New multicomponent catalysts for the selective aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine
Aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine was carried out on new gold-based catalysts using as support bimodal UVM-7-like mesoporous silica containing Ni and Ce (or Sn) as oxide nanodomains partially embedded inside the mesoporous UVM-7 silica walls. These nanodomains acted as effective and stable inorganic anchors favoring the nucleation, growth and stability of supported gold particles. Following the atrane method (a “one-pot” strategy able to harmonize the hydrolytic reactivity of different heteroelements through the use of complexes containing triethanolamine-derived ligands (atranes) as precursors) the stability of the oxide nanodomains during oxidation …
Selective hydrogenation of nitroderivatives over Au/TiO2/UVM-7 composite catalyst
Abstract Hydrogenation of nitroderivatives (4-nitrostyrene or 7-nitro-1-tetralone) was performed using as support a silica mesoporous material with high specific surface area (1091 m2/g) and a bimodal pore size distribution (UVM-7). Gold and/or TiO2 were deposited inside the pores of this support with the aim to achieve high activity and selectivity for this reaction. The morphology and structure of the powders have been characterized by adsorption-desorption isotherms, XRD, TEM, STEM-HAADF, XPS and ATR-FTIR. Structural characterizations shown differences between the catalysts with and without titania. The presence of TiO2 provides a better size distribution of the spherical gold nanopartic…
AlTf-UVM-7—Highly active catalysts for the synthesis of long chain symmetrical ethers and non-ionic surfactant structures
New Lewis acid AlTf-UVM-7 catalysts with bimodal pore system and different Si to Al ratios were prepared in a two-step synthesis in which triflic acid (Tf) was incorporated into previously synthesized mesoporous aluminum-containing silica. The Al incorporation inside the pore walls was carried out through the Atrane method. The characterization of the resulted catalysts showed that the triflic acid treatment step did not damage the texture or the structure of the catalysts. These materials were used as green catalysts for the etherification of fatty alcohols and the conversion of ethylene glycol (EG) with n-octanol resulting in mixtures of short ethoxylated structures with a large distribut…
Mesoporous Materials Incorporating Metal Triflates
Metal triflates attracted a large interest as catalysts in the past three decades especially due to the Lewis acid properties exhibited by these compounds and the variety of the functional group transformations. This chapter proposes an overview presenting the catalytic performances of triflates both as molecular compounds and as triflates dispersed in different solid matrices. In the first part the performances of molecular triflates in organic reactions carried out in the presence of water or water as solvent considering both water-sensitive and -insensitive metals are discussed. Then, the importance of materials incorporating triflates is demonstrated for catalysts obtained via immobiliz…
Photoluminescence study of terbium-exchanged ultrastable Y zeolites: Number of species, photoluminescence decays and decay-associated spectra
Terbium-exchanged ultrastable Y (USY) zeolites were investigated by using time-resolved photoluminescence spectroscopy techniques and methods. To determine the distribution of terbium species in USY zeolites together with their photoluminescence properties, several analysis methods for the time-resolved luminescence spectra were used such as the area normalization of time-resolved photoluminescence spectra, singular value decomposition, global nonlinear least squares, and the maximum entropy. Except for a questionable long lifetime, small contribution of a terbium species with lifetime of 1.9¿2.1 ms, all the experimental and analysis results converged to a two terbium species distribution w…
Comparative hydroamination of aniline and substituted anilines with styrene on different zeolites, triflate based catalysts and their physical mixtures
Abstract Catalytic performances of different zeolites (Beta and mordenites), scandium triflate based catalysts, mesoporous UVM-7 encapsulated scandium triflate and physical mixtures prepared under ultrasound irradiation were evaluated in the hydroamination of aniline and substituted anilines with styrene. The performances of these catalysts were controlled by the type of acidity and strength. Thus, the conversion was mainly controlled by the strength of the acid sites and their accessibility, while the selectivity appeared to be controlled by the Lewis/Bronsted type of acidity. Lewis acid catalysts directed the reactions mainly to the formation of the Markovnikov adducts while Bronsted acid…
Heterogeneous Gold Catalyst: Synthesis, Characterization, and Application in 1,4-Addition of Boronic Acids to Enones
The new 1 wt % Au/TiO2–UVM-7 catalyst was prepared and fully characterized. This heterogeneous catalyst proved to be active, selective and recyclable for the unprecedented gold-catalyzed 1,4-addition of various functionalized arylboronic acids to 2-cyclohexen-1-one and other selected enones using toluene as a solvent. The gold-based catalyst was recycled two times and played an active role in this reaction, and the nature of the solvent determined a remarkable change in the products’ selectivities.
