103-50-4Relevant articles and documents
Cobalt-Catalyzed Secondary Alkylation of Arenes and Olefins with Alkyl Ethers through the Cleavage of C(sp2)-H and C(sp3)-O Bonds
Dong, Xunqing,Li, Qun,Li, Guigen,Lu, Hongjian
, p. 13402 - 13413 (2018)
A novel cobalt-catalyzed C-H alkylation of arenes and olefins is achieved with (pyridin-2-yl)isopropyl amine as an N,N-bidentate directing group. Different linear, branched, and cyclic alkyl ethers were used as practical secondary alkylating reagents through cleavage of C(sp3)-O bond, providing an efficient approach to the synthesis of verstile o-alkylated arylamides and tetrasubstituted acrylamides. Mechanistic studies indicate that cleavage of the inert C(sp3)-O bond involves a cobalt-promoted radical process and that cleavage of the inert C(sp2)-H bond by a cobalt catalyst is a rate-limiting step.
Sulfonated polypyrene (S-PPR) as efficient catalyst for esterification of carboxylic acids with equimolar amounts of alcohols without removing water
Tanemura, Kiyoshi,Suzuki, Tsuneo
, p. 1972 - 1975 (2013)
Sulfonated polypyrene (S-PPR) efficiently catalyzed the reactions between carboxylic acids and equimolar amounts of alcohols with and without heptane to give the corresponding esters in good to excellent yields. Esterification was carried out at 110 °C without removing water. Transesterification of carboxylic esters with a slight excess of alcohols smoothly proceeded without heptane to give the corresponding esters in good yields. For these reactions, S-PPR was recycled without significant loss of activities.
Spontaneous water release inducing nucleation during the nonaqueous synthesis of TiO2 nanoparticles
Zimmermann, Mandy,Garnweitner, Georg
, p. 8562 - 8568 (2012)
The formation of anatase nanoparticles by reaction of titanium(iv) isopropoxide in benzyl alcohol was studied. In contrast to previous reports on the nonaqueous synthesis, in this system the particle formation occurs within a very limited time span in the course of the synthesis, concurrently to a fast step-type pressure increase within the closed reaction system. By Karl Fischer titration and 1H NMR spectroscopy of both the liquid and the gaseous phase at different stages of the reaction, it is shown that water formation occurs during the pressure increase due to catalytic ether formation from benzyl alcohol. The generated water leads to instant nucleation and fast growth of crystalline nanoparticles, which is traced by powder X-ray diffraction as well as small-angle X-ray scattering and thereby shown to play a crucial role in the particle formation process. The Royal Society of Chemistry.
Preparation of a platinum nanoparticle catalyst located near photocatalyst titanium oxide and its catalytic activity to convert benzyl alcohols to the corresponding ethers
Akiyama, Toshiki,Arisawa, Mitsuiro,Harada, Kazuo,Honma, Tetsuo,Naka, Hiroshi,Saito, Susumu,Wada, Yuki
, p. 22230 - 22237 (2021)
A novel platinum nanoparticle catalyst closely located near the surface of titanium oxide, PtNP/TiO2, has been prepared. This catalyst has both the properties of a photocatalyst and a metal nanoparticle catalyst, and acquired environmentally friendly catalytic activity, which cannot be achieved by just one of these catalysts, to afford ethers from benzyl alcohols under the wavelength of 420 nm.
Zinc-catalyzed reduction of aldehydes with a hydrosilane leading to symmetric ethers and silyl ethers
Sakai, Norio,Nonomura, Yoshifumi,Ikeda, Reiko,Konakahara, Takeo
, p. 489 - 491 (2013)
The efficient reductive etherification of aromatic or aliphatic aldehydes using a reducing system that combines Zn(OTf)2 with either TMDS or Et3SiH is described. The present reducing system can also be applied to the hydrosilylation of aromatic aldehydes having either a strong electron-withdrawing group or a pyridine ring.
