- Optimization of the synthesis of glycerol derived monoethers from glycidol by means of heterogeneous acid catalysis
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We present an efficient and green methodology for the synthesis of glycerol monoethers, starting from glycidol and different alcohols, by means of heterogeneous acid catalysis. A scope of Br?nsted and Lewis acid catalysts were applied to the benchmark reaction of glycidol and methanol. The selected catalysts were cationic exchangers, such as Nafion NR50, Dowex 50WX2, Amberlyst 15 and K10-Montmorillonite, both in their protonic form and exchanged with Al(III), Zn(II) and Fe(III). Thus, total conversions were reached in short times by using 1 and 5% mol catalyst loading and room temperature, without the need for excess glycidol or the presence of a solvent. Finally, these conditions and the best catalysts were successfully applied to the reaction of glycidol with several alcohols such as butanol or isopropanol.
- Pires, Elisabet,García, José Ignacio,Leal-Duaso, Alejandro,Mayoral, José Antonio,García-Peiro, José Ignacio,Velázquez, David
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- 3-(5-HYDROXY-1-OXOISOINDOLIN-2-YL)PIPERIDINE-2,6-DIONE DERIVATIVES AND USES THEREOF
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The present disclosure provides a compound of Formula (I′): or a pharmaceutically acceptable salt, hydrate, solvate, prodrug, stereoisomer, or tautomer thereof, wherein Rx, X1, X2, and R1 are as defined herein, and methods of making and using same.
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Paragraph 1706-1707
(2020/02/05)
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- PNN tridentate ligand, ruthenium complex, and preparation method and application of ruthenium complex
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The invention discloses a PNN tridentate ligand, a ruthenium complex, and a preparation method and an application of the ruthenium complex. The structure of the ruthenium complex is represented by formula I, and the ruthenium complex has good catalytic activity in a reaction of converting cyclic carbonate into methanol and a reaction of hydrogenating and degrading polyester and polycarbonate. In addition, the PNN tridentate ligand and the ruthenium complex of the PNN tridentate ligand are good in stability, and the synthesis process is simple.
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Paragraph 0187-0192
(2020/06/04)
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- Catalytic Hydrogenolysis of Solketal on Bifunctional Catalysts with Production of High Octane Components of Motor Fuels
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The possibility of implementing the concept of converting bioglycerin into a blend of oxygenates, potentially applicable as components of gasoline by ketalization with acetone (T = 30°C–40°C, atmospheric pressure), accompanied by mild hydrogenolysis of ketal [T = 100°C–140°C, p(H2) = 2 MPa] to obtain a mixture of of glycerol and solketal isopropyl ethers was demonstrated. Results showed that the preferred method of conversion was the separate performing of ketalization and hydrogenolysis, since when these stages are combined, the side reaction of the formation of free isopropyl alcohol was highly selective. The regularities in the influence of the composition of the catalytic system (Pd/C + para-toluenesulfonic acid) on its activity were observed in the reaction of catalytic hydrogenation of solketal to a mixture of glycerol and solketal isopropyl ethers (optimal ratio of Pd/para-toluenesulfonic acid = 0.811 mol). The addition of 4%–5% glycerol to raw materials increased the yield of target hydrogenation products from 25% to 36%. Using a flow unit, the catalytic hydrogenation of solketal was optimized. In the optimal mode [T = 170°C, p(H2) = 4 MPa, v = 0.5 h?1, H2/feedstock = 660 nL L?1], the conversion of solketal to a mixture of target products (glycerol monoisopropyl ether, glycerol diisopropyl ethers, and solketal isopropyl ether) reached 98%. The possibility of carrying out the reaction on heterogeneous bifunctional catalysts of the Pd/sulfonated coal type was shown.
- Goncharova, A. V.,Knyazeva, M. I.,Maksimov, A. L.,Ni, D. S.,Ramazanov, D. N.,Samoilov, V. O.
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p. 108 - 117
(2020/03/27)
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- Glycerol acetal(ketal) ether and synthesis method thereof
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The invention discloses glycerol acetal(ketal) ether and a synthesis method thereof, and relates to the technical field of chemical industry synthesis. According to the method, two functional groups acetal(ketal) and ether are integrated into one molecule by using glycerol as a raw material, wherein the glycerol acetal(ketal) ether can improve the use efficiency of unit fuel additives; the method comprises two synthesis routes, etherification and acetalization (ketalization) can be sequentially performed, or acetalization (ketalization) and etherification can be sequentially performed, wherein the etherification reaction is an atomic economic reaction; the by-product of the acetalization (ketalization) reaction is only one molecule of water, such that the method is environmentally friendly and efficient; the yield of the glycerol acetal(ketal) ether is high, and can be up to 99%; and the solid acid catalyst is used, is clean and efficient, and can be recycled so as to greatly reduce the cost and achieve the high industrial value.
