Aldol Condensation Of Acetone Research Articles

One-pot sequential aldol condensation and hydrodeoxygenation of furfural and acetone to 1-octanol over multifunctional acid-based catalytic system

Furfural and acetone are two of the most promising chemicals derived from lignocellulosic biomass. Coupling these two compounds expands the broad range of value-added chemicals that can be derived from biomass. In this study, 1-octanol, a promising medium chain-length alcohol, was produced from furfural and acetone through a series of reactions: aldol condensation (R1), hydrogenation (R2), and hydrogenolysis (R3). Each step was individually investigated to understand its mechanism and requirements, enabling seamless integration into one-pot, two-step (R1, R2 + R3) and one-pot, three-step (R1 + R2 + R3) processes. To facilitate these reactions, bifunctional alumina–zirconia-based catalysts were synthesized. Additionally, to enhance the yield of 1-octanol, solid acidic additives, particularly sulfonic acid-functionalized silica (KCC-1-APSO3H), were incorporated into the reaction. The highest yield of 1-octanol (69.1 %) was achieved with the three-step process (R1, R2, R3), followed by the one-pot two-step process (R1, R2 + R3, 64.8 %), and the one-pot, three-step process (R1 + R2 + R3, 48.7 %) using the combined Ni/Al2O3-ZrO2 and KCC-1-APSO3H catalyst. Among all the processes investigated, the one-pot, two-step process emerged as the best approach balancing the efficiency of the process integration and 1-octanol yield. The present study offers valuable insights into the development of catalytic methods for producing linear alcohols from biomass.

Investigating base-catalyzed aldol condensation reactions on alkali-free hydrotalcites and the role of thermal decomposition

Aldolization is a crucial carbon–carbon coupling reaction used in the conversion of biomass-derived platform molecules into valuable chemicals and fuels. In this work, we combine experiment and theory to explore the role thermal decomposition has in controlling the structure of alkali-free Mg-Al layered double hydroxides (LDHs) and their subsequent performance in the base-catalyzed aldol condensation of acetone, focusing on the constituent aldolization and dehydration steps. LDHs were synthesized via co-precipitation and subjected to calcination at temperatures up to 600 °C to produce mixed metal oxides of the form Mg3AlOz which were further examined by SEM, N2 physisorption, XRD, and CO2-TPD. Aldolization and dehydration behaviors were examined in a batch reactor and fit with kinetic models to capture the sensitivities of both reactions to calcination temperature. Additional experiments involving the selective blocking of base sites by CO2 poisoning and reversal at varying temperatures showed that both aldolization and dehydration are likely driven by the strongest base sites, yielding a site density (0.19 μmol m−2) in agreement with separate propionic acid titration studies. Density functional theory (DFT) simulations of Mg5Al2O8 surfaces were employed to gain microscopic insights into these materials, revealing the importance of Al substitution in creating cation vacancies which can drive aldol condensation through enolate intermediates stabilized in the oxyanion resonance form. High-coverage simulations of the surface show participation of the vacancy in both aldolization and dehydration, rationalizing the coupling of rate trends observed experimentally. Ultimately, this study provides new insights and approaches useful in the design of heterogeneous aldolization catalysts.

Aqueous Phase Hydrogenation of 4-(2-Furyl)-3-buten-2-one over Different Re Phases.

4-(2-furyl)-3-buten-2-one (FAc) is obtained by aldol condensation of furfural and acetone and has been used in hydrodeoxygenation reactions to obtain fuel products using noble metal catalysts. The hydrogenation of FAc in the aqueous phase using metallic- and Re oxide-supported catalysts on graphite was studied, within a temperature range of 200-240 °C, in a batch reactor over a 6 h reaction period. The catalysts were characterized using N2 adsorption-desorption, TPR-H2, TPD-NH3, XRD, and XPS analyses. Catalytic reactions revealed that metallic rhenium and rhenium oxide-supported catalysts are active for the hydrogenation and Piancatelli rearrangement of FAc. Notably, metallic rhenium exhibited a fourfold higher initial rate than rhenium oxide, which was attributed to the higher dispersion of Re in the Re/G catalyst over graphite. Re/G and ReOx/G catalysts tended to rearrange and hydrogenate FAc to 2-(2-oxopropyl)cyclopenta-1-one in water.