In Situ Generation of Br?nsted Acidity in the Pd-I Bifunctional Catalysts for Selective Reductive Etherification of Carbonyl Compounds under Mild Conditions
Wu, Dan,Hernández, Willinton Y.,Zhang, Songwei,Vovk, Evgeny I.,Zhou, Xiaohong,Yang, Yong,Khodakov, Andrei Y.,Ordomsky, Vitaly V.
, p. 2940 - 2948 (2019)
Selective synthesis of ethers from biomass-derived carbonyl compounds is an important academic and industrial challenge. The existing processes based on strong acid or metallic catalysts cannot provide high selectivity to ethers due to the occurrence of side reactions. Hereby we propose a Pd-I bifunctional heterogeneous catalyst for the selective reductive etherification of aldehydes with alcohols. Extensive catalyst characterizations uncovered the presence of iodine species on the surface of Pd nanoparticles. Heterolytic dissociation of hydrogen on the I-Pd surface sites leads to the "in situ" generation of a Br?nsted acid, which promotes the reaction toward the corresponding ethers with extremely high selectivity under very mild reaction conditions.
Sulfonic acid functionalized hyperbranched poly(ether sulfone) as a solid acid catalyst
Nabae, Yuta,Liang, Jie,Huang, Xuhui,Hayakawa, Teruaki,Kakimoto, Masa-Aki
, p. 3596 - 3602 (2014)
Sulfonic acid functionalized hyperbranched poly(ether sulfone) (SHBPES) was studied as a novel type of solid acid catalyst. Various molecular weights of SHBPESs were tested for the esterification reaction between acetic acid and 1-butanol. The SO3H terminal groups of the SHBPESs work as catalytically active sites, but all tested SHBPESs are totally or partially soluble under the current reaction conditions. To overcome the solubility problem, SHBPES was grafted onto carbon black, and this material, SHBPES/CB, shows fairly good catalytic activity and promising recyclability. The turnover frequency of SHBPES decreased upon grafting it onto carbon black, but it was still much better than that of Amberlyst-15. SHBPES/CB was also tested for the Friedel-Crafts alkylation of anisole and its durability seems to be much better than that of Amberlyst-15 under the operating conditions at 130°C. This journal is the Partner Organisations 2014.
Synthesis, characterization, and catalytic properties of H-Al-YNU-1 and H-Al-MWW with different Si/Al ratios
Fan, Weibin,Wei, Shuquan,Yokoi, Toshiyuki,Inagaki, Satoshi,Li, Junfen,Wang, Jianguo,Kondo, Junko N.,Tatsumi, Takashi
, p. 268 - 278 (2009)
H-Al-MWW with different Si/Al ratios has been synthesized in the presence of hexamethyleneimine by the postsynthesis method with the ion-exchange of Na+ with NH4+ unnecessary. However, irrespective of the framework Si/Al r
MoO3 supported on ordered mesoporous zirconium oxophosphate: An efficient and reusability solid acid catalyst for alkylation and esterification
Miao, Zhichao,Li, Zhenbin,Zhao, Jinping,Si, Weijiang,Zhou, Jin,Zhuo, Shuping
, p. 10 - 21 (2018)
A series of molybdenum oxide supported on ordered mesoporous zirconium oxophosphate (MoO3/M-ZrPO) materials with different MoO3 loadings (0–20 wt%) and calcination temperatures (500–900 °C) have been designed, synthesized and employed as solid acid catalysts in alkylation and esterification. The XRD, TG-DSC, H2-TPR, N2-physisorption and TEM characterizations were taken to investigate the structural properties and states of introduced MoO3 species. The influence of MoO3 loadings and calcination temperatures in catalytic performance was detailedly investigated and optimal catalytic activity was reached at 10 wt% MoO3 loadings and treated at 700 °C. Moreover, MoO3/M-ZrPO catalysts exhibited outstanding catalytic performance in Friedel-Crafts alkylation of different aromatic compounds and esterification of levulinic acid with 1-butanol. Furthermore, it was noteworthy that the catalyst had superior reusability and no noticeable declines were observed in catalytic performance even after seven runs.