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Paragraph 0099; 0103
(2019/10/04)
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- Regioselective Ring-Opening of Glycidol to Monoalkyl Glyceryl Ethers Promoted by an [OSSO]-FeIII Triflate Complex
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A FeIII-triflate complex, bearing a bis-thioether-di-phenolate [OSSO]-type ligand, was discovered to promote the ring-opening of glycidol with alcohols under mild reaction conditions (0.05 mol % catalyst and 80 °C). The reaction proceeded with high activity (initial turnover frequency of 1680 h?1 for EtOH) and selectivity (>95 %) toward the formation of twelve monoalkyl glyceryl ethers (MAGEs) in a regioselective fashion (84–96 % yield of the non-symmetric regioisomer). This synthetic approach allows the conversion of a glycerol-derived platform molecule (i.e., glycidol) to high-value-added products by using an Earth-crust abundant metal-based catalyst.
- Monica, Francesco Della,Ricciardi, Maria,Proto, Antonio,Cucciniello, Raffaele,Capacchione, Carmine
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p. 3448 - 3452
(2019/08/01)
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- Synthesis of 3-alkoxypropan-1,2-diols from glycidol: Experimental and theoretical studies for the optimization of the synthesis of glycerol derived solvents
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A straightforward synthetic methodology has been derived for the synthesis of glycerol monoethers from glycidol and alcohols. Several homogeneous and heterogeneous basic catalysts have been tested, the best results being obtained with readily available and inexpensive alkaline metal hydroxides. In the best case, good yield of the desired monoether is obtained under smooth reaction conditions, always with total conversion of glycidol. The selectivity of the reactions mainly depends on the alcohol used, due to the concurrence of undesired side reactions. A mechanistic study carried out through computational DFT calculations, in which solvent effects are taken into account, also complemented the experiments, has allowed to identify the main reaction paths taking place under reaction conditions, giving insights into the main causes affecting the reaction selectivity and also into how it could be improved.
- Leal-Duaso,Caballero,Urriolabeitia,Mayoral,García,Pires
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p. 4176 - 4185
(2017/09/07)
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- Glycerol as a source of designer solvents: Physicochemical properties of low melting mixtures containing glycerol ethers and ammonium salts
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In this work we report the preparation of mixtures of several alkyl glyceryl ethers, as hydrogen bond donor compounds, with two ammonium salts, choline chloride and N,N,N-triethyl-2,3-dihydroxypropan-1-aminium chloride. The stability of the mixtures at different molar ratios and temperatures has been evaluated in order to determine the formation of low melting mixtures. Liquid and stable mixtures have been characterized and their physico-chemical properties such as density, viscosity, refractive index, conductivity and surface tension have been measured in the temperature range of 293.15 K to 343.15 K. Comparison of the mixtures prepared herein with the ones containing glycerol and choline chloride evidences the possibility of tuning the physico-chemical properties by changing the substitution pattern in the hydrogen bond donor compound or in the ammonium salt, thus broadening the scope of application of these mixtures.
- Leal-Duaso, Alejandro,Pérez, Pascual,Mayoral, José A.,Pires, Elisabet,García, José I.
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p. 28302 - 28312
(2017/11/06)
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- Glycerol Isopropyl Ethers: Direct Synthesis from Alcohols and Synthesis by the Reduction of Solketal
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The catalytic reduction of solketal ((2,2-dimethyl-1,3-dioxolan-4-yl)methanol) over bifunctional heterogeneous palladium catalysts is proposed as an alternative to the synthesis of glycerol isopropyl ethers by the etherification of glycerol. The direct synthesis of glycerol isopropyl ethers from isopropanol and glycerol requires severe conditions (T=130–150 °C, p(H2)=20–35 bar) and a large excess of isopropanol to reach a considerable yield. The main reaction products in the catalytic reduction of solketal are glycerol mono- and di-isopropyl ethers and solketal isopropyl ether. Solketal conversion over Al-HMS-supported palladium catalysts (T=120 °C and p(H2)=20 bar) affords a mixture of ethers with a high degree of conversion (87 %), 78 % selectivity, and excellent regioselectivity between isomeric ethers. Zeolite-BEA-supported palladium catalysts also exhibit high activity but much lower selectivity because of intense acetone aldol condensation. The effects of Si/Al ratios in BEA zeolites and Al-HMS aluminosilicates and the amounts of supported palladium (1 and 2 wt %) on the properties of the catalysts at different reaction temperatures and hydrogen pressures are considered.
