- MBA-cross-linked poly(N-vinyl-2-pyrrolidone)/ferric chloride macromolecular coordination complex as a novel and recyclable Lewis acid catalyst: Synthesis, characterization, and performance toward for regioselective ring-opening alcoholysis of epoxides
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A novel macromolecular-metal coordination complex, MBA-cross-linked PNVP/FeCl3 material was fabricated by immobilization of water intolerant ferric chloride onto the porous cross-linked poly(N-vinyl-2-pyrrolidone) carrier beads as a macromolecular ligand or carrier which was prepared by suspension free-radical copolymerization of N-vinyl-2-pyrrolidone (NVP) and N,N′-methylene bis-acrylamide (MBA) as a crosslinking agent in water. The obtained PNVP/FeCl3 was characterized by UV/vis and FT-IR spectroscopies, TGA, FE-SEM, EDX, and ICP techniques. This heterogenized version of ferric chloride is a convenient and safe alternative to highly water intolerant ferric chloride. The catalytic performance of (PNVP/FeCl3) as an efficient and recyclable polymeric Lewis acid catalyst was appropriately probed in the regio-and stereoselective nucleophilic ring opening of various epoxides with various alcohols in excellent yields with TOF up to 182.48 h?1 without generating any waste. The activity data indicate that this heterogeneous catalyst is very active and could be easily recovered, and reused at least six times without appreciable loss of activity indicating its stability under experimental conditions.
- Rahmatpour, Ali,Zamani, Maryam
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- Hydrogen bonding-catalysed alcoholysis of propylene oxide at room temperature
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Alcoholysis of propylene oxide (PO) is achieved over azolate ionic liquids (IL,e.g., 1-hydroxyethyl-3-methyl imidazolium imidazolate) at room temperature, accessing glycol ethers in high yields with excellent selectivity (e.g., >99%). Mechanism investigation indicates that cooperation of hydrogen-bonding of the anion with methanol and that of the cation with PO catalyses the reaction.
- Li, Ruipeng,Liu, Zhimin,Wang, Yuepeng,Xiang, Junfeng,Xu, Yueting,Zhang, Fengtao,Zhao, Yanfei
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supporting information
p. 8734 - 8737
(2021/09/08)
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- Bio-based solvents and gasoline components from renewable 2,3-butanediol and 1,2-propanediol: Synthesis and characterization
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In this study approaches for chemical conversions of the renewable compounds 1,2-propanediol (1,2-PD) and 2,3-butanediol (2,3-BD) that yield the corresponding cyclic ketals and glycol ethers have been investigated experimentally. The characterization of the obtained products as potential green solvents and gasoline components is discussed. Cyclic ketals have been obtained by the direct reaction of the diols with lower aliphatic ketones (1,2-PD + acetone→ 2,2,4-trimethyl-1,3-dioxolane (TMD) and 2,3-BD + butanone-2→2-ethyl-2,4,5-trimethyl-1,3-dioxolane (ETMD)), for which the ΔH0 r, ΔS0 r and ΔG0 r values have been estimated experimentally. The monoethers of diols could be obtained through either hydrogenolysis of the pure ketals or from the ketone and the diol via reductive alkylation. In the both reactions, the cyclic ketals (TMD and ETMD) have been hydrogenated in nearly quantitative yields to the corresponding isopropoxypropanols (IPP) and 3-sec-butoxy-2-butanol (SBB) under mild conditions (T = 120-140 °C, p(H2) = 40 bar) with high selectivity (>93%). Four products (TMD, ETMD, IPP and SBB) have been characterized as far as their physical properties are concerned (density, melting/boiling points, viscosity, calorific value, evaporation rate, Antoine equation coe°Cients), as well as their solvent ones (Kamlet-Taft solvatochromic parameters, miscibility, and polymer solubilization). In the investigation of gasoline blending properties, TMD, ETMD, IPP and SBB have shown remarkable antiknock performance with blending antiknock indices of 95.2, 92.7, 99.2 and 99.7 points, respectively.