Probing the active catalytic sites of zeolites with benzyl chloride
Van Herwijnen, Hendrikus W.G,Brinker, Udo H
, p. 4963 - 4967 (2002)
Zeolites contain numerous catalytic sites. In order to conduct organic chemistry properly, it is necessary to know which site catalyzes the reaction. The conversion of benzyl chloride was tested as a probe reaction. Different products are obtained when th
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Wender et al.
, p. 4375,4277 (1950)
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Silica sulfuric acid as an efficient reagent for the synthesis of symmetrical ethers under mild and heterogeneous conditions
Shirini, Farhad,Zolfigol, Mohammad Ali,Mohammadi, Kamal
, p. 2357 - 2361 (2003)
A mild and efficient method for the synthesis of symmetrical ethers using silica sulfuric acid is reported. All reactions are performed under compeletly heterogeneous conditions in good to high yields.
Synthesis and catalytic evaluation of acidic carbons in the etherification of glycerol obtained from biodiesel production
Chiosso, María E.,Casella, Mónica L.,Merlo, Andrea B.
, p. 107 - 114 (2021)
In this paper, the catalytic behaviour of carbonaceous system (Ccs) functionalized with –SO3H groups were studied in the etherification of refined (Gly) and crude glycerol (GlyC), with benzyl alcohol (BA). This Ccs was obtained by a synthetic method with low energetic cost in only 24 h. Its catalytic activity and selectivity were studied varying the catalyst percentage (2.5, 5 and 10 wt.%), the initial reactant molar ratio and temperature (between 80 and 120 °C). A very good catalytic performance was achieved (97 % conversion after 360 min of reaction), at 120 °C, Gly:BA = 3:1 and 10 wt.% of Ccs. The high activity can be attributed to high acid site density (6.4 mmol H+/g), that also allowed us to working at lower reaction temperature (100 °C) and with less catalyst concentration (2.5 wt.%), without observing significant loss in BA conversion. Monoether (ME1) was the major product of the reaction with 72 % selectivity. The material can be reused and still gives a notable conversion of BA (about 43 %) after three successive reuses. Finally, the Ccs was active and selective to the desired products in the etherification of crude glycerol (GlyC) derived of biodiesel industry. An important BA conversion (45 %) was obtained only reducing the water content of GlyC and without carrying out any other purification and/or neutralization treatment.
SELECTIVE BENZYLATION OF ALCOHOLS AND AMINES UNDER MILD CONDITIONS
Liotta, Louis J.,Ganem, Bruce
, p. 4759 - 4762 (1989)
A new synthesis of benzyl ethers and N-benzylamines is described under nonbasic conditions using the fluoboric catalyzed reaction of phenyldiazomethane
Aluminium exchanged heteropoly tungstate supported on titania catalysts: The generation of Lewis acidity and its role for benzylation reaction
Ramesh Kumar, Ch.,Sai Prasad,Lingaiah
, p. 83 - 90 (2011)
Aluminium exchanged heteropoly tungstate (AlTPA) supported on titania catalysts were prepared and characterized by FT-Infra red, X-ray diffraction, Laser Raman, temperature programmed desorption of ammonia and X-ray photo electron spectroscopy. The catalytic properties of the catalysts were evaluated for benzylation of anisole with benzyl alcohol. The catalysts showed high activity for anisole benzylation and the catalyst with 20 wt% of AlTPA exhibited highest activity. The presence of Al resulted in generation of Lewis acidic sites. Acidic property and chemical structure of AlTPA on different supports also evaluated by supporting AlTPA on Nb2O5, ZrO 2 and SnO2. The catalytic activity of these catalysts is in the order of AlTPA/TiO2 > AlTPA/SnO2 > AlTPA/ZrO2 > AlTPA/Nb2O5. The benzylation activity and selectivity towards benzylated product also depends on the reaction temperature, catalyst weight and anisole to benzyl alcohol ratio.
