Synthesis Of Benzoic Acid Research Articles

Synthesis of Benzoic Acids from Electrochemically Reduced CO2 Using Heterogeneous Catalysts.

A method for the synthesis of benzoic acids from aryl iodides using two of the most abundant and sustainable feedstocks, carbon dioxide (CO2) and water, is disclosed. Central to this method is an effective and selective electrochemical reduction of CO2 (eCO2RR) to CO, which mitigates unwanted dehalogenation reactions occurring when H2 is produced via the hydrogen evolution reaction (HER). In a 3-compartment set-up, CO2 was reduced to CO electrochemically by using a surface-modified silver electrode in aqueous electrolyte. The ex-situ generated CO further underwent hydroxycarbonylation of aryl iodides by MOF-supported palladium catalyst in excellent yields at room temperature. The method avoids the direct handling of hazardous CO gas and gives a wide range of benzoic acid derivatives. Both components of the tandem system can be recycled for several consecutive runs while keeping a high catalytic activity.

Synthesis of benzoic acid from catalytic co-pyrolysis of waste wind turbine blades and biomass and their kinetic analysis

This work aims to study the catalytic co-pyrolysis of waste wind turbine blades (WTB: consists of fiberglass/unsaturated polyester resin) and woody biomass (WB) over ZSM-5 and Y-type zeolite catalysts for the production of benzoic acid. The experiments were performed on an equal combination of WTB and WB (WTB/WB) and a fixed amount of catalyst (50 wt%) using a thermogravimetric (TG) analyser at 10, 20 and 30 °C/min. The evolved products from the catalytic co-pyrolysis process were recognized using TG-FTIR and GC/MS. The kinetic and thermodynamic characteristics of catalytic co-pyrolysis was studied using various linear and nonlinear approaches. Also, the decomposition curves were predicted mathematically using an artificial neural network algorithm. The results revealed that the mixture was decomposed in the presence of both catalysts in the form of dual decomposition peaks at 361–374 °C and 428–443 °C, respectively. Based on TG-FTIR results, the CO stretching and carbon dioxide clusters were their main functional groups. While the GC-MS analysis revealed that the released vapours were completely free of toxic styrene (the main compound of resin) and the catalytic co-pyrolysis treatment succeeded in converting it into highly abundant benzoic acid, especially at 10 °C/ min, with an estimated 71.4 % (ZSM-5) and 64 % (Y-type). Whereas the activation energy was estimated at 262–295 kJ/mol (ZSM-5) and 319–357 kJ/mol (Y-type) with almost similar reaction complexity when compared to the case of absence of catalysts. Finally, the developed ANN algorithm showed high efficiency in predicting TG decomposition zones for both WTB/WB mixtures over zeolite catalysts with R2 more than 0.99. These results demonstrate that WB and zeolite catalysts can be used for upgrading the pyrolysis oil of WTB and eliminate its toxic styrene and convert it into benzoic acid and other aromatic hydrocarbons compounds (such as benzene, alanine, and 2-Propanamine).

High-Efficiency Photocatalytic Oxidation of Benzyl Alcohol by NH2-UiO-66-(Indole-2,3-Dione)-Fe.

The photocatalytic oxidation of biomass-derived benzyl alcohol provides a promising way for the synthesis of benzoic acid, which is an important intermediate with wide applications. To improve the efficiency of photocatalytic benzyl alcohol oxidation to benzoic acid is of great interest. In this work, we propose the utilization of NH2-UiO-66-ID-Fe catalyst for photocatalytic oxidation of benzyl alcohol to benzoic acid, where NH2-UiO-66 is a typically used metal-organic framework, ID is indole-2,3-dione (ID) that has biocompatibility, light absorption property and can be covalently combined with amino-functionalized substances. The NH2-UiO-66-ID-Fe catalyst exhibits improved light absorption and photo-generated electron-hole separation ability compared with NH2-UiO-66. The photocatalytic performance of NH2-UiO-66-ID-Fe was examined for the oxidation of bio-based benzyl alcohol under mild conditions of air atmosphere, room temperature and no additive or additional oxidant involved. The results show that the conversion of benzyl alcohol and the selectivity to benzoic acid could both reach over 99 % in 6 h, and the generation rate of benzoic acid per gram of catalyst is 3.36 mmol g-1 h-1. The reaction mechanism was detected by radical trapping method and in situ electron paramagnetic resonance. This study presents an efficient and environmentally benign avenue for the synthesis of carboxylic acid compounds.

