FT-IR spectroscopic measurements. By combining these results with the stability of the polymer film, which tends to lose its structural integrity due to the erosion caused by the aminolysis reaction, the optimal contact time with the aqueous solution of ethylenediamine was found. Mechanical measurements showed that the presence of PCL increased the elongation at break of films by 3 times compared to neat PLA. Finally, the films developed starting from the optimized formulations based on PLA/PCL blends, containing GNP and surface functionalized, proved to be effective electrodes for the voltammetric determination of ascorbic acid. In addition, it is of utmost relevance that both amino functionalization and GNP conferred high capacity to the films to retain fluorescein, a model dye.

3D Contour Printing of Anatomically Mimetic Cartilage Grafts with Microfiber-Reinforced Double-Network Bioink.

Bioprinting is an emerging technology for fabricating cell-laden scaffolds with custom shapes that resemble the complex architecture of human tissues, however, construction of mechanically competent tissue grafts which mimic irregular cartilage defect is still a big challenge. Here, 3D printing of short fiber-reinforced double-network bioink to generate anatomically accurate and mechanical tunable scaffold for cartilage regeneration is reported. Poly(lactic acid) (PLLA) short fibers are first prepared by electrospinning and then fragmented through aminolysis reaction. Composite inks are constructed with an incorporation of fragmented microfibers with varied amounts and lengths into oxidized alginate bioink. The results show that incorporation of PLLA short fibers not only improves the printing fidelity but also facilitates in generating mechanically strong constructs. By incorporating gelatin methacryloyl (GelMA) and optimizing the bioink composition, the fabricated constructs with a compressive stress of ≈150 kPa even after 100 cyclical compression loading (up to 40% of strain) are achieved. In addition, this mechanically reinforced alginate/GelMA double-network bioink displays good biocompatibility and supports bone marrow-derived stromal cell chondrogenesis in vitro. Collectively, these findings demonstrate this approach is capable of printing engineered grafts which resemble the irregular size and mechanical properties of cartilage and thus hold potential for functional tissue regeneration.

Choline Chloride/Urea Deep Eutectic Solvents: A Promising Reaction Medium for the Synthesis of Bio-Based Poly(hydroxyurethane)s.

The development of more sustainable and eco-friendly polymers has attracted much attention from researchers over the past decades. Among the different strategies that can be implemented towards this goal, the substitution of the toxic reagents/monomers often used in polyurethane chemistry has stimulated much innovation leading to the development of the hydroxylated version of PURs, namely, the poly(hydroxyurethane)s (PHURs). However, some PHURs remain far from being sustainable as their synthesis may involve monomers and/or solvents displaying poor environmental impacts. Herein, we report on the use of more sustainable conditions to synthesize the biobased polycarbonates involved in the aminolysis reaction. In addition, we demonstrate that the use of renewable deep eutectic solvents (DESs) can act both as excellent solvents and organocatalysts to promote the aminolysis reaction.

Homopolymer-block-Alternating Copolymers Composed of Acrylamide Units: Design of Transformable Divinyl Monomers and Sequence-Specific Thermoresponsive Properties.

In this work, we synthesized an acrylamide-based terpolymer that is a block copolymer composed of an AB alternating copolymer and a C homopolymer. The key to the unprecedented achievement is rational design of an acrylate-acrylamide divinyl monomer carrying CF3-substituted salicylic acid ester bonds (AAm-CF3) to realize the efficient and selective cyclopolymerization as well as the quantitative transformation of the resultant cyclorepeating units. The selectivity in the cyclopolymerization and the pendant transformation ability were evaluated through reactivity ratios of the corresponding model monomers and quantitative aminolysis reactions of the model compound. The cyclopolymerization via the photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) process with a macrochain-transfer agent and subsequent aminolysis reaction afforded the homopolymer-block-alternating copolymer. The sequence-controlled terpolymer exhibited a very unique thermal response behavior in water that was strikingly different from the corresponding sequence-uncontrolled terpolymers, such as homopolymer-block-statistical copolymers and all statistical terpolymers, despite the fact that the structure cannot be distinguished by 1H NMR.

From Waste to Schiff Base: Upcycling of Aminolysed Poly(ethylene terephthalate) Product.

Recycling plastic waste into valuable materials is one of the contemporary challenges. Every year around 50 million tons of polyethylene terephthalate (PET) bottles are used worldwide. The fact that only a part of this amount is being recycled is putting a burden on the environment. Therefore, a technology that can convert PET-based waste materials into useful ones is highly needed. In the present work, attempts have been made to convert PET-based waste materials into a precursor for others. We report an aminolysed product (3) obtained by aminolysis reaction of PET (1) with 1,2 diaminopropane (DAP, 2) under solvent and catalytic free conditions. The highest amount of monomeric product was obtained upon heating the mixture of diamine and PET at 130 °C. The resulting aminolysed product was then converted to a Schiff-base (5) in 25% yield. The chemical structure of the synthesized compounds was confirmed using multi-spectroscopic techniques. The results of this study will be a valuable addition to the growing body of work on plastic recycling.

Synthesis, characterization, and spectroscopic properties of the new type of aminoquinoline-modified cyclotriphosphazenes

The aminolysis reactions of hexachlorocyclotriphosphazene, [N3P3Cl6] (1a) and dispiro-2,2′-biphenoxydichlorocyclotriphosphazene [N3P3Cl2[(2,2′-biphenoxy)2] (1b) with 6-aminoquinoline (2) were carried out to examine the spectroscopic properties of cyclotriphosphazene derivatives combined with 6-aminoquinoline. For the first time, two new aminoquinoline-substituted cyclotriphosphazene derivatives (3a, b) were obtained in this study. Both compounds (3a, b) have been characterized by elemental analysis, FT-IR analysis, MALDI-TOF mass spectrometry, 13C, 1H, and 31P NMR spectroscopies. The molecular structure of 3b has been confirmed by single crystal X-Ray crystallography. The crystal structure of 3b was investigated in detail to determine the remarkable intermolecular interactions. Furthermore, the photophysical properties of compounds 3a and 3b were determined by using UV/vis and fluorescence spectroscopies.

Synthesis of a new bifunctional molecule based on castor oil and CO2 useful for polyurethanes

AbstractA new bifunctional biobased molecule, the carbonated methyl ester of ricinoleic acid maleate (CME‐RAM), useful for polyurethanes, was obtained from castor oil and CO2. This molecule bears carbonate and maleate functionalities that can participate, respectively, in aza‐Michael and aminolysis reactions. Maleate moieties are strong Michael acceptors and they were introduced into the fatty molecule using mild conditions. The synthetic steps include maleinization of castor oil followed by the simultaneous esterification and transesterification at 60°C. The subsequent stages were the epoxidation with acidic resins and the carbonation with CO2. The best results for epoxidation were obtained using Amberlite IR‐120 as catalyst at 48°C (84% conversion of double bonds). The carbonation of the oxirane ring with CO2 at 130°C, 6 MPa CO2 and 6 h reaction afforded 98% conversion of epoxides. It was demonstrated that aza‐Michael reaction of maleate groups was faster than aminolysis of carbonate groups, using hexylamine as a model molecule. CME‐RAM was oligomerized with ethylenediamine and used in the formulation of a conventional rigid polyurethane. Petrochemical polyol and isocyanate can be partially replaced by this bio‐based oligomer, producing a rigid material with a high percentage of green component and good mechanical properties.