Synthesis Of Jasminaldehyde Research Articles

Synthesis of Jasminaldehyde (α-pentylcinnamaldehyde) using Cs-AlMCM-41 Nanoparticle as Heterogeneous Solid Base Catalyst

In this study, the ultra-small mesoporous Cs-AlMCM-41 nanoparticle materials were obtained with high specific BET surface areas in the range of 426 m2g-1 with 1.97 nm pore size. The pore volume was found to be 0.86 cm3. The material possesses a basic site due to caesium ions (Cs+) counterbalancing the negative rise by Al in the mesoporous framework. The basicity of the sample was found to be 115.48 mol g-1. The basicity was proven via the condensation reaction of heptanal and benzaldehyde using microwave irradiation with a microwave power of 800 W. The sample (Cs-MCM-41) gave a higher conversion of heptanal (73.8%) with (70.1%) selectivity to jasminaldehyde. The CsMCM-41 can be a promising base catalyst in aldol condensation reaction for the synthesis of jasminaldehyde under autogenous pressure. Hence, the solid catalyst is easily recycled up to five (5) times with minimal loss of activity due to washing.

Defects tune the acidic strength of amorphous aluminosilicates

Crystalline zeolites have high acidity but limited utility due to microporosity, whereas mesoporous amorphous aluminosilicates offer better porosity but lack sufficient acidity. In this work, we investigated defect engineering to fine-tune the acidity of amorphous acidic aluminosilicates (AAS). Here we introduced oxygen vacancies in AAS to synthesize defective acidic aluminosilicates (D-AAS). 1H, 27Al, and 17O solid-state nuclear magnetic resonance (NMR) studies indicated that defects induced localized structural changes around the acidic sites, thereby modifying their acidity. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy studies substantiated that oxygen vacancies alter the chemical environment of Brønsted acidic sites of AAS. The effect of defect creation in AAS on its acidity and catalytic behavior was demonstrated using four different acid-catalyzed reactions namely, styrene oxide ring opening, vesidryl synthesis, Friedel-Crafts alkylation, and jasminaldehyde synthesis. The defects played a role in activating reactants during AAS-catalyzed reactions, enhancing the overall catalytic process. This was supported by in-situ FTIR, which provided insights into the molecular-level reaction mechanism and the role of defects in reactant activation. This study demonstrates defect engineering as a promising approach to fine-tune acidity in amorphous aluminosilicates, bridging the porosity and acidity gaps between mesoporous amorphous aluminosilicates and crystalline zeolites.

Effect of divalent cations on the basicity and catalytic performance of layered double hydroxide heterogeneous catalyst in microwave-assisted aldol-condensation of benzaldehyde with 1–heptanal

In this study, we investigated the catalytic activity of bimetallic layered double hydroxide catalysts (M–Al–LDH) in the aldol condensation reaction between benzaldehyde (B) and 1–heptanal (H). Specifically, we used M–Al–LDH, where M represents magnesium (Mg), nickel (Ni), and zinc (Zn) with the same molar ratio of M/Al = 3, as heterogeneous basic catalysts for the aldol–condensation to produce jasminaldehyde (J). To prepare the M–Al–LDH catalysts, we employed the co-precipitation method using the nitrate precursors under a nitrogen atmosphere. Sodium hydroxide was used as the precipitating agent. The resulting solids were characterized using various techniques, including X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA/DTA), and BET textural analysis, to study their structural properties. The performance of the catalysts was evaluated and compared in the aldol condensation reaction of benzaldehyde with 1–heptanal under solvent-free conditions, which were carried out in a microwave oven. We also investigated the influence of several reaction parameters on the conversion of 1–heptanal and the selectivity ratio (J/P) in detail to determine the optimal reaction conditions. The results obtained showed that the optimized Mg–Al–NO3 catalyst exhibited a higher conversion of 1–heptanal (99.7%) with a good selectivity ratio (J/P) of 4.00 compared to the other materials studied. Furthermore, the reaction proceeded rapidly in all cases, indicating the practicality of our protocol for the synthesis of jasminaldehyde.