Celecoxib Catalyzed the Coupling Reaction of Epoxide and CO2

Abstract: In this study, high yields of various cyclic carbonates are obtained by employing the drug celecoxib to promote the coupling reaction of CO2 and epoxide using tetrabutylammonium bromide. This strategy enables the synthesis of benzoic acid, phenylpropiolic acid, and 2, 4- quinazolinedione. In addition, the model reaction mechanism is proposed.

Iodine/DMSO-catalyzed oxidative deprotection of N-tosylhydrazone for benzoic acid synthesis.

An oxidative deprotection of tosylhyrdazones has been demonstrated to afford benzoic acids using iodine and DMSO system. This efficient oxidative deprotection protocol offers exceptional functional group toleration under mild reaction conditions without any initiators or bases. Notably, the tosylhydrazone with the heteroaryl ring or with the aryl ring having base-sensitive hydroxyl and ester functional groups smoothly afforded the corresponding benzoic acid analogues under developed conditions. Moreover, this method features short reaction times, high product yields and easy purification by avoiding column-chromatographic purification.

Selective electrocatalytic oxidation of C(OH)–C bond in lignin with Pt@CeO2 toward the synthesis of benzoic acid

The synthesis of carboxylic acid compounds by the selective electrooxidation cleavage of the C(OH)-C bond in lignin is significant to biomass conversion to produce high-value-added chemicals. However, it is challenging to selectively cleave the C(OH)-C bond due to its extremely high dissociation energy of 260–300 kJ mol−1. Herein, a simple and effective method of hydrothermal process and wet impregnation is proposed to synthesize Pt@CeO2 catalysts. The cleavage of the C(OH)-C bond by Pt@CeO2, a catalyst loaded with a small amount of noble metal, triggered the electrochemical oxidation of lignin, resulting in the highly selective synthesis of carboxylic acid compounds. Consequently, more reactive oxygen species (ROS) are produced in the electrocatalytic oxidation process, which enhances the cleavage of C(OH)-C bond and the oxidation of benzaldehyde. In addition, Pt@CeO2 can also be used for the electrochemical depolymerization of industrial alkali lignin to produce carboxylic acids. This research proposes an efficient way of producing carboxylic acids of high value by utilizing an electrocatalyst for the electrocatalytic oxidation of lignin.

PIDA-Catalysed oxidative C–C bond cleavage for the direct synthesis of benzoic acids and antibacterial studies of the amides derivatives

A hypervalent iodine, (diacetoxyiodo)benzene (PIDA) catalysed facile synthesis of benzoic acids has been developed from aromatic ketone through oxidative C–C bond cleavage. A series of aromatic ketones get converted to the corresponding aromatic acid via oxime intermediate. Additionally, we have also utilized the resulted benzoic acid for the amide compounds using drug intermediate and studied the antibacterial activities. The use of hypervalent iodine, milder reaction conditions, good to high yields, clean protocols, the biological application are the notable features of the method.

Solar-driven photocatalytic transformation of toluene to benzoic acid over perovskite-type NiTiO3 decorated with reduced GO and g-C3N4 nanosheets