Thiazolium-based catalysts for the etherification of benzylic alcohols under solvent-free conditions
Bivona, Lucia Anna,Quertinmont, Fran?ois,Beejapur, Hazi Ahmad,Giacalone, Francesco,Buaki-Sogo, Mireia,Gruttadauria, Michelangelo,Aprile, Carmela
, p. 800 - 810 (2015)
Thiazolium and imidazolium hybrid materials were prepared by radical reactions between a mercaptopropyl-modified SBA-15 mesoporous silica and bis-vinylthiazolium or bis-vinylimidazolium dibromide salts. These hybrid materials were characterized by several techniques and were employed in the etherification reaction of 1-phenylethanol. Solvent-free conditions at 160C under different gas phases (oxygen, air, nitrogen and argon) were used. The thiazolium-based material displayed excellent performances. Further studies were carried out using unsupported thiazolium salts, with or without a methyl group at the C-2 position of the thiazolium moiety. These studies allowed us to propose a reaction mechanism. The supported thiazolium-based material was successfully used in the etherification reaction of two other benzylic alcohols and also in seven consecutive cycles. This work represents the first use of thiazolium-based compounds as catalysts for the etherification reaction of alcohols.
Synthesis of germanium dioxide nanoparticles in benzyl alcohol - A comparison
Kitschke, Philipp,Schulze, Steffen,Hietschold, Michael,Mehring, Michael
, p. 209 - 214 (2013)
The surfactant-free synthesis ofβphase germanium dioxide nanoparticles in ortho-methoxy benzyl alcohol and benzyl alcohol has been reported. Characterisation of the hexagonal β-GeO2 crystals, which involves powder X-ray diffraction, nitrogen adsorption measurements (Brunauer-Emmett Teller method), dynamic light scattering measurements, IR spectroscopy, transmission electron microscopy and energy-dispersive X-ray analysis has been presented. Synthesis of β-GeO2under ambient conditions in benzyl alcohol results in nanoparticles with diameters below 20 nm, whereas the synthesis under inert conditions in benzyl alcohol at reflux (205°C) gives larger nanoparticles. In ortho-methoxy benzyl alcohol, agglomerates with particle sizes above 100 nm are observed under inert atmosphere conditions at room temperature.
Sulfated mesoporous Au/TiO2 spheres as a highly active and stable solid acid catalyst
Li, Cheng Chao,Zheng, Yan Ping,Wang, Tai Hong
, p. 13216 - 13222 (2012)
In this work, we reported several kinds of highly stable, effective mesoporous Au/TiO2 sphere-based solid acid catalysts with large specific surface areas and good monodispersity in the reaction medium. In this process, monodisperse titanium glycolate spheres were first formed by an antisolvent precipitation route, and were then converted to mesoporous TiO 2 by in situ hydrolysis under hydrothermal conditions. The resultant uniform TiO2 spheres were subsequently functionalized with sulfate anions at different temperatures or incorporated with tungstophosphoric acid (TPA); the solid acid catalysts were thus fabricated. In particular, our monodisperse spherical catalysts with large specific surface area have shown remarkable performance in a wide range of acid-catalyzed reactions such as Friedel-Crafts alkylation, esterification and hydrolysis of acetate. The TiO2-based catalysts could be separated and reused showing no deactivation.
A Catalyst System Based on Copper(II) Bromide Supported on Zeolite HY with a Hierarchical Pore Structure in Benzyl Butyl Ether Synthesis
Agliullin, M. R.,Bayguzina, A. R.,Gallyamova, L. I.,Khusnutdinov, R. I.
, p. 937 - 941 (2020)
Abstract: Novel catalyst systems based on CuBr2 supported on zeolite HY with a hierarchical pore structure have been proposed for benzyl butyl ether synthesis by the intermolecular dehydration of benzyl and butyl alcohols. It has been shown that catalyst systems with a CuBr2 content of ~10 wt percent provide a benzyl butyl ether yield of ~95percent at 150°C.
CaS2O8: An efficient reagent for etherification of alcohols under microwave irradiation in solvent-free conditions
Badri, Rashid,Kiasat, Ali Reza,Nazari, Simin
, p. 589 - 593 (2007)
A new facile and efficient one-pot method for the synthesis of ethers by the reaction of alcohols with calcium peroxodisulfate under microwave irradiation is described. Copyright Taylor & Francis Group, LLC.