Solvent-free synthesis of jasminaldehyde over chitosan–layered double hydroxide catalyst assisted by microwave irradiation

This research paper reports on the use of chitosan-modified layered double hydroxide (LDH) composite catalysts (CS/MgAl–NO3) for the synthesis of jasminaldehyde under microwave irradiation. The catalysts were prepared by co-precipitation in an inert nitrogen atmosphere. The resulting samples were characterized by mean of X–ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric/differential thermal analysis (TGA/DTA), scanning electron microscope (SEM) with energy-dispersive X–ray (EDX), and N2 adsorption/desorption isotherm (BET) analysis. The basicity of each catalyst was determined by the acid-base titration method. The performance of the catalysts was evaluated in the solvent-free synthesis of jasminaldehyde from aldol by condensation reaction between benzaldehyde and 1–heptanal in a microwave oven at P = 100 W and T = 90 °C. The effects of different parameters that are involved in the reaction, such as the catalyst amount and the benzaldehyde to 1–heptanal molar ratio, and reaction temperature, are investigated in detail. The results showed that the CS-functionalization of the catalyst leads to the enhancement of its basic sites making it more efficient than the naked MgAl–NO3 catalyst, in terms of the initial reaction rate, the conversion of the reactants and the selectivity toward the jasminaldehyde. The CS/MgAl–NO3 catalyst was also evaluated in successive regeneration reaction cycles.

Effect of microwave method on jasminaldehyde synthesis using solvent-free over Mg–Al–NO3 hydrotalcite catalyst

Jasminaldehyde is a widely used starting material in the chemical industry. One method for synthesizing jasminaldehyde is through the aldol condensation of benzaldehyde with 1–heptanal, using a heterogeneous catalyst called hydrotalcite Mg–Al–NO3. The synthesized catalyst was characterized using various techniques, including XRD, FT–IR, TGA, DTA, SEM, EDX, and N2 adsorption–desorption isotherm (BET) to determine its structure, morphology, thermal stability, and properties. This catalyst was tested in the studied reaction under solvent-free conditions, using both microwave and conventional heating methods (in an oil bath) to evaluate the efficiency of each method in producing jasminaldehyde. The results showed that the use of microwave heating in this reaction is particularly advantageous. It allowed for the highest conversion (>99%) of 1–heptanal, with a good selectivity (80%) towards jasminaldehyde, after only 50 min of reaction time. In contrast, conventional heating required a longer reaction time of about 8 h to achieve similar conversion and selectivity values. Furthermore, Mg–Al–NO3 demonstrated nearly sustained activity in three consecutive reuse experiments, and the durability of this catalyst was characterized using several techniques.

Greener Synthesis of Jasminaldehyde via Cross Aldol Condensation Reaction Using Recyclable Phase Transfer Catalysis and its Cosmetic Application

Jasminaldehyde or alpha amyl cinnamic aldehyde is a commonly used aroma molecule in perfume formulationsThe aldol condensation of equimolar n-heptanal and benzaldehyde in NaOH using a surfactant catalyst cetyltrimethylammonium bromide to achieve high cross aldol product Jasminaldehyde selectivity was studied. The process is highly efficient due to the recyclability of the catalyst. The process was studied for four cycles of catalyst reusability. The selectivity of the cross product was dependent on the temperature, surfactant concentration, and mixing. The olfactive profile of Jasminaldehyde obtained with 0.1 M surfactant solution was identical to the standard. Jasminaldehyde formulation was created and applied to in-home care applications.

Investigations on different efficient strategies for the selective synthesis of jasminaldehyde over HRhCO(PPh3)3–hexagonal mesoporous silica and chitosan catalysts

Investigations on different efficient strategies for the selective synthesis of jasminaldehyde over HRhCO(PPh3)3–hexagonal mesoporous silica and chitosan catalysts

Solvent-Free Synthesis of Jasminaldehyde in a Fixed-Bed Flow Reactor over Mg-Al Mixed Oxide