In this work, a perovskite-type nickel (II) titanate (NiTiO3; labeled as NTO) was synthesized and supported with reduced graphene oxide (rGO) and graphitic carbon nitride (CN: g-C3N4) nanosheets by ultrasound-assisted impregnation method. The solar-induced photocatalytic activity and selectivity of the prepared NTO-based perovskite catalysts were evaluated for toluene (TOL) oxidation to benzoic acid (B_COOH) under varying operating conditions. Results revealed that the NTO perovskite exhibited a higher selectivity (95–98%) for the photooxidation of TOL to B_COOH by 125–95 times higher than benzaldehyde (B_CHO) and benzyl alcohol (B_CH2OH) at 1 vol% H2O2 and O2 flow. At zero H2O2 level, the selective oxidation of TOL to B_CHO and B_CH2OH enhanced by 5.4 and 2.7 times as compared with the B_COOH production rate. Besides, NTO@CN (NTN) outperformed NTO@rGO (NTG) for the selective photocatalytic oxidation of TOL to B_COOH in solvent-free and water media under UV, visible, and sunlight irradiation. The production yield of B_COOH was 388.4, 491.2, and 455.6 µmol/L over NTO, NTN, and NTG, respectively at 1 vol% H2O2 and O2 flow for 3 h of solar irradiation. In both composites, carbon sheets supported the photocatalytic stability of NTO and potential energy for H2O2 decomposition to ∙OH radicals. This is validated by the radical scavenger test and electron paramagnetic resonance (EPR) analysis, which verified the crucial role of hydroxyl (•OH) radicals in the photocatalytic oxidation of TOL to B_COOH. These findings proved the effectiveness of NTN and NTG perovskite composites for solar-induced organic synthesis of benzoic acid from water contaminated with toluene using sunlight (as a renewable energy source).

Microbial synthesis of 4-hydroxybenzoic acid from renewable feedstocks

4-Hydroxybenzoic acid (4HBA) and its esterified forms can be used as preservatives in the pharmaceutical and food industries. Here, we reported the establishment of a coenzyme-A (CoA) free multi-enzyme cascade in Escherichia coli to utilize biobased L-tyrosine for efficient synthesis of 4HBA. The multi-enzyme cascade contains L-amino acid deaminase from Proteus mirabilis, hydroxymandelate synthase from Amycolatopsis orientalis, (S)-mandelate dehydrogenase and benzoylformate decarboxylase from Pseudomonas putida, and aldehyde dehydrogenase from Saccharomyces cerevisiae. The whole-cell biocatalysis afforded the synthesis of 128 ± 1 mM of 4HBA (17.7 ± 0.1 g/L) from 150 mM L-tyrosine with > 85% conversion within 96 h. In addition, the artificial enzymatic cascade also allowed the synthesis of benzoic acid from 100 mM L-phenylalanine with a conversion ∼ 90%. In summary, our research offers a sustainable alternative for synthesizing 4HBA and benzoic acid from renewable feedstocks.

Synthesis of procaine analogues containing pentafluoroethoxy groups in the aromatic nucleus

In order to synthesize procaine analogs containing one or two pentafluoroethoxy groups, a method for the synthesis of benzoic acids containing a pentafluoroethoxy group in the ortho-position of the benzene nucleus has been developed. An effective method for the synthesis of procaine structural analogues containing one or two pentafluoroethoxy groups has been proposed. It has been shown that the replacement of the amino group by the pentafluoroethoxy group in the procaine molecule leads to a significant increase in the local anesthetic activity of the obtained compounds. The most active compound was a structural analogue of procainamide containing two pentafluoroethoxy groups in positions 2 and 4. The formation of fluorine-containing analogues of procaine was confirmed by 1H, 19F and 13C NMR spectroscopy and mass spectrometry.

CO2 activation by electrogenerated divalent samarium for aryl halide carboxylation.

The reductive carboxylation of aryl halides has been investigated using a samarium electrode as a sacrificial anode to yield the corresponding benzoic acids, providing a smooth strategy for CO2 activation. Carboxylation occurred after an efficient reduction of carbon dioxide mediated by an electrogenerated Sm(ii)-complex acting as a strong monoelectronic reductive reagent.

Zeolitic intralayer microchannels of magadiite, a natural layered silicate, to boost green organic synthesis.

