- 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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- PROCESS FOR MAKING FORMIC ACID UTILIZING LOWER-BOILING FORMATE ESTERS
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Disclosed is a process for recovering formic acid from a formate ester of a C3 to C4 alcohol. Disclosed is also a process for producing formic acid by carbonylating a C3 to C4 alcohol, hydrolyzing the formate ester of the alcohol, and recovering a formic acid product. The alcohol may be dried and returned to the reactor. The process enables a more energy efficient production of formic acid than the carbonylation of methanol to produce methyl formate.
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Paragraph 00177; 00178
(2019/02/15)
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- Nano metal oxides as efficient catalysts for selective synthesis of 1-methoxy-2-propanol from methanol and propylene oxide
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Nano metal oxides such as Fe2O3, Fe3O4, CuO, NiO, ZnO and SnO2 were prepared and characterized using XRD, SEM and TEM analysis. These as-prepared metal oxide materials were used as catalysts for the etherification of methanol with propylene oxide (PO). The results showed that α-Fe2O3 exhibited outstanding catalytic performance with 97.7% conversion and 83.0% selectivity to MP-2 at 160 °C for 8 h. Furthermore, the relationship between the catalytic activity or selectivity and surface basicity or energy gap was investigated. This catalyst could be easily recovered and reused due to its heterogeneous catalytic nature.
- Zhang, Jiawei,Cai, Qinghai,Zhao, Jingxiang,Zang, Shuying
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p. 4478 - 4482
(2018/02/07)
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- METHODS OF CONVERTING POLYOLS
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Methods for converting polyols are provided. The methods provided can include using a metal pincer catalyst (e.g., an iridium pincer catalyst) to remove at least one alcohol group from a polyol. The methods provided can include converting glycerol to 1,3-propanediol.
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Paragraph 0091-0092
(2015/01/06)
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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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- 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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- Catalytic deoxygenation of 1,2-propanediol to give n-propanol
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Deoxygenation of 1,2-propanediol (1.0M in sulfolane) catalyzed by bis(dicarbonyl)(μhydrido)(pentamethylcyclopentadiene)ruthenium trifluoromethanesulfonate ({[Cp*Ru(CO)2]2(μ.-H)} +OTf-) (0.5 mol%) at 110°C under hydrogen (750 psi) in the presence of trifluoromethanesulfonic acid (HOTf) (60 mM) gives n-propanol as the major product, indicating high selectivity for deoxygenation of the internal hydroxy group over the terminal hydroxy group of the diol. The deoxygenation of 1,2-propanediol is strongly influenced by the concentration of acid, giving faster rates and proceeding to higher conversions as the concentration of HOTf is increased. Propionaldehyde was observed as an intermediate, being formed through acid-catalyzed dehydration of 1,2-propanediol. This aldehyde is hydrogenated to n-propanol through an ionic pathway involving protonation of the aldehyde, followed by hydride transfer from the neutral hydride, dicarbonyl(pentamethylcyclopentadiene)ruthenium hydride [Cp*Ru(CO)2H]. The proposed mechanism for the deoxygenation/hydrogenation reaction involves formation of a highly acidic dihydrogen complex [Cp*Ru(CO)2(η2-H 2)]+ OTf-.
- Schlaf, Marcel,Ghosh, Prasenjit,Fagan, Paul J.,Hauptman, Elisabeth,Morris Bullock
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experimental part
p. 789 - 800
(2009/12/03)
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- PROCESS FOR RECOVERING ORGANIC COMPOUNDS FROM AQUEOUS STREAMS CONTAINING SAME
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A method for a liquid-liquid extraction of hydrophilic organic compounds from aqueous solutions thereof is described. The method generally includes intermixing a sufficient quantity of a specified glycol ether with the aqueous liquor at a first temperature to form a suspension comprising an aqueous raffinate phase and a glycol ether extract phase; separating the glycol ether extract phase from the aqueous raffinate phase; heating the glycol ether extract phase to a second, higher temperature to form a suspension comprising an aqueous extract phase containing a portion of the hydrophilic organic compound and a glycol ether raffinate phase; and separating this glycol ether raffinate phase from the aqueous extract phase. The selected glycol ether has an inverse solubility in water and the partition ratio, value K, for the hydrophilic organic compound is greater than 0.1. This method is useful for recovering valuable hydrophilic organic acids produced via fermentation or produced or used in various manufacturing processes.
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Page/Page column 20
(2008/06/13)
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- PROCESS FOR SPLITTING WATER-SOLUBLE ETHERS
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A process for production of 1,3-propanediol including the steps: (a) hydrating acrolein in the presence of an acid hydration catalyst; (b) catalytically hydrogenating the reaction mixture of step (a), which reaction mixture comprises 3-hydroxypropionaldehyde and is freed of unreacted acrolein; (c) refining the reaction mixture of step (b) containing water, 1,3-propanediol and the by-products boiling higher than 1,3-propanediol; and (d) treating 4-oxa-1,7-heptanediol to form 1,3-propanediol by (1) removing a boiler sump comprising 4-oxa-1,7-heptanediol from the refining step (c), (2) treating the boiler sump in an aqueous solution in the presence of an acid catalyst at about 200 to about 300° C. to form a solution comprising 1,3-propanediol, (3) neutralizing the solution obtained is step (2), and returning the neutralized solution from step (3) to the refining step (c). In addition, a process for splitting oligomeric water-soluble ether comprising: (a) treating an aqueous solution comprising oligomeric water-soluble ether in the presence of homogeneous acid catalyst at a temperature of from about 200 to about 300 ° C. to form the monomer of the oligomeric water-soluble ether; and (b) neutralizing the solution obtained in step (a),
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- Metal-catalyzed selective deoxygenation of diols to alcohols
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The internal OH group of 1,2-propanediol is selectively removed in the deoxygenation catalyzed by [{Cp*Ru(CO)2}2(μ-H)]+OTf - (1, Cp=C3Me5, OTf=trifluoromethanesulfonate; see scheme). This reaction provides a model for deoxygenation of polyols derived from carbohydrates, for use in alternative, biomass-based feedstock applications. An ionic mechanism is proposed that involves the dihydrogen complex [Cp*Ru(CO)2(η2-H2)]+.
- Schlaf, Marcel,Ghosh, Prasenjit,Fagan, Paul J.,Hauptman, Elisabeth,Morris Bullock
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p. 3887 - 3890
(2007/10/03)
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- Highly chemoselective hydrogenation with retention of the epoxide function using a heterogeneous Pd/C - Ethylenediamine catalyst and THF
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In general, palladium-carbon (Pd/C) catalyzed hydrogenation of epoxides affords the corresponding primary and secondary alcohols as a mixture. It has been found that the catalytic activity of a Pd/C - ethylenediamine complex catalyst [Pd/C(en)] in the hydrogenolysis of epoxide functions is drastically reduced. Herein we describe a mild and chemoselective method for the hydrogenation of olefin, nitro, and azide functions with retention of the epoxide function. The chemoselectivity was accomplished by using a combination of 5% Pd/C(en) and THF as solvent. A significant drop in the chemoselectivity of the hydrogenation is observed with 5% Pd/C(en) in MeOH. These results reinforce the utility of epoxides as important precursors of alcohols in synthetic chemistry.
- Sajiki, Hironao,Hattori, Kazuyuki,Hirota, Kosaku
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p. 2200 - 2204
(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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