- Bermeshev, Maxim,Goncharova, Arina,Kniazeva, Mariia,Kosyakov, Dmitry,Ladesov, Anton,Maximov, Anton,Ni, Denis,Samoilov, Vadim,Zarezin, Danil
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- PROCESSES FOR CONVERSION OF BIOLOGICALLY DERIVED MEVALONIC ACID
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The invention relates to a process comprising reacting mevalonic acid, or a solution comprising mevalonic acid, to yield a first product or first product mixture, optionally in the presence of a solid catalyst and/or at elevated temperature and/or pressure. The invention further relates to a process comprising: (a) providing a microbial organism that expresses a biosynthetic mevalonic acid pathway; (b) growing the microbial organism in fermentation medium comprising suitable carbon substrates, whereby biobased mevalonic acid is produced; and (c) reacting said biobased mevalonic acid to yield a first product or first product mixture.
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Paragraph 0095-0103
(2016/06/13)
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- Tunable synthesis of propylene glycol ether from methanol and propylene oxide under ambient pressure
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A series of basic and acidic ionic liquids, 1-butyl-3-methylimidazolium hydroxide (BMIMOH), 1-acetyl-3-methylimidazolium chloride (AcMIMCl) and AcMIMCl-FeCl3, or analogues of AcMIMCl, namely 1-potassium acetate-3-methylimidazolium chloride (KAcMIMCl), 1-potassium (sodium, ammonium) acetate-3-methylimidazolium hydroxides (KAcMIMOH, NaAcMIMOH and NH 4AcMIMOH), were prepared and used as catalysts for catalytic synthesis of propylene glycol ether via reaction of propylene oxide (PO) with methanol under mild reaction conditions. KAcMIMOH exhibited outstanding catalytic performance with 94.2% of conversion of PO and 99.1% of selectivity to 1-methoxy-2-propanol (MP-2) at 60°C and ambient pressure for 4 h. However, AcMIMCl-FeCl3 showed a good catalysis performance with high selectivity to 2-methoxy-1-propanol (MP-1). The tunable synthesis of MP-2 or MP-1 catalyzed by basic compound KAcMIMOH or acidic ionic liquid AcMIMCl-FeCl3 was realized.
- Bai, Yu,Cai, Qinghai,Wang, Xiaoguang,Lu, Bin
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experimental part
p. 386 - 390
(2011/08/04)
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- An atom-economic reaction for synthesis of 1-phenoxy-2-propanol over Al2O3/MgO
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Al2O3/MgO materials with various Mg/Al molar ratios were prepared and characterized by XRD, FT-IR, SEM and BET analysis. These materials were used as catalysts for synthesis of 1-phenoxy-2-propanol (1-PhP) from phenol and propylene oxide as compared with some oxides, i.e. MgO, CaO, ZnO and Al2O3, etc. Al2O3/MgO with Al/Mg molar ratio of 1.5% exhibited outstanding catalytic performance with 98.2% conversion and 99.3% selectivity to 1-PhP at 120 °C for 5 h. This catalyst can be easily recovered and reused due to its heterogeneous catalytic nature.
- Zhang, Yongbo,Lu, Bin,Wang, Xiaoguang,Zhao, Jingxiang,Cai, Qinghai
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experimental part
p. 125 - 129
(2012/05/04)
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- Immobilization of β-cyclodextrin onto Dowex resin as a stationary microvessel and phase transfer catalyst
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In this study, immobilization of β-cyclodextrin onto commercial Dowex resin by covalent bond was reported. The efficiency of this biocatalyst system as a stationary microvessel and new solid-liquid phase transfer catalyst in reduction of epoxides by NaBH4 was studied.
