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12 pages, 1496 KiB

Open AccessArticle

A New Pd-Based Catalytic System for the Reductive Carbonylation of Nitrobenzene to Form N-(4-hydroxyphenyl)acetamide Selectively in One Pot

by Andrea Vavasori, Marco Capponi and Lucio Ronchin

Reactions 2023, 4(4), 725-736; https://doi.org/10.3390/reactions4040042 - 17 Nov 2023

Viewed by 1543

Abstract

N-(4-hydroxyphenyl)acetamide (commonly named paracetamol or acetaminophen) is a target molecules for many industries that produce chemicals for pharmaceutical applications. The industrial processes, however, use multistep procedures with low overall yield and/or severe drawbacks and problems in terms of sustainability. In the present paper, [...] Read more.

N-(4-hydroxyphenyl)acetamide (commonly named paracetamol or acetaminophen) is a target molecules for many industries that produce chemicals for pharmaceutical applications. The industrial processes, however, use multistep procedures with low overall yield and/or severe drawbacks and problems in terms of sustainability. In the present paper, a one-pot synthesis is proposed based on the reductive carbonylation of nitrobenzene catalyzed by Pd(II)-complexes. Usually, such a reaction leads to a mixture of different products, including aniline, 4-aminophenol and 1,3-diphenylurea. However, the selectivity towards the possible products strongly depends by the ligands on the Pd(II)-catalyst, but also by the nature of the solvent. According to this, we have found that when the reaction was carried out in dilute acetic acid as a solvent, the [PdCl₂(dppb)] catalyst precursor leads in one pot to N-(4-hydroxyphenyl)acetamide. Under optimized reaction conditions, it was possible to produce N-(4-hydroxyphenyl)acetamide with a 85 mol % of selectivity in ca. 5 h. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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17 pages, 5315 KiB

Open AccessArticle

Multicomponent Reactions Promoted by Ecocatalyst from Metal Hyperaccumulating Plant Pluchea sagittalis

by Leonardo H. R. Alponti, Monize Picinini, Ernesto A. Urquieta-Gonzalez, Caroline S. da Silva, Simone Y. S. Silva, Sebastião C. Silva, Marilene N. de Oliveira, Juliana Viera, Maria Fatima das G. F. da Silva and Arlene G. Corrêa

Reactions 2023, 4(4), 552-568; https://doi.org/10.3390/reactions4040033 - 07 Oct 2023

Viewed by 1049

Abstract

Phytoremediation has been considered a sustainable environmental technology for heavy metals decontamination. In this work, we evaluated the metal contents by inductively coupled plasma optical emission spectrometry (ICP-OES) of three plant species collected in a mine in the Brazilian Amazonia area. Based on [...] Read more.

Phytoremediation has been considered a sustainable environmental technology for heavy metals decontamination. In this work, we evaluated the metal contents by inductively coupled plasma optical emission spectrometry (ICP-OES) of three plant species collected in a mine in the Brazilian Amazonia area. Based on this analysis, Pluchea sagitallis leaves were selected to prepare metallic ecocatalysts. The leaf ashes and the obtained ecocatalysts were characterized by ICP-OES, X-ray diffraction (XRD), scanning electron microscopy (SEM) and N₂-physisorption measurements. Moreover, they were evaluated in the Biginelli and Hantzsch multicomponent reactions, furnishing the corresponding 3,4-dihydropyrimidin-2-(1H)-ones and 1,4-dihydropyridines with good to excellent yields. The best ecocatalyst was easily recovered and recycled in up to six reactions without a significant decrease in its performance. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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13 pages, 1945 KiB

Open AccessArticle

Comparative Analysis of Bio- and Chemo-Catalysts for the Synthesis of Flavour Compound Hexanal from Linoleic Acid

by Jan Drönner, Valentin Gala Marti, Simone Bandte, Anna Coenen, Ulrich Schörken and Matthias Eisenacher

Reactions 2023, 4(3), 518-530; https://doi.org/10.3390/reactions4030031 - 18 Sep 2023

Viewed by 889

Abstract

Hexanal, hexenal, nonenal and their corresponding alcohols are used as green notes in the fragrance and flavour industry. The production of bio-based hexanal starts from linoleic acid, which can be obtained from sunflower or safflower oil. The biocatalytic process utilizes C₁₃-specific [...] Read more.