- Samoilov, Vadim O.,Onishchenko, Maria O.,Ramazanov, Dzhamalutdin N.,Maximov, Anton L.
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p. 2839 - 2849
(2017/07/28)
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- Synthesis of Monoalkyl Glyceryl Ethers by Ring Opening of Glycidol with Alcohols in the Presence of Lewis Acids
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The present work deals with the production of monoalkyl glyceryl ethers (MAGEs) through a new reaction pathway based on the reaction of glycidol and alcohols catalyzed by Lewis acid-based catalysts. Glycidol is quantitatively converted with high selectivity (99 %) into MAGEs under very mild reaction conditions (80 °C and 0.01 mol % catalyst loading) in only 1 h using Al(OTf)3 or Bi(OTf)3 as catalyst. The proposed method enhances the choice of possible green synthetic approaches for the production of value-added products such as MAGEs.
- Cucciniello, Raffaele,Ricciardi, Maria,Vitiello, Rosa,Di Serio, Martino,Proto, Antonio,Capacchione, Carmine
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p. 3272 - 3275
(2016/12/16)
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- Aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) as a highly efficient and reusable catalyst for alcoholysis, hydrolysis, and acetolysis of epoxides
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Alcoholysis, hydrolysis, and acetolysis of epoxides were carried out in the presence of a catalytic amount of aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) to give the corresponding β-substituted alcohols in good yields. Alcoholysis and hydrolysis of epoxides catalyzed by ATRT proceeded faster than those by pyridinium p-toluenesulfonate (PPTS).
- Tanemura, Kiyoshi,Suzuki, Tsuneo
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supporting information
p. 1781 - 1789
(2016/11/17)
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- A highly efficient protocol for regioselective ring-opening of epoxides with alcohols, water, acetic acid, and acetic anhydride catalyzed by SbF3
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SbF3as an efficient catalyst has been used for regioselective alcoholysis, acetolysis and hydrolysis of epoxides to the corresponding β-alkoxy, β-acetoxy alcohols, and 1,2-diols in high to excellent yields. This study also represents a convenient synthesis of vic-diacetates from ring-opening of epoxides with acetic anhydride.
- Zeynizadeh, Behzad,Gilanizadeh, Masumeh,Aminzadeh, Farkhondeh Mohammad
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p. 1051 - 1056
(2016/07/06)
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- Modular synthesis of dihydroxyacetone monoalkyl ethers and isosteric 1-hydroxy-2-alkanones
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Straightforward methods for the efficient, systematic preparation of libraries of the title compound classes have been evaluated. A general and efficient modular route to dihydroxyacetone monoethers was developed based on trityl glycidol, which, through epoxide opening, oxidation, and deprotection, provided variously alkylated ethers by three routine operations in good overall yields (eight examples, 24-59 %). The preparation of structurally related 1-hydroxyalkanones depends on the availability of the most economic starting materials and on their physicochemical properties. Thus, the most practical one-step approaches consisted of the sec-selective oxidation of short-chain 1,2-diols (≤ C6) using NaOCl, and the direct ketohydroxylation of 1-alkenes (≥ C6) using buffered stoichiometric KMnO4 or catalytic RuO4 with reoxidation by oxone, for which mostly good overall yields were achieved on a multigram scale (nine examples, 15-78 %).
- Güclü, Deniz,Rale, Madhura,Fessner, Wolf-Dieter
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supporting information
p. 2960 - 2964
(2015/04/27)
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- Thermodynamic characteristics of the sorption of glycerol ethers on stationary phase OV-101
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Retention characteristics, temperature dependences of the retention characteristics, and thermodynamic characteristics of sorption on the nonpolar OV-101 phase are determined for 33 glycerol mono-, di-, and triethers with linear and branched monobasic alc
- Zhabina,Krasnykh,Levanova
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p. 1590 - 1593
(2014/10/16)
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- POLYOL ETHERS AND PROCESS FOR MAKING THEM
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New polyol ether compounds and a process for their preparation. The process comprises reacting a polyol, a carbonyl compound, and hydrogen in the presence of hydrogenation catalyst, to provide the polyol ether. The molar ratio of polyol to carbonyl compound in the process is greater than 5:1.