In spite of the rapid developments in synthesis methodologies in different fields, the traditional methods are still used for the synthesis of organic compounds, and regardless of the type of chemistry, these reactions are typically performed in standardized glassware. The high-throughput chemical synthesis of organic compounds such as fragrant molecules, with more economic benefits, is of interest to investigate and develop a process that is more economical and industrially favorable. In this research, the catalytic activity of Mg-Al catalyst derived from hydrotalcite-like precursors with the Mg/Al molar ratio of 3 was investigated for the solvent-free synthesis of jasminaldehyde via aldol condensation of benzaldehyde and heptanal. The reaction was carried out in a fixed-bed flow reactor, at 1 MPa, and at different temperatures. Both Brønsted and Lewis (O2− anions) base sites, and Lewis acid sites exist on the surface of the Mg-Al catalyst, which can improve the catalytic performance. Increasing the reaction temperature from 100 °C to 140 °C enhanced both heptanal conversion and selectivity to jasminaldehyde. After 78 h of reaction at 140 °C, the selectivity to jasminaldehyde reached 41% at the heptanal conversion 36%. Self-condensation of heptanal also resulted in the formation of 2-n-pentyl-2-n-nonenal. The presence of weak Lewis acid sites creates a positive charge on the carbonyl group of benzaldehyde, and makes it more prone to attack by the carbanion of heptanal. Heptanal, is an aliphatic aldehyde, with higher activity than benzaldehyde. Therefore, the possibility of activated heptanal reacting with other heptanal molecules is higher than its reaction with the positively charged benzaldehyde molecule, especially at a low molar ratio of benzaldehyde to heptanal.

Catalytic nanosponges of acidic aluminosilicates for plastic degradation and CO2 to fuel conversion

The synthesis of solid acids with strong zeolite-like acidity and textural properties like amorphous aluminosilicates (ASAs) is still a challenge. In this work, we report the synthesis of amorphous “acidic aluminosilicates (AAS)”, which possesses Brønsted acidic sites like in zeolites and textural properties like ASAs. AAS catalyzes different reactions (styrene oxide ring-opening, vesidryl synthesis, Friedel−Crafts alkylation, jasminaldehyde synthesis, m-xylene isomerization, and cumene cracking) with better performance than state-of-the-art zeolites and amorphous aluminosilicates. Notably, AAS efficiently converts a range of waste plastics to hydrocarbons at significantly lower temperatures. A Cu-Zn-Al/AAS hybrid shows excellent performance for CO2 to fuel conversion with 79% selectivity for dimethyl ether. Conventional and DNP-enhanced solid-state NMR provides a molecular-level understanding of the distinctive Brønsted acidic sites of these materials. Due to their unique combination of strong acidity and accessibility, AAS will be a potential alternative to zeolites.

Activity Coefficients for Liquid Organic Reactions: Towards a Better Understanding of True Kinetics with the Synthesis of Jasmin Aldehyde as Showcase.

The aldol condensation of benzaldehyde and heptanal is taken as an example of reversible liquid phase organic reactions to show that inclusion of activity coefficients reveal distinct differences in conversion and product distribution when different solvents methanol, ethanol, n-propanol, or n-butanol are used. The purpose of this work is to show a pronounced solvent effect for a given set of identical kinetic parameters, i.e., the same liquid phase kinetics can result in different conversion and yield values, depending on the choice of solvent. It was shown that subsequent parameter estimation without inclusion of the activity coefficients resulted in a pronounced deviation from the ‘true’ kinetics, up to a factor of 30. It is proposed that the usage of average activity coefficients gives already a significant improvement, resulting in acceptable parameter estimates.

Acid–base bifunctional magnesium oxide catalyst prepared from a simple hydrogen peroxide treatment for highly selective synthesis of jasminaldehyde

ABSTRACT The aldol reaction between benzaldehyde and heptanal for jasminaldehyde synthesis has been widely tested over various heterogeneous catalysts. The reaction is preferred to be conducted over acid-base bifunctional catalyst for high jasminaldehyde selectivity. Generally, Magnesium oxide (MgO) is not considered to be suitable for jasminaldehyde synthesis due to its monobasic property and low jasminaldehyde selectivity. In this work, the MgO sample was treated through a simple hydrogen peroxide reflux-calcination process to create acid-base bifunctional surface. The resulting catalyst afforded high selectivity to jasminaldehyde of 88–90% even at a benzaldehyde to heptanal molar ratio of 5. The mechanism of this high jasminaldehyde selectivity was investigated in this paper, and the results indicate that this novel acid-base bifunctional MgO catalyst is preferential adsorption of benzaldehyde over heptanal, which leads to a higher benzaldehyde: heptanal ratio on its surface. In addition, the presence of weak Lewis acid sites on catalyst’s surface induces a partial positive charge on carbonyl group of benzaldehyde, making it susceptible to a nucleophilic attack by the heptanal carbanion. The reusability of this novel acid-base bifunctional MgO catalyst was also studied.