- Kiasat, Ali Reza,Sayyahi, Soheil
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scheme or table
p. 484 - 486
(2010/12/19)
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- PROCESS FOR PREPARING AN ALKOXYLATED ALCOHOL OR PHENOL
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Process for preparing an alkoxylated alcohol comprising reacting a starting monohydroxy alcohol selected from secondary alcohols, tertiary alcohols and mixtures thereof with an alkylene oxide in the presence of hydrogen fluoride and a boron-containing compound comprising at least one B-O bond. The alcohol may also be a primary monohydroxy alcohol when the boron containing compound is boric acid or boric acid anhydride or a mixture thereof, or may be a primary mono hydroxy alcohol, except a C14/C15 alcohol when reacted with ethylene oxide in the presence of HF and trimethyl borate. A phenol may be alkoxylated in the same way instead of the mono-hydroxyalcohol.
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Page/Page column 19
(2008/06/13)
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- A new and efficient epoxide ring opening via poor nucleophiles: Indole, p-nitroaniline, borane and O-trimethylsilylhydroxylamine in lithium perchlorate
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Highly regioselective ring opening of 2,3-dimethyloxirane, 2-epoxyphenylether and allyl(2-epoxymethyl) ether are observed through reactions with poor nucleophiles such as indole, borane, O-trimethylsilylhydroxylamine, p-nitroaniline and sterically hindered tert-butylamine in the presence of 5.0 M lithium perchlorate-Et2O solution. These reactions are fast, convenient, with rather high yields and are carried out at ambient temperatures.
- Heydari, Akbar,Mehrdad, Morteza,Maleki, Aziz,Ahmadi, Nafiseh
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p. 1563 - 1565
(2007/10/03)
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- The Use of Proton-exchanged X-Type Zeolite in Catalysing Ring-opening Reactions of 2-Substituted Epoxides with Nucleophiles and its Effect on Regioselectivity
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The use of proton-exchanged X-type zeolite in catalysing ring-opening reactions of 2-alkyl substituted epoxides with nucleophiles gives a high regioselectivity and functional-selective catalysis giving allylic products from allylic nucleophiles.Mechanistic aspects are discussed.
- Takeuchi, Hiroshi,Kitajima, Kunio,Yamamoto, Yasuhiro,Mizuno, Kiyokazu
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p. 199 - 203
(2007/10/02)
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- 13C-N.M.R.-SPECTRAL AND RELATED STUDIES ON THE DISTRIBUTION OF SUBSTITUENTS IN O-(2-HYDROXYPROPYL)CELLULOSE
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Information about the degree of substitution at individual oxygen atoms of O-(2-hydroxypropyl)cellulose, and the total molar substitution, was obtained from 13C-n.m.r. spectra of the intact polymer and of its hydrolyzate.On the basis of their 13-CH3 chemical-shifts, O-(2-hydroxypropyl) (HOPr) substituents occurring singly, or as terminal units of substituent chains, were radily distinguished from inner HOPr units of chains.Differentiation between monomeric HOPr units and longer chains located at O-2 of D-glucosyl residues was effected by the transformation of appropriatly substituted sugars in the hydrolyzate into 1,2-cyclic acetals incorporating a 2-O-(2-hydroxypropyl) group.Similarly, the pattern of substitution at O-6 of D-glucosyl residues was determined, through selective degradation, from the identity of HOPr derivatives of ethylene glycol, representing C-5 and C-6 of the residues.Overall, it was found that, although O-2 and O-6 are more readily substituted than O-3, the rate at which each, initially introduced, HOPr substituent is converted into a dimeric structure is not materially affected by its location.Also described are the synthesis and the n.m.r. spectra of several HOPr derivatives of D-glucose, and of simple alkanols that served as model compounds.
- Lee, Dae-Sil,Perlin, Arthur S.
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- Opening of Cyclic Acetals by Trichloro-, Dichloro- and Tribromo-borane
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The rate-determining step in the ring opening of cyclic acetals by trichloroborane to yield α-chloro-ethers is shown to be consistent with the formation of an oxocarbenium ion.Subsequent reduction provides a general route for the conversion of a diol into a hydroxy-ether.Tribromoborane is a more powerful and dichloroborane a less powerful reagent than trichloroborane.
- Bonner, Trevor G.,Lewis, David,Rutter, Keith
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p. 1807 - 1810
(2007/10/02)
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