Synthesis of Long Chain Oxygenates via Aldol Condensation of Furfural and Acetone over Metal-Organic Frameworks.

Enormous efforts have been made to convert biomass to liquid fuels and products catalytically. Long molecules with a suitable structure are ideal precursors for fuels and value-added products. Here, a C21 oxygenate was synthesized for the first time in one step through aldol condensation of furfural and acetone over the amine-functionalized zirconium-based metal-organic framework (MOF), UiO-66-NH2. Structural changes of UiO-66-NH2 were investigated to improve the yield and evaluate the role of the ligand, cluster node, defectiveness, modulator, surface area, and textural properties on the product distribution. We demonstrate the possibility of making long-chain oxygenates without using vegetable oil-derived fatty acids toward 100% waste biomass-derived renewable fuels, lubricants, and surfactants.

Effect of interlayer anions on the catalytic activity of Mg-Al layered double hydroxides for furfural and acetone aldol condensation reaction

The aldol condensation reaction between furfural (F) and acetone (A), which typically produces 4-(2-Furyl)-3-buten-2-one (FA), is a critical reaction due to the application of the final product as a flavoring agent in various food items. Traditionally, this reaction is catalyzed by liquid-based catalysts. However, homogeneous liquid-base catalysis often leads to environmental damage. Solid-base catalysis is highly desirable to address the environmental issue due to liquid-base catalysis as it reduces the need for excessive solvents and reagents, thus preserving the environment. In this study, a series of Mg-Al hydrotalcites (HT) intercalated with nitrate ion (HT-NO3), carbonate ion (HT-CO3), or acetate ion (HT-CH3COO) were prepared using three different coprecipitation procedures. Upon calcination at 450 °C, the solids were transformed into mixed metal oxides. Among the calcined hydrotalcites, the catalysts with acetate anion (cHT-CH3COO) or carbonate anion (cHT-CO3) exhibited the highest basicity and thus showed superior catalytic activity for the aldol condensation reaction. Optimal conversion and selectivity were achieved at 90 °C for 2 h using the most basic catalysts (cHT-CO3 and cHT-CH3COO). These catalysts yielded over 98 % conversion with FA selectivity of 76 % for cHT-CO3 and 65 % for cHT-CH3COO, respectively. Notably, the catalyst cHT-CH3COO exhibited higher selectivity towards F2A (32 %) than the cHT-CO3 catalyst (18 %). The effect of interlayer anions on the structural properties of the Mg-Al hydrotalcites was analyzed using X-ray diffraction. Fourier-transform infrared spectroscopy (FT-IR) was employed to investigate the interactions corresponding to different types of anions. The specific surface area and pore volume of the calcined Mg-Al hydrotalcites were determined using nitrogen adsorption (BET), while their total basicity was evaluated through acid-base titration. The reaction kinetics were monitored using gas chromatography.

Tuning aldol condensation product selectivity by controlling diffusion and reaction rates in zeolites

This study presents a method for quantifying mass-transfer limitations in microporous acid zeolites that combines a titration technique and a reaction–diffusion model. The method involves partially exchanging H+ sites with Na+ sites to adjust the site density and observing the resulting reaction rates for the aldol condensation of acetone and cyclopentanone. When the intrinsic activity per site is uniform throughout the zeolite and in the absence of mass-transport limitations, a linear decrease in the reaction rate is expected as the density of sites is systematically lowered by gradual titration. Conversely, if mass-transport limitations are present, the initial decrease in rate with increasing number of titrated sites is much lower than that observed when a large fraction of the active sites have been titrated. This non-linear variation of observed rate as a function of the density of titrated sites indicates the presence of mass-transport limitations in the system. Near the limit where the density of remaining active sites is low enough to avoid generating a concentration gradient inside the zeolite crystallite, the variation in rate becomes linear. The titration results can be coupled with reaction–diffusion modeling to fit and calculate the Thiele modulus, which provides quantitative information on the extent of mass-transport limitations in the studied porous acidic domains. In the case of acetone-cyclopentanone cross-condensation reaction, the selectivity towards the different products was found to be influenced by the degree of mass transfer limitations. That is, kinetically driven systems favor the cyclopentanone self-condensation product while diffusion-limited environments favor products of the reactant with faster diffusion rates. Accordingly, the manipulation of site density was found to be useful in tuning product selectivity towards specific desired products, which demonstrates the potential of this method for developing and optimizing microporous catalysts with controllable acid site density and provide valuable insight into the relationship between mass-transfer limitations and product selectivity.