Hexanal, hexenal, nonenal and their corresponding alcohols are used as green notes in the fragrance and flavour industry. The production of bio-based hexanal starts from linoleic acid, which can be obtained from sunflower or safflower oil. The biocatalytic process utilizes C₁₃-specific lipoxygenase (LOX) for hydroperoxidation and consecutive splitting with hydroperoxide lyase (HPL). In this study, we investigated the chemical splitting of the LOX product 13-HPODE in comparison to HPL catalysis. In addition, 13-HPODE was synthesized using enriched linoleic acid from safflower oil. Varying amounts of soybean flour suspension as a source of LOX yielded up to 60% HPODE with a regioselectivity of 92% towards 13-HPODE. Using low-toxicity Lewis acids like AlCl₃ and ZrCl₄, cleavage of the produced 13-HPODE was possible. A maximum hexanal yield of 22.9% was reached with AlCl₃ under mild reaction conditions, though product degradation was an interfering process. Comparative trials with N-terminal truncated HPL from papaya revealed hexanal recovery within a comparable range. Additionally, we successfully demonstrated the viability of Hock rearrangement of 13-HPODE through heterogeneous catalysts. Notably, Beta zeolite and Montmorillonite K10 exhibited a turnover frequency (TOF) on par with common heterogeneous catalysts employed in industrial processes. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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13 pages, 2312 KiB

Open AccessArticle

Catalytic Valorisation of Biomass-Derived Levulinic Acid to Biofuel Additive γ-Valerolactone: Influence of Copper Loading on Silica Support

by Rajender Boddula, Paramasivam Shanmugam, Rajesh K. Srivatsava, Nabila Tabassum, Ramyakrishna Pothu, Ramachandra Naik, Aditya Saran, Balaga Viswanadham, Ahmed Bahgat Radwan and Noora Al-Qahtani

Reactions 2023, 4(3), 465-477; https://doi.org/10.3390/reactions4030028 - 05 Sep 2023

Cited by 3 | Viewed by 1468

Abstract

γ-valerolactone (GVL) is a crucial chemical feedstock used in the production of fuel additives, renewable fuels, and fine chemicals alternative to petroleum-based solvents and chemicals, supporting the transition to sustainable energy solutions. It is promptly acquired by hydrogenating levulinic acid (LA) in a [...] Read more.

γ-valerolactone (GVL) is a crucial chemical feedstock used in the production of fuel additives, renewable fuels, and fine chemicals alternative to petroleum-based solvents and chemicals, supporting the transition to sustainable energy solutions. It is promptly acquired by hydrogenating levulinic acid (LA) in a gaseous or liquid phase with a homogeneous or heterogeneous catalyst using a variety of recognized catalytic processes. Herein, this work focuses on the use of silica-supported copper (Cu/SiO₂) catalysts for the gas-phase hydrogenation of LA to GVL under mild reaction conditions. The study analyzes how copper loading can affect the catalytic activity of the Cu/SiO₂, while the flow rate of LA, time-on-stream, reaction temperature, and LA concentration affect the catalytic efficiency. The SiO₂ support’s various Cu loadings are crucial for adjusting the catalytic hydrogenation activity. One of the studied catalysts, a 5 wt% Cu/SiO₂ catalyst, demonstrated ~81% GVL selectivity with ~78% LA conversion and demonstrated stability for ~8 h while operating at atmospheric pressure and temperature (265 °C) and 0.5 mL/h of LA flow rate. The ability to activate hydrogen, high amount of acidic sites, and surface area were all discovered to be advantageous for increased GVL selectivity. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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14 pages, 3693 KiB

Open AccessArticle

Study of the Synthetic Approach Influence in Ni/CeO₂-Based Catalysts for Methane Dry Reforming

by Marco Pizzolato, Giulia Da Pian, Elena Ghedini, Alessandro Di Michele, Federica Menegazzo, Giuseppe Cruciani and Michela Signoretto

Reactions 2022, 3(4), 634-647; https://doi.org/10.3390/reactions3040043 - 16 Dec 2022

Cited by 1 | Viewed by 1348

Abstract

This study focuses on the synthetic approach influence in morphostructural features and catalytic performances for Ni/CeO₂ catalysts. Incipient wetness impregnation, coprecipitation and nitrate combustion were studied as catalyst preparation approaches, and the materials were then tested at 700 °C for methane dry [...] Read more.

This study focuses on the synthetic approach influence in morphostructural features and catalytic performances for Ni/CeO₂ catalysts. Incipient wetness impregnation, coprecipitation and nitrate combustion were studied as catalyst preparation approaches, and the materials were then tested at 700 °C for methane dry reforming (MDR). The morphostructural properties of the materials were deeply studied using several techniques, such as temperature programmed reduction (TPR), to investigate reducibility and support-metal interaction, N₂ physisorption to evaluate the porosity and the surface area, scanning electron microscopy (SEM) and X-ray diffraction (XRD) to estimate Ni dispersion, and temperature programmed oxidation (TPO) to identify the type and amount of coke formed on catalysts’ surface after reaction. From the data obtained, coprecipitation turned out to be the most suitable technique for this application because this catalyst was able to reach 70% of CO₂ conversion and 30% methane conversion, with an H₂ yield of 15% and 30% yield of CO at the end of the 30 h test. Moreover, it was also the catalyst with the highest metal dispersion, the strongest interaction with the support, and the lowest coke deposition. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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12 pages, 7432 KiB

Open AccessArticle

C-N, C-O and C-S Ullmann-Type Coupling Reactions of Arenediazonium o-Benzenedisulfonimides

by Achille Antenucci and Stefano Dughera

Reactions 2022, 3(2), 300-311; https://doi.org/10.3390/reactions3020022 - 02 Jun 2022

Cited by 5 | Viewed by 3091

Abstract

Arenediazonium o-benzenedisulfonimides have been used as efficient electrophilic partners in Cu(I) catalysed Ullmann-type coupling. The synthetic protocols are mild and easy, and produced either N-alkylanilines, aryl ethers, or thioethers in fairly good yields (18 positive examples, average yield 66%). o-Benzenedisulfonimide was [...] Read more.