P-Toluene sulfonic acid (PTSA)-MCM-41 as a green, efficient and reusable heterogeneous catalyst for the synthesis of jasminaldehyde under solvent-free condition

This paper reports the synthesis of p-Toluene sulfonic acid (PTSA)-MCM-41 by impregnation method and its characterization XRD, FT-IR, TGA, N2 adsorption–desorption isotherms, SEM, and TEM. The impregnated catalysts were used to catalyse cross-aldol condensation of active methylene bearing aliphatic aldehydes with aromatic aldehydes under solvent and metal-free condition particularly in the synthesis perfumery chemical-jasminaldehyde and related compounds. The as synthesized catalyst PTSA-MCM-41 has displayed high efficiency (selectivity up to 91%) in catalyzing cross-aldol condensation reaction and was reusable (5 cycles) with no apparent loss in activity. The catalytic performance of PTSA-MCM-41 was compared with other catalysts viz., ZnO, proline, proline-LDH, PTSA, PTSA-zirconia and PTSA-zeolite where PTSA-MCM-41 showed better performance particularly in synthesis of jasminaldehyde.

Amorphous metal-aluminophosphate catalysts for aldol condensation of n-heptanal and benzaldehyde to jasminaldehyde

Amorphous aluminophosphate (AlP) and metal-aluminophosphates (MAlPs, where M = 2.5 mol% Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesis of jasminaldehyde through the aldol condensation of n-heptanal and benzaldehyde were investigated. The nitrogen adsorption-desorption isotherms showed that the microporosity exhibited by the aluminophosphate was changed to a mesoporous and macroporous structure which depended on the metal incorporated, with a concomitant change in the surface area. Temperature-programmed desorption of NH3 and CO2 revealed that the materials possessed both acidic and basic sites. The acidic strength of the material was either increased or decreased depending on the nature of the metal. The basicity was increased compared to AlP. All the materials were X-ray amorphous and powder X-ray diffraction studies indicated the absence of metal oxide phases. The Fourier transform infrared analysis confirmed the presence of phosphate groups and also the absence of any M-O moieties in the materials. The selected organic reaction occurred only in the presence of the AlP and MAlPs. The selectivity for the jasminaldehyde product was up to 75% with a yield of 65%. The best conversion of n-heptanal with a high selectivity to jasminaldehyde was obtained with FeAlP as the catalyst, and this material was characterized to have less weak acid sites and more basic sites.

An elegant synthesis of chitosan grafted hydrotalcite nano-bio composite material and its effective catalysis for solvent-free synthesis of jasminaldehyde

A novel nano-bio composite of chitosan and a layered double hydroxide elegantly synthesized by a co-precipitation method had effectively and selectively catalysed the jasminaldehyde synthesis.

산, 염기 이원기능 금속-유기 구조체 촉매를 이용한 알돌 축합반응

Various types of MOFs (metal-organic frameworks) were prepared via hydrothermal and post-grafting methods and applied as catalysts for the synthesis of jasminaldehyde, one of the representative perfume intermediates, by Aldol condensation of benzaldehyde with heptanal. Although both acid and base sites could catalyze the reaction, the catalytic performance was strongly dependent on the physical properties as well as the nature of functionalization on MOFs. While the use of sulfonated MOF catalysts led to decrease of jasminaldehyde selectivity regardless of MOFs used, the selectivity change was found to rely on the MOF types in the case of the amine-functionalization. Among the catalysts tested, MIL-101 shows the best catalytic per- formance, which may suggest that MIL-101 has suitable acid properties to promote the Aldol condensation and the large pore of MIL-101 is also advantageous to alleviate the diffusion problem of bulky products.