Temperature Stable Ion Exchange Resins as Catalysts for the Manufacturing of Vitamin Precursors by Aldol Reaction.

This study explores the potential of robust, strongly basic type I ion exchange resins-specifically, Amberlyst® A26 OH and Lewatit® K 6465-as catalysts for the aldol condensation of citral and acetone, yielding pseudoionone. Emphasis is placed on their long-term stability and commendable performance in continuous operational settings. The aldol reaction, which traditionally is carried out using aqueous sodium hydroxide as the catalyst, holds the potential for enhanced sustainability and reduced waste production through the use of basic ion exchange resins in heterogeneous catalysis. Density Functional Theory (DFT) calculations are employed to investigate catalyst deactivation mechanisms. The result of these calculations indicates that the active sites of Amberlyst® A26 OH are cleaved more easily than the active sites of Lewatit® K 6465. However, the experimental data show a gradual decline in catalytic activity for both resins. Batch experiments reveal Amberlyst® A26 OH's active sites diminishing, while Lewatit® K 6465 maintains relative consistency. This points to distinct deactivation processes for each catalyst. The constant count of basic sites in Lewatit® K 6465 during the reaction suggests additional factors due to its unique polymer structure. This intriguing observation also highlights an exceptional temperature stability for Lewatit® K 6465 compared to Amberlyst® A26 OH, effectively surmounting one of the prominent challenges associated with the utilization of ion exchange resins in catalytic applications.

Influence of Water on the Production of Liquid Fuel Intermediates from Furfural via Aldol Condensation over MgAl Catalyst

The aldol condensation of furfural and acetone is considered a promising method for the production of liquid fuel intermediates. 4-(2-furyl)-3-buten-2-one (FAc) and 1,5-di-2-furanyl-1,4-pentadien-3-one (F2Ac) are the main products of the reaction, which can go through the hydrodeoxygenation process to convert to diesel and jet fuel range fuels. Considering the present situation at the fuel-market related to crude oil shortage, the above-mentioned process seems to be a convenient path to obtain fuels in the diesel and kerosene range. This research focuses on the effect of water on the furfural conversion and product distribution during the aldol condensation. The catalyst chosen for this research was MgAl mixed oxide in molar ratio 3:1. The reaction was performed at 40 °C and 1 MPa in a continuous-flow reactor with and without water in the feedstock. The physicochemical properties of the catalyst were evaluated using different techniques. The catalyst lifetime decreased and the catalyst deactivation started faster by the addition of 5 wt.% water to the feedstock with the furfural to acetone ratio (F:Ac) of 1:2.5. Selectivity to FAc increased by 10% in the presence of water. The catalyst lifetime enhanced by increasing the F:Ac ratio from 1:2.5 to 1:5, in the presence of 5 wt.% water. The furfural conversion was 100% after 28 h of reaction, and then decreased gradually to 40% after 94 h of reaction. At higher F:Ac ratio, the selectivity to FAc was 10% higher, while the F2Ac was about 8% lower.

Potassium-modified bifunctional MgAl-SBA-15 for aldol condensation of furfural and acetone

Potassium modified acid–base bifunctionalized MgAl-SBA-15 for mild aldol condensation of furfural and acetone to high-quality jet-fuel range or chemical intermediates.

Controlling the toxicity of biomass-derived difunctional molecules as potential pharmaceutical ingredients for specific activity toward microorganisms and mammalian cells.