Arenediazonium o-benzenedisulfonimides have been used as efficient electrophilic partners in Cu(I) catalysed Ullmann-type coupling. The synthetic protocols are mild and easy, and produced either N-alkylanilines, aryl ethers, or thioethers in fairly good yields (18 positive examples, average yield 66%). o-Benzenedisulfonimide was recovered at the end of the reactions and was reused to prepare the starting salts for further reactions. It is noteworthy that diazonium salts have been used as electrophilic partners in the Ullmann-type protocol for the first time. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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11 pages, 1512 KiB

Open AccessArticle

High Yielding, One-Pot Synthesis of Bis(1H-indazol-1-yl)methane Catalyzed by 3d-Metal Salts

by Natalie M. Lind, Natalie S. Joe, Brian S. Newell and Aimee M. Morris

Reactions 2022, 3(1), 59-69; https://doi.org/10.3390/reactions3010005 - 04 Jan 2022

Viewed by 2476

Abstract

Synthetic access to poly(indazolyl)methanes has limited their study despite their structural similarity to the highly investigated chelating poly(pyrazolyl)methanes and their potentially important indazole moiety. Herein is presented a high yielding, one-pot synthesis for the 3d-metal catalyzed formation of bis(1H-indazol-1-yl)methane [...] Read more.

Synthetic access to poly(indazolyl)methanes has limited their study despite their structural similarity to the highly investigated chelating poly(pyrazolyl)methanes and their potentially important indazole moiety. Herein is presented a high yielding, one-pot synthesis for the 3d-metal catalyzed formation of bis(1H-indazol-1-yl)methane from 1H-indazole utilizing dimethylsulfoxide as the methylene source. Complete characterization of bis(1H-indazol-1-yl)methane is given with ¹H and ¹³C NMR, UV/Vis, FTIR, high resolution mass spectrometry and for the first time, single crystal X-ray diffraction. This simple, inexpensive pathway to yield exclusively bis(1H-indazol-1-yl)methane provides synthetic access to further investigate the coordination and potential applications of the family of bis(indazolyl)methanes. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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Review

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13 pages, 1628 KiB

Open AccessReview

Chlorophyll Sensitization of TiO₂: A Mini-Review

by Maria E. K. Fuziki, Angelo M. Tusset, Onélia A. A. dos Santos and Giane G. Lenzi

Reactions 2023, 4(4), 766-778; https://doi.org/10.3390/reactions4040044 - 01 Dec 2023

Viewed by 1299

Abstract

Recent studies have shown that chlorophyll sensitization can improve the performance of semiconductors like TiO₂ in photocatalytic reactions and light-harvesting technologies, such as solar cells. Faced with the search for renewable energy sources and sustainable technologies, the application of this natural pigment [...] Read more.

Recent studies have shown that chlorophyll sensitization can improve the performance of semiconductors like TiO₂ in photocatalytic reactions and light-harvesting technologies, such as solar cells. Faced with the search for renewable energy sources and sustainable technologies, the application of this natural pigment has been gaining prominence. The present work addresses some of the main possibilities of chlorophyll-TiO₂ combination, presenting the most relevant aspects affecting chlorophyll extraction and TiO₂ sensitization. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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22 pages, 1984 KiB

Open AccessReview

Zeolite-Containing Co Catalysts for Fischer–Tropsch Synthesis with Tailor-Made Molecular-Weight Distribution of Hydrocarbons

by Lilia Sineva, Vladimir Mordkovich, Ekaterina Asalieva and Valeria Smirnova

Reactions 2023, 4(3), 359-380; https://doi.org/10.3390/reactions4030022 - 15 Jul 2023

Cited by 3 | Viewed by 1297

Abstract

The review is dedicated to the topical field of research aimed at creating catalysts combining several types of active sites. At the same time, the composition of Fischer–Tropsch synthesis (FTS) products can be controlled by changing the strength and concentration of the active [...] Read more.

The review is dedicated to the topical field of research aimed at creating catalysts combining several types of active sites. At the same time, the composition of Fischer–Tropsch synthesis (FTS) products can be controlled by changing the strength and concentration of the active sites and inter-site distances. A comparative analysis of the literature data allows to formulate the main principles of catalytic particles formation active in FTS and acid-catalyzed transformations of hydrocarbons: (1) the presence of weak Bronsted acid sites to control the cracking depth, (2) an availability of Bronsted acid sites for re-adsorption hydrocarbons and (3) weak Co-zeolite interaction to reduce methane formation. Full article

(This article belongs to the Special Issue Traditional and Innovative Catalysts for Reactions of Industrial Interest)

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