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Paragraph 0089
(2011/05/14)
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- TMDS-Pd/C: A convenient system for the reduction of acetals to ethers
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A simple and practical procedure for the reduction of acetals to ethers is described. It is based on the use of a 1,1,3,3-tetramethyldisiloxane (TMDS)-Pd/C system in the presence of a Br?nsted acid as the co-catalyst. The reaction occurs under mild conditions and ethers are obtained in high yields.
- Shi, Yan,Dayoub, Wissam,Chen, Guo-Rong,Lemaire, Marc
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experimental part
p. 1281 - 1283
(2011/03/22)
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- Investigation of the catalytic activity of an electron-deficient vanadium(IV) tetraphenylporphyrin: A new, highly efficient and reusable catalyst for ring-opening of epoxides
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In this work, the catalytic activity of high-valent tetraphenylporphyrinatovanadium(IV) trifluoromethanesulfonate, [V IV(TPP)(OTf)2], in the nucleophilic ring-opening of epoxides is reported. This new V(IV) catalyst was used as an efficient catalyst for alcoholysis with primary (methanol, ethanol and n-propanol), secondary (iso-propanol) and tertiary alcohols (tert-butanol), hydrolysis and acetolysis of epoxides with acetic acid and also for the conversion of epoxides to 1,2-diacetates with acetic anhydride, conversion of epoxides to thiiranes with ammonium thiocyanate and thiourea, and for conversion of epoxides to acetonides with acetone. The catalyst was reused several times without loss of its activity.
- Taghavi, S. Abdolmanaf,Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram,Mirkhani, Valiollah,Khosropour, Ahmad Reza,Ahmadi, Venus
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experimental part
p. 2244 - 2252
(2011/10/03)
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- MCM-41 grafted quaternary ammonium salts as recyclable catalysts for the sequential synthesis of dimethyl carbonate from epoxides, CO2, and methanol
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One kind of novel heterogenous bifunctional catalyst, MCM- 41 grafted quaternary ammonium salts with terminal amino group, was prepared. These catalysts exhibited excellent catalytic performance and good reusability in the sequential synthesis of dimethyl carbonate from epoxides, CO2, and methanol.
- Li, Jian,Wang, Liguo,Liu, Shimin,Li, Xueli,Shi, Feng,Deng, Youquan
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supporting information; experimental part
p. 1277 - 1278
(2011/02/17)
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- POLYOL ETHERS AND PROCESS FOR MAKING THEM
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New polyol ether compounds and a process for their preparation. The process comprises reacting a polyol, a carbonyl compound, and hydrogen in the presence of hydrogenation catalyst, to provide the polyol ether. The molar ratio of polyol to carbonyl compound in the process is greater than 5:1.
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Page/Page column 9-10
(2010/03/31)
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- Intramolecular hydrogen bonding (P=O-H) stabilizes the chair conformation of six-membered ring phosphates
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Six-membered cyclic phosphates (2-phenoxy-2-oxo-1,3,2-dioxaphosphorinanes) bearing an internal protected or unprotected hydroxyl group were designed, synthesized, and studied by NMR and computational methods. Selective opening of O-isopropylidene-protecte
- Cruz-Gregorio, Silvano,Sanchez, Mario,Clara-Sosa, Angel,Bernes, Sylvain,Quintero, Leticia,Sartillo-Piscil, Fernando
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p. 7107 - 7113
(2007/10/03)
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- Stereospecific and regioselective opening of an oxirane system. A new efficient entry to 1- or 3-monoacyl- and 1- or 3-monoalkyl-sn-glycerols
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Acyl or alkyl glycidols in the presence of trifluoroacetic anhydride (TFAA) and trifluoroacetate anions, undergo a regioselective and stereospecific opening of the oxirane system to produce the bis(trifluoroacetylated) derivatives, from which the corresponding 1(3)-monoacyl-sn-glycerols or 1(3)-monoalkyl-sn-glycerols can be obtained directly in high purity (>99%) and in quantitative yields.