A biomass-derived difuran compound, denoted as HAH (HMF-Acetone-HMF), synthesized by aldol-condensation of 5-hydroxyfurfural (HMF) and acetone, can be partially hydrogenated to provide an electron-rich difuran compound (PHAH) for Diels-Alder reactions with maleimide derivatives. The nitrogen (N) site in the maleimide can be substituted by imidation with amine-containing compounds to control the hydrophobicity of the maleimide moiety in adducts of furans and maleimide by Diels-Alder reaction, denoted as norcantharimides (Diels-Alder adducts). The structural effects on the toxicity of various biomass-derived small molecules synthesized in this manner to regulate biological processes, defined as low molecular weight (≤ 1000 g/mol) organic compounds, were investigated against diverse microbial and mammalian cell types. The biological toxicity increased when hydrophobic N-substitutions and C=C bonds were introduced into the molecular structure. Among the synthesized norcantharamide derivatives, some compounds demonstrated pH-dependent toxicities against specific cell types. Reaction kinetics analyses of the norcantharimides in biological conditions suggest that this pH-dependent toxicity of norcantharimides could arise from retro Diels-Alder reactions in the presence of a Brϕnsted acid that catalyzes the release of an N-substituted maleimide, which has higher toxicity against fungal cells than the toxicity of the Diels-Alder adduct. These synthetic approaches can be used to design biologically-active small molecules that exhibit selective toxicity against various cell types (e.g., fungal, cancer cells) and provide a sustainable platform for production of prodrugs that could actively or passively affect the viability of infectious cells.

Talc modified by milling and alkali activation: Physico-chemical characterization and application in base catalysis

The work aimed at the development of benign solid base catalysts as alternatives for presently used noxious liquid bases. Talc, possessing intrinsic basic properties, was chosen as a particularly attractive and cost-effective precursor. Activation of talc by grinding in a planetary mill followed by treatment with 2 M NaOH was employed as means for basicity enhancement. Such protocol enabled profound modification of talc structure, otherwise resistant to treatment with a basic solution. Deep changes, not addressed in the literature reports so far, took place in the course of combined mechanical and alkali treatment. The amorphized ground talc transformed to the magnesium silicate hydrate (MSH) phase and brucite. Treatment with NaOH led to significant enhancement of surface basicity with respect to the parent materials. The effect was particularly spectacular for alkali-treated, strongly ground talc samples, containing the MSH component. The materials were tested in a base-catalyzed reaction of aldol condensation of acetone. The trend of catalytic activity followed closely the order of surface basicity, which pointed to the key role of MSH as a catalytically active phase in the modified talc solids. Joint mechanical and alkali activation of talc proved to be a simple, yet promising way of developing solid base materials for catalytic applications.

Reactivity of Formaldehyde during 4-Hydroxy-2-butanone Synthesis in Supercritical State.

4-Hydroxy-2-butanone, an important intermediate for vitamin A and fragrances, is usually produced by aldol condensation of acetone and formaldehyde. Noncatalytic synthesis of 4-hydroxy-2-butanone in supercritical state, which was fast and had high production yield, was widely applied. Previous research on 4-hydroxy-2-butanone synthesis in the supercritical state focused on the formation and dehydration of 4-hydroxy-2-butanone while ignoring side reactions involving formaldehyde, which were studied in this paper. A reaction pathway of 4-hydroxy-2-butanone supercritical synthesis containing formaldehyde side reactions was proposed. The cross-disproportionation of formaldehyde and formic acid was found to be the main consumption of formic acid. The effects of initial formaldehyde and formic acid mass fractions in the feed on side reactions were studied. Based on the experiments conducted from 523.15 K to 563.15 K and 17 MPa, a kinetic model was suggested. The relative deviations between experimental and simulated data were less than 10%.