New heterogeneous catalysts for greener routes in the synthesis of fine chemicals
Abstract New strong Lewis acid SnTf-MCM-41 and SnTf-UVM-7 catalysts with unimodal and bimodal pore systems were prepared in a two-step synthesis in which the triflic acid (Tf) was incorporated to previously synthesized mesoporous tin-containing silicas. The Sn incorporation inside the pore walls was carried out through the Atrane method. The SnTf-UVM-7 catalysts were prepared by aggregating nanometric mesoporous particles defining a hierarchic textural-type additional pore system. Following these procedures, catalysts with different Si/Sn ratios—21.8 to 50.8 for SnTf-MCM-41 and 18.4 for SnTf-UVM-7—were prepared. These new materials were tested in the acylation of aromatic sulfonamides using…
Epoxidation of dibenzocycloalkenes on Ti–Ge-MCM-41 and Ti-SBA-15 catalysts
Abstract Epoxidation of a series of dibenzocycloalkenes: phenanthrene, 5H-dibenzo[ a , e ]cycloheptene, 5H-dibenzo[ a , c ] cycloheptene, 5,6-dihydrodibenzo[ a , e ]cyclo-octene, and dibenzo[ a , e ]cyclooctene with hydrogen peroxide was investigated on Ti- and Ge-modified Ti-incorporated-type mesoporous catalysts including MCM-41 and SBA-15 structures looking for the effect of the porous texture and Ge-promoting on both activity and selectivity to epoxide and H 2 O 2 efficiency. Ti–Ge-MCM-41 catalysts (Si/Ti = 43; Si/Ge = 85 and Si/Ti = 41; Si/Ge = 62) were prepared by a one-pot surfactant-assisted procedure based on the use of a cationic surfactant (CTAB, cetyltrimethylammonium bromide), …
Efficient Sc triflate mesoporous-based catalysts for the synthesis of 4,4′-methylenedianiline from aniline and 4-aminobenzylalcohol
Abstract Sc triflate mesoporous-based catalysts have been prepared using a two-step strategy (i.e., Atrane method) based on the formation of the hierarchic bimodal porosity in the first step and the formation of Sc triflate complexes at the materials surface in the second step. All solids were analyzed by EPMA, surface area, and pore size values, XRD, TEM, FTIR, and 45Sc NMR static spectra. The catalysts have been investigated in the synthesis of 4,4′-methylenedianiline (4,4′-MDA) from aniline and 4-aminobenzylalcohol. 4,4′-MDA was obtained with selectivities over 85.0% for a conversion of aniline of 31%, at 80 °C and after 24 h. Using microwaves, selectivities of 90% in 4,4′-MDA were reach…
Synthesis, characterization and catalytic behavior of AlTf/UVM-7 as new green catalysts for the glycols etherification reactions
Abstract Bimodal porous Al–UVM-7 system materials with different Si-to-Al ratios were prepared using the Atrane route. These were converted in strong acid heterogeneous AlTf-based catalysts after the treatment with methanolic solutions of triflic acid. The materials so obtained were used as catalysts for the conversion of ethylene glycol (EG) and propylene glycol (PG) with octanol under solvent-free conditions. The process is selective to short ethoxylated structures resulting in the corresponding monoethers. While the conversion of EG and PG was very high (>94%) irrespective of the support characteristics, 1-octanol was transformed only in low degree (3–35%), and its conversion depends on …
Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts.
Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)-imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions p…
A new chiral dimanganese(iii) complex: synthesis, crystal structure, spectroscopic, magnetic, and catalytic properties
Two enantiomeric complexes of formula [MnIII2(μ-OCH3)2(R-valBINAM)2]·1.75DMF (1) and [MnIII2(μ-OCH3)2(S-valBINAM)2]·2DMF (2) [valBINAM = 1,1′-binaphthalene-2,2′-bis(3-methoxysalicylideneiminate)] have been synthesized using as a ligand the chiral Schiff bases resulting from the condensation reactions between o-vanillin and the chiral 1,1′-binaphthyl-2,2′-diamine. The structures of 1 and 2 which have been solved by single crystal X-ray diffraction consist of neutral dimers, the manganese(III) ions being bridged by two methoxido anions, arising from the solvent, and by two valBINAM2− ligands. Their circular dichroism spectra at room temperature emphasize the occurrence of the exciton coupling…
CCDC 1482464: Experimental Crystal Structure Determination
Related Article: Alina S. Dinca, Natalia Candu, Sergiu Shova, Francesc Lloret, Miguel Julve, Vasile I. Parvulescu, Marius Andruh|2016|RSC Advances|6|86569|doi:10.1039/C6RA18989J
CCDC 1482465: Experimental Crystal Structure Determination
Related Article: Alina S. Dinca, Natalia Candu, Sergiu Shova, Francesc Lloret, Miguel Julve, Vasile I. Parvulescu, Marius Andruh|2016|RSC Advances|6|86569|doi:10.1039/C6RA18989J