Despite the considerable attention given to the applications of magadiite in previous research, the properties of this natural layered silicate have remained mysterious due to the lack of crystal structure information. On the other hand, no one has doubted the intercalation capability between the layers. Here we succeed in determining the structure of magadiite using X-ray pair distribution functions and synchrotron powder diffractometry. We discover unexpected zeolitic microchannels within the layers. We describe efficient synthesis of 100% pure benzoic acid from toluene by using magadiite as an additive in a TiO2 photocatalytic system oxidizing toluene. Based on the uncovered structure of magadiite, we clarify the mechanism of this unique photocatalytic system: the microchannels of magadiite not only separate/accommodate the desired partially oxidized product formed on TiO2 but also prevent the accumulation of the overoxidized products on the TiO2 surface that deactivates the photocatalytic activity.

炭素と炭素をつなげよう : グリニャール反応(デモ実験虎の巻)

炭素と炭素をつなげよう : グリニャール反応(デモ実験虎の巻)

Yeast response and tolerance to benzoic acid involves the Gcn4- and Stp1-regulated multidrug/multixenobiotic resistance transporter Tpo1

The action of benzoic acid in the food and beverage industries is compromised by the ability of spoilage yeasts to cope with this food preservative. Benzoic acid occurs naturally in many plants and is an intermediate compound in the biosynthesis of many secondary metabolites. The understanding of the mechanisms underlying the response and resistance to benzoic acid stress in the eukaryotic model yeast is thus crucial to design more suitable strategies to deal with this toxic lipophilic weak acid. In this study, the Saccharomyces cerevisiae multidrug transporter Tpo1 was demonstrated to confer resistance to benzoic acid. TPO1 transcript levels were shown to be up-regulated in yeast cells suddenly exposed to this stress agent. This up-regulation is under the control of the Gcn4 and Stp1 transcription factors, involved in the response to amino acid availability, but not under the regulation of the multidrug resistance transcription factors Pdr1 and Pdr3 that have binding sites in TPO1 promoter region. Benzoic acid stress was further shown to affect the intracellular pool of amino acids and polyamines. The observed decrease in the concentration of these nitrogenous compounds, registered upon benzoic acid stress exposure, was not found to be dependent on Tpo1, although the limitation of yeast cells on nitrogenous compounds was found to activate Tpo1 expression. Altogether, the results described in this study suggest that Tpo1 is one of the key players standing in the crossroad between benzoic acid stress response and tolerance and the control of the intracellular concentration of nitrogenous compounds. Also, results can be useful to guide the design of more efficient preservation strategies and the biotechnological synthesis of benzoic acid or benzoic acid-derived compounds.

Honeycomb hybrid crystal TiO2 film electrode for efficient benzoic acid synthesis

Highly ordered TiO2 nanotube film on a titanium foil was prepared by an anodization process. Then, the anatase–rutile hybrid crystal TiO2 materials fabricated at 700 °C were used as an anode for electrochemical synthesis of benzoic acid from toluene. At this anode, the highest yield of benzoic acid at ambient temperature is 27.5%, but it rises to 32.8% at 90 °C with a toluene conversion rate of 49.1%. The yield is increased mainly due to the hybrid crystal of the novel anode, and the formation of carbonized TiO2 nanotube surface at the Ti substrate together facilitates the charge transfer and induces a significant enhancement in the anode reactivity. Moreover, the effects of calcination temperature on the morphology, structures and crystallization of the TiO2 nanotubes were discussed in detail. A synergistic effect of electric field, visible light irradiation, and temperature for benzoic acid synthesis at the anatase–rutile hybrid crystal TiO2 was discussed. To our knowledge, this is the first study about the use of the carbonized anatase–rutile hybrid TiO2 nanotube films electrode in benzoic acid synthesis under the coupling fields. This study provides new insights into high-performance metal oxide electrode materials for organic synthesis.

Utility of Autoclave in the Synthesis of Organic Compounds

Synthesis of Benzimidazole and 2-Methylbenzimidazole from o-Phenylenediamine has been reported by conventional method of heating the reaction mixture on a water bath. Synthesis of Benzoic acid from Benzaldehyde by Cannizzaro reaction has also been reported. The authors of this article have synthesized these compounds by heating the reaction mixture in an autoclave. The yield obtained was found to be greater than that obtained using reported conventional methods, which emphasizes the utility of autoclave in the synthesis of organic compounds. The structure of synthesized compound was confirmed by Fourier-Transform Infrared Spectroscopy (FT-IR).