Formation of the CaSnO3 crystalline phase during catalytic aldol condensation of acetone under supercritical conditions

Formation of the CaSnO3 crystalline phase during catalytic aldol condensation of acetone under supercritical conditions

Catalytic aldol condensation of bio-derived furanic aldehydes and acetone: Challenges and opportunities

Bio-derived furfural and 5-hydroxymethylfurfural can be combined with acetone to yield aldol condensation products that may serve as biofuel and polymer precursors. We have explored different catalytic systems to obtain and purify each product in the most efficient way. The results of the catalytic tests of the cross-condensations and of the self-condensation of acetone allowed the comparison of the different reactivity of the two aldehydes. Online and in situ/operando ATR-IR was used to monitor the reaction over time and to study the interaction of the reaction species with the solid catalyst, especially the formation of deactivating organic matter that covers the surface, which is a major issue in heterogeneous condensation processes. In situ NMR was used to study the ongoing reaction, assessing its stereoselectivity, and to study the behavior of deuterated species in the catalytic system. Finally, the preparation of C14, a hetero-double-condensation product, was also explored.

Consequences of Intrapore Liquids on Reactivity, Selectivity, and Stability for Aldol Condensation Reactions on Anatase TiO2 Catalysts

AbstractThis study provides evidence and mechanistic interpretations for the significant consequences of intrapore non‐polar liquids on acetone aldol condensation turnover rates, selectivity to primary dimer products, and catalyst stability for reactions at Lewis acid‐base site pairs on TiO2 surfaces. These non‐polar liquids confer such benefits through the preferential stabilization of transition states (TS) for adsorption (“entry”) and desorption (“exit”) steps, which place their respective reactants or products within a solvating outer sphere environment. The extent to which non‐polar fluids (n‐heptane) form an intrapore liquid phase within TiO2 voids was obtained from N2 uptakes using established formalisms that consider the different molal volume, surface tension, and volatility between N2 and n‐heptane. Acetone condensation rates are limited by C−H activation, an “entry” step that forms bound prop‐1‐en‐2‐olates via a TS stabilized by intrapore liquids, leading to higher aldol condensation turnover rates as n‐heptane pressure increases and active TiO2 surfaces become increasingly immersed within a non‐polar liquid phase. These liquids solvate the late TS structures that mediate the desorption of primary C6 condensation products even more effectively than those involved in prop‐1‐en‐2‐olate formation or in nucleophilic attack events that later form C−C bonds. Such preferential solvation favors desorption over C−C coupling events, thus disfavoring the formation of larger oligomers that become stranded at active sites, thus leading to much slower deactivation. Moreover, solvation by non‐polar liquids also leads to C6 alkanones as the sole products formed in a single surface sojourn. These effects of a non‐polar dense phase circumvent the inherent stability, reactivity, and selectivity hurdles that have precluded practical aldol condensation catalysis on Lewis acid‐base pairs at oxide surfaces; these consequences are demonstrated here for TiO2 catalysts, acetone aldol condensation reactions, and n‐heptane as the non‐polar liquid but through strategies, concepts, and mechanistic features that extend to other systems. More generally, these observations and their mechanistic origins demonstrate how a contacting liquid preferentially solvates TS structures for elementary steps that involve either reactants arriving from or products entering into an outer sphere environment that contains a dense non‐polar phase.

Value addition of lignin to zingerone using recyclable AlPO4 and Ni/LRC catalysts

Value-addition of lignin to chemicals and medicinal compounds is highly desirable for bio-refineries and chemical industries. We present a simple and intriguing two-step method for synthesizing zingerone from vanillin. The first step was to make dehydrozingerone via aldol condensation of vanillin and acetone in the presence of an AlPO4 catalyst. At 120 °C for 24 h, this catalyst showed outstanding activity, with 99% selectivity of dehydrozingerone. Second, utilizing lignin residual carbon assisted Ni nanocatalyst (Ni/LRC), the dehydrozingerone was transformed into targeted zingerone by selective hydrogenation of the C–C double bond. The reaction parameters significantly influenced the formation of both dehydrozingerone and zingerone. The Physico-chemical properties of both the catalysts (AlPO4 and Ni/LRC) were thoroughly investigated by NH3 and CO2 TPD, Py-FTIR, XRD, N2 adsorption–desorption, 27Al, and 31P MAS NMR and FT-IR analysis. Interestingly, both AlPO4 and Ni/LRC catalysts were effectively recovered and reused for 10 cycles without apparent loss in catalytic activity for their respective reactions. Zingerone was eventually synthesized directly from lignin for the first time, with yields of 9.25 wt% on initial lignin intake.