Efficient Catalysts In situ Generated from Zinc, Amide and Benzyl Bromide for Epoxide/CO2 Coupling Reaction at Atmospheric Pressure
Zhang, Shuai,Han, Feng,Yan, Shaorui,He, Mingyue,Miao, Chengxia,He, Liang-Nian
, p. 1311 - 1316 (2019)
Herein, in situ generated efficient catalysts were designed for fixation of CO2 to cyclic carbonates under mild conditions. Zinc bromide and N,N-dibenzyl-N,N-dimethylammonium bromide, being proved as active catalyst species, were in situ generated from cheap Zn powder, dimethyl formamide and benzyl bromide, and catalyzed the cycloaddition reaction of CO2 and various terminal epoxides in moderate to excellent yields at 80 °C and atmospheric pressure of CO2. The protocol circumvents the preparation of active catalysts, simultaneously possesses good catalytic activity under mild conditions.
Effects of the Framework and Mesoporosity on the Catalytic Activity of Hierarchical Zeolite Catalysts in Benzyl Alcohol Conversion
Li, Chao,Cho, Hong Je,Wang, Zhuopeng,Gou, Jinsheng,Ren, Yanqun,Xi, Hongxia,Fan, Wei
, p. 2406 - 2414 (2016)
The catalytic performance of three-dimensionally ordered mesoporous imprinted (3DOm-i) zeolite catalysts with different frameworks (3DOm-i MFI, 3DOm-i BEA, and 3DOm-i LTA) were investigated by the liquid-phase catalytic conversion of benzyl alcohol in mesitylene and compared to that of other microporous and mesoporous catalysts with a high external surface area, which included MCM-22, 300 nm MFI, ITQ-2, and Al-MCM-41. The mesoporosity in MFI and BEA zeolites can effectively enhance the catalytic performance of the zeolite catalysts for benzyl alcohol self-etherification catalyzed by both the acid sites on the external and internal surface and the alkylation of mesitylene with benzyl alcohol catalyzed exclusively by the acid sites on the external surface. For 3DOm-i LTA, MCM-22, and Al-MCM-41, only the acid sites on the external surface can be utilized in the catalytic reactions. A distinct difference in the product selectivity was also observed for the microporous and mesoporous catalysts.
Antimony(v) cations for the selective catalytic transformation of aldehydes into symmetric ethers, α,β-unsaturated aldehydes, and 1,3,5-trioxanes
Arias Ugarte, Renzo,Devarajan, Deepa,Mushinski, Ryan M.,Hudnall, Todd W.
, p. 11150 - 11161 (2016)
1-Diphenylphosphinonaphthyl-8-triphenylstibonium triflate ([2][OTf]) was prepared in excellent yield by treating 1-lithio-8-diphenylphosphinonaphthalene with dibromotriphenylstiborane followed by halide abstraction with AgOTf. This antimony(v) cation was found to be stable toward oxygen and water, and exhibited exceptional Lewis acidity. The Lewis acidity of [2][OTf] was exploited in the catalytic reductive coupling of a variety of aldehydes into symmetric ethers of type L in good to excellent yields under mild conditions using Et3SiH as the reductant. Additionally, [2][OTf] was found to selectively catalyze the Aldol condensation reaction to afford α-β unsaturated aldehydes (M) when aldehydes with 2 α-hydrogen atoms were used. Finally, [2][OTf] catalyzed the cyclotrimerization of aliphatic and aromatic aldehydes to afford the industrially-useful 1,3,5 trioxanes (N) in good yields, and with great selectivity. This phosphine-stibonium motif represents one of the first catalytic systems of its kind that is able to catalyze these reactions with aldehydes in a controlled, efficient manner. The mechanism of these processes has been explored both experimentally and theoretically. In all cases the Lewis acidic nature of the antimony(v) cation was found to promote these reactions.