Synthesis of natural fragrance jasminaldehyde using silica-immobilized piperazine as organocatalyst

Jasminaldehyde (α-pentyl cinnamaldehyde) is a natural fragrance that can be produced via aldol-type C–C bond formation between heptanal and benzaldehyde. The use of bases like NaOH to form jasminaldehyde typically leads to significant waste and by-product formation. To provide sustainable options with diminished waste formation and high conversions and selectivities, herein a silica-immobilized piperazine is used as organocatalyst for the jasminaldehyde synthesis either in bio-based solvents (e.g. 2-methyltetrahydrofuran, 2-MeTHF) or in solvent-free conditions (using neat substrates as reaction media). Under reported conditions, a production of ∼7 g jasminaldehyde L−1 h−1 is observed, delivering on-spec conversions and selectivities (>90% each). Selectivity remains unaltered during catalyst recycling, whereas a loss of conversion is significantly observed after reusing the catalyst for several cycles.

Mesoporous cubic Ia3d materials for the preparation of fine chemicals: Synthesis of jasminaldehyde

The synthesis of mesoporous Al-KIT-6 is synthesized by direct hydrothermal method with different Si/Al ratios (20, 30, 50, 100 and 150) were characterized by XRD, ICP-AES, BET, SEM and HR-TEM. Mesoporous Al-KIT-6 was synthesized from assembly of polymer surfactant micelle as a template in acidic media. Mesoporous Al-KIT-6 was good phase purity from XRD analysis. The HR-TEM picture of Al-KIT-6 (50) showed formation of particles of cubic morphology and SEM images are also shown rod like morphology. α-n-Amylcinnamaldehyde (jasminaldehyde) has been prepared with high selectivity and using low ratios of benzaldehyde/heptanal by means of mesoporous Al-KIT-6 molecular sieves.

Kinetic investigations on the modified chitosan catalyzed solvent-free synthesis of jasminaldehyde

Kinetic investigations were performed for the modified chitosan catalyzed solvent-free synthesis of jasminaldehyde. The rates of formation for both jasminaldehyde and 2-pentyl nonenal were calculated. Kinetic investigations were performed as a function of the amount of the catalyst, heptanal, benzaldehyde and temperature. The rate of formation of jasminaldehyde was first order with respect to the lower amount of catalyst and showed saturation at higher amounts. A critical amount of heptanal was needed for the formation of jasminaldehyde. The maximum rate was showed for heptanal–benzaldehyde ratio of 1:4. The Langmuir–Hinshelwood rate model used for the formation of jasminaldehyde was found to fit with R 2 value of 0.95. The computational studies were indicative for the rate determining steps, as the reaction of benzaldehyde with deprotonated heptanal on surface for jasminaldehyde, and proton abstraction for the formation of 2-pentyl nonenal. Mass transfer effects for the condensation reaction were studied.

ChemInform Abstract: Synthesis of Jasminaldehyde by Solid-Liquid Phase Transfer Catalysis Without Solvent, Under Microwave Irradiation.

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Reconstructed Mg/Al hydrotalcite as a solid base catalyst for synthesis of jasminaldehyde

Reconstructed hydrotalcites (Mg/Al molar ratio = 3.5) of varied reconstruction time were synthesized and used as catalysts for solvent free condensation of 1-heptanal with benzaldehyde. Maximum conversion of 1-heptanal with higher selectivity to jasminaldehyde was obtained using reconstructed hydrotalcites of 8–12 h reconstruction time. Catalytic activity of reconstruction hydrotalcite was compared with as-synthesized and activated hydrotalcite of Mg/Al molar ratio 3.5 and significantly higher conversion of 1-heptanal was observed in case of reconstructed hydrotalcite of 8 h reconstruction time as a catalyst. Similar to the conversion, higher selectivity to jasminaldehyde was also obtained using reconstructed hydrotalcite. Effect of reconstruction time on conversion and selectivity to jasminaldehyde was studied by varying the reconstruction time of hydrotalcite from 0.5 to 72 h. Kinetic experiments were carried out to study the effect of stirring speed, benzaldehyde to 1-heptanal molar ratio, amount of catalyst and reaction temperature on the rate of reaction using reconstructed hydrotalcite as a catalyst.