- Stamatov, Stephan D.,Stawinski, Jacek
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p. 1601 - 1605
(2007/10/03)
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- A highly regio- and chemoselective reductive cleavage of benzylidene acetals with EtAlCl2-Et3SiH
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A highly regio- and chemoselective reductive cleavage of benzylidene acetals derived from 1,2- and 1,3-diols was achieved under mild conditions using EtAlCl2-Et3SiH reagent system in good to excellent yields. Labile protecting groups
- Balakumar, Vijayakrishnan,Aravind, Appu,Baskaran, Sundarababu
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p. 647 - 650
(2007/10/03)
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- Rapid and efficient ring opening of epoxides catalyzed by a new electron deficient tin(IV) porphyrin
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The new electron deficient tin(IV) tetraphenylporphyrinato trifluoromethanesulfonate, [SnIV(tpp)(OTf)2], was used as an efficient catalyst for the alcoholysis, hydrolysis and acetolysis of epoxides. Conversion of epoxides to thiiranes and acetonides were also performed efficiently in the presence of this catalyst.
- Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Shaibani, Reza
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p. 6105 - 6111
(2007/10/03)
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- Efficient regio- and stereoselective ring opening of epoxides with alcohols, acetic acid and water catalyzed by ammonium decatungstocerate(IV)
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Epoxides can be cleaved in a regio- and stereoselective manner under neutral conditions with alcohols and acetic acid in the presence of catalytic amounts of decatungstocerate(IV) ion, ([CeW10O36] 8-), affording the corresponding β-alkoxy and β-acetoxy alcohols in high yields. In water, ring opening of epoxides occurs with this catalyst to produce the corresponding diols in good yields.
- Mirkhani, Valiollah,Tangestaninejad, Shahram,Yadollahi, Bahram,Alipanah, Ladan
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p. 8213 - 8218
(2007/10/03)
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- Ferric perchlorate: An efficient reagent for regio- and stereoselective alcoholysis and hydrolysis of epoxides
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Regio- and stereoselective ring opening reaction of epoxides is achieved efficiently by aliphatic alcohols and water in the presence of catalytic amounts of ferric perchlorate.
- Salehi, Peyman,Seddighi, Behnam,Irandoost, Mohsen,Kargar Behbahani, Farahnaz
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p. 2967 - 2973
(2007/10/03)
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- Bismuth(III) chloride (BiCl3); an efficient catalyst for mild, regio- and stereoselective cleavage of epoxides with alcohols, acetic acid and water
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Epoxides can be cleaved in a regio- and stereoselective manner with alcohols, acetic acid and water in the presence of catalytic amounts of bismuth(III) chloride, affording the corresponding β-alkoxy and β-acetoxy alcohols and diols in high yields.
- Mohammadpoor-Baltork,Tangestaninejad,Aliyan,Mirkhani
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p. 2365 - 2374
(2007/10/03)
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- TiCl3(OTf) and TiO(TFA)2 efficient catalysts for ring opening of epoxides with alcohols, acetic acid and water
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TiCl3 (OTf) and TiO(TFA)2 can efficiently catalyze nucleophilic ring opening of epoxides in primary, secondary and tertiary alcohols, acetic acid and water to give the corresponding β-alkoxy alcohols, β-acetoxy alcohols and vicinal diols with high stereo- and regioselectivity in excellent yields. The reaction of optically active styrene oxide in MeOH with two titanium reagents was found to be highly stereospecific and afforded the corresponding S-(+)-2-methoxy-2-phenyl ethanol in 89-95% ee.
- Iranpoor, Nasser,Zeynizadeh, Behzad
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p. 1017 - 1024
(2007/10/03)
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- FeCl3·6H2O supported on SiO2 catalysed ring opening of epoxides with alcohols, acetic acid, water, chloride, bromide and nitrate ions
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FeCl3·6H2O absorbed on chromatographic silica gel can act as an efficient catalyst for alcoholysis, hydrolysis and acetolysis of epoxides. Methanolysis of (R)-styrene oxide proceeds with high stereospecificity and in excellent yield. This catalyst can also convert epoxides to their corresponding β-halohydrins and β-nitrato alcohols in the presence of chloride, bromide and nitrate ions respectively.
- Iranpoor, Nasser,Tarrian, Tahere,Movahedi, Zarangiz
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p. 1473 - 1476
(2007/10/03)
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