Theoretical Study of 4-(Hydroxymethyl)benzoic Acid Synthesis from Ethylene and 5-(Hydroxymethyl)furoic Acid Catalyzed by Sn-BEA

A sustainable route has been reported for the production of terephthalic acid (PTA) from 5-(hydroxymethyl)furoic acid (HMFA) and ethylene, both of which can be derived from biomass. This process starts with the production of 4-(hydroxymethyl)benzoic acid (HMBA) from HMFA and ethylene catalyzed by Sn-BEA. The subsequent oxidation of HMBA leads to PTA. The present study reports the results of a detailed computational investigation of the mechanism of HMBA synthesis from ethylene and HMFA mediated by Sn-BEA. Density functional theory calculations show that the formation of HMBA proceeds via Diels–Alder cycloaddition of HMFA and ethylene, which is rate-limiting, followed by Lewis acid-catalyzed dehydration. The solution-phase reaction and six different pathways in Sn-BEA, including one pathway on the Si site and five different pathways on the Sn site, are investigated for the Diels–Alder cycloaddition of HMFA and ethylene. Energy decomposition analysis (EDA) shows that the Sn site stabilizes the transition st...

Solar thermoelectric field plus photocatalysis for efficient organic synthesis exemplified by toluene to benzoic acid

The solar thermal electrochemical process synthesis of benzoic acid is an efficient way for organic synthesis based upon solar energy utilization. Graphite and platinum anodes have been developed with high yield and selectivity of benzoic acid. In this article, we present the first demonstration of the solar thermal-electro-photo field for efficient benzoic acid synthesis by using TiO2 nanotubes electrode. By adjusting the three-solar field process, toluene is oxidized at the surface of the photoactive, electrically driven, heat activated TiO2 nanotubes electrode. Results showed that, the synergistic effect of the three fields was found for enhancement of toluene oxidation at TiO2 electrode. The yield of benzoic acid and conversion of toluene is greatly improved with temperature, and arriving to 26.1% and 62.6% at 90°C, respectively. In this process, solar thermal decreases the electrolysis potential of toluene oxidation. Hydroxyl, carboxyl and OOH groups, as well as the emergence of TiOC bond at the surface of the TiO2 nanotubes electrode, lead to an increased UV and visible absorption and a significant enhancement of TiO2 photocatalytic properties to increase the yield of benzoic acid. Simultaneously, an applied solar electric potential promotes the separation of photogenerated electrons and holes. As a result the efficiency of TiO2 photocatalysis enhanced.

Iodine-catalyzed oxidative C–C bond cleavage for benzoic acids and benzamides from alkyl aryl ketones

Iodine-catalyzed, aerial oxygen supported C–C bond cleavage reaction of aryl alkyl ketones for the synthesis of benzoic acids and benzamides. Also benzylidene acetones and phenylacetylenes were converted to their aromatic acids at this conditions.

Diels–Alder and Dehydration Reactions of Biomass-Derived Furan and Acrylic Acid for the Synthesis of Benzoic Acid

Routes to benzoic acid starting from furan—obtained from hemicellulose in high yield—and methyl acrylate are reported. These routes involve Diels–Alder and dehydration reactions of furan and acrylic acid (or methyl acrylate) in a two-step reaction protocol that minimizes side reactions. The Diels–Alder reaction of furan and methyl acrylate (or acrylic acid) was run at 298 K and was catalyzed by Lewis acidic (Hf-, Zr-, and Sn-Beta) zeolite catalysts, and achieving a high turnover frequency (∼2 h–1) and no side reactions were observed. The oxanorbornene product was dehydrated at low temperatures (298 to 353 K) in mixtures of methanesulfonic acid and acetic anhydride in 96% yield. This is compared to an only 1.7% yield of methyl benzoate obtained for the dehydration of the oxanorbornene in neat methanesulfonic acid. The effect of oxanorbornene concentration and stereochemistry was found not to decrease the yield of aromatics, while dehydration of the carboxylic acid form of the oxanorbornene led to a decreas...