Cooperativity in the Aldol Condensation Using Bifunctional Mesoporous Silica-Poly(styrene) MCM-41 Organic/Inorganic Hybrid Catalysts.

This work explores the efficacy of silica/organic hybrid catalysts, where the organic component is built from linear aminopolymers appended to the silica support within the support mesopores. Specifically, the role of molecular weight and polymer chain composition in amine-bearing atom transfer radical polymerization-synthesized poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione) copolymers is probed in the aldol condensation of 4-nitrobenzaldehyde and acetone. Controlled polymerization produces protected amine-containing poly(styrene) chains of controlled molecular weight and dispersity, and a grafting-to thiol-ene coupling approach followed by a phthalimide deprotection step are used to covalently tether and activate the polymer hybrid catalysts prior to the catalytic reactions. Site-normalized batch kinetics are used to assess the role of polymer molecular weight and chain composition in the cooperative catalysis. Lower-molecular-weight copolymers are demonstrated to be more active than catalysts built from only molecular organic components or from higher-molecular-weight chains. Molecular dynamics simulations are used to probe the role of polymer flexibility and morphology, whereby it is determined that higher-molecular-weight hybrid structures result in congested pores that inhibit active site cooperativity and the diffusivity of reagents, thus resulting in lower rates during the reaction.

Structural and evolutionary analysis unveil functional adaptations in the promiscuous behavior of serum albumins

Promiscuous activities have been related to the capacity to catalyze reactions different from those a protein has evolved to sustain. In this work, we rethought the serum albumin's promiscuous behavior using evolutionary and structural analysis. We found that the cross aldol condensation of acetone and p-formylbenzonitrile is a promiscuous reaction conserved in humans serum albumin and in closely related albumins from other mammals. Evolutionary analysis indicates that the residues involved in this promiscuous reaction are evolving under positive selection, an evolutionary pattern indicating a putative functional adaptation. Also, key residues are located in an evolutionary conserved cavity connected with the protein surface with an also conserved tunnel and mutations involving these residues are described in human diseases. Overall, our results suggest that albumin could have evolved to sustain a still unknown biological function among the many others it maintains. Our results could contribute to better characterize the serum albumin family and raise questions about the evolution of protein promiscuity and function.

Enhancing β-hydroxy ketone selectivity in the aldol condensation of furfural and acetone over N–B–O sites in calcined boron nitride

Air-calcined BN can catalyze the aldol reaction of furfural and acetone while suppressing dehydration to afford β-hydroxy ketone. Two types of O-substituted N defect sites were identified and a B-centered Lewis acid-catalyzed mechanism was proposed.

Controlled hydrogenation of a biomass-derived platform chemical formed by aldol-condensation of 5-hydroxymethyl furfural (HMF) and acetone over Ru, Pd, and Cu catalysts.

We studied the hydrogenation at temperatures from 313 - 393 K of a biomass-derived platform molecule, 5-hydroxymethyl furfural (HMF)-Acetone-HMF (HAH) over Pd, Ru, and Cu based catalysts. HAH was selectively hydrogenated to produce partially-hydrogenated monomers (PHAH) over Cu and Ru catalysts and to fully-hydrogenated HAH monomers (FHAH) over the Ru catalyst. Pd based catalysts yielded a mixture of partially and fully hydrogenated monomers. Lumped reaction kinetics models were employed to quantify the kinetic behavior for hydrogenation over Ru, Cu, and Pd catalysts. The 5-step pathway exhibited over Pd and Ru catalysts consists of both series and parallel reaction steps, where HAH is both converted to fully hydrogenated products sequentially via series reactions of partially hydrogenated intermediates, as well as converted directly in parallel reactions to form the fully hydrogenated products. In contrast, the 3-step pathway over the Cu catalyst consists only of the consecutive reaction steps, where the final product was formed via series reactions of intermediate products. Additionally, reaction over the Cu catalyst did not hydrogenate the furan rings of the HAH molecule and yielded a different final product than those hydrogenation over Pd and Ru catalysts. Batch conditions are determined for each hydrogenated product that give the highest yields in both batch and plug flow reactors.