Hydrothermal synthesis of a layered-type W-Ti-O mixed metal oxide and its solid acid activity
Murayama, Toru,Nakajima, Kiyotaka,Hirata, Jun,Omata, Kaori,Hensen, Emiel J. M.,Ueda, Wataru
, p. 243 - 250 (2017)
A layered-type W-Ti-O mixed oxide was synthesized by hydrothermal synthesis from an aqueous solution of ammonium metatungstate and titanium sulfate. To avoid the formation of titania, oxalic acid was used as a reductant. Optimized synthesis led to rod-like particles comprised of MO6 (M = W, Ti) octahedra connected in a corner-sharing fashion in the c-direction and in the form of micropore-containing {W6O21} units in the a-b plane. The surface area, acidity and acid catalytic activity (alkylation) increased with the amount of the layered-type W-Ti-O phase. Strong Br?nsted acid sites formed due to the thermal release of ammonia from the uncalcined precursor. Calcination at 400 °C led to the highest acidity and alkylation activity. Alkylation of benzyl alcohol and toluene led to heavy product formation due to over-alkylation of the product. The selectivity to the mono-alkylated product was improved by the addition of water, which competes with the selectively formed products for adsorption on the acid sites. FT-IR measurements showed that the layered-type W-Ti-O possesses Br?nsted acid sites and at least two different Lewis acid sites. The stronger Lewis acid sites can be converted into Br?nsted acid sites in the presence of water, and the weaker Lewis acid sites functioned in the presence of water. This water tolerance of Lewis acid sites is an important characteristic of layered-type W-Ti-O, as it allows the bifunctional catalyst to convert 1,3-DHA into lactic acid in water.
Ether synthesis using trifluoromethanesulfonic anhydride or triflates under mild reaction conditions
Nishiyama, Tomihiro,Kameyama, Hideaki,Maekawa, Hideki,Watanuki, Kouhei
, p. 258 - 262 (1999)
Reactions of magnesium alkoxides with trifluoromethanesulfonic anhydride or triflates gave corresponding symmetrical or unsymmetrical ethers in moderate to good yields under mild reaction conditions. The scope and limitations of the reaction are discussed.
Silver(I)-Catalyzed Reductive Cross-Coupling of Aldehydes to Structurally Diverse Cyclic and Acyclic Ethers
Dong, Guichao,Li, Chuang,Liang, Ting,Xu, Xin,Xu, Zhou
supporting information, p. 1817 - 1821 (2022/03/16)
A range of medium-sized cyclic ethers (5 to 11 membered) have been effectively synthesized through intramolecular reductive coupling of dialdehydes initiated by 50 ppm to 0.5% of AgNTf2 with hydrosilane at 25 °C. The catalytic system is also suitable for the coupling of two different monoaldehydes to provide unsymmetrical ethers. This protocol features broad functional group compatibility, high product diversity, high efficiency, and utility in the late-stage modification of complex biorelevant molecules.
Bis(pertrifluoromethylcatecholato)silane: Extreme Lewis Acidity Broadens the Catalytic Portfolio of Silicon
Thorwart, Thadd?us,Roth, Daniel,Greb, Lutz
supporting information, p. 10422 - 10427 (2021/05/27)
Given its earth abundance, silicon is ideal for constructing Lewis acids of use in catalysis or materials science. Neutral silanes were limited to moderate Lewis acidity, until halogenated catecholato ligands provoked a significant boost. However, catalytic applications of bis(perhalocatecholato)silanes were suffering from very poor solubility and unknown deactivation pathways. In this work, the novel per(trifluoromethyl)catechol, H2catCF3, and adducts of its silicon complex Si(catCF3)2 (1) are described. According to the computed fluoride ion affinity, 1 ranks among the strongest neutral Lewis acids currently accessible in the condensed phase. The improved robustness and affinity of 1 enable deoxygenations of aldehydes, ketones, amides, or phosphine oxides, and a carbonyl-olefin metathesis. All those transformations have never been catalyzed by a neutral silane. Attempts to obtain donor-free 1 attest to the extreme Lewis acidity by stabilizing adducts with even the weakest donors, such as benzophenone or hexaethyl disiloxane.
