102-76-1Relevant articles and documents
Selective esterification of glycerol to bioadditives over heteropoly tungstate supported on Cs-containing zirconia catalysts
Jagadeeswaraiah,Balaraju,Prasad, P.S. Sai,Lingaiah
, p. 166 - 170 (2010)
Esterification of glycerol with acetic acid was carried out over tungstophosphoric acid (TPA) supported on Cs-containing zirconia. The catalysts were prepared by impregnation method and characterized by FT-infrared spectroscopy, X-ray diffraction and temperature program desorption of NH 3. The catalysts exhibited more than 90% conversion within a short reaction time. The catalytic activity depends on the amount of exchangeable Cs with TPA on zirconia, which is in tern related to the acidity of the catalysts. The acidity of the catalysts varied with the presence of residual protons of TPA. The effects of various parameters, such as reaction temperature, catalyst concentration and molar ratio of glycerol to acetic acid, were studied and optimized reaction conditions are established.
Synthesis of Triacetin and Evaluation on Motor
Lacerda, Claudia V.,Carvalho, Maria J.S.,Ratton, Alice R.,Soares, Itania P.,Borges, Luiz E.P.
, p. 1625 - 1631 (2015)
Triacetin (or glycerol triacetate) was obtained by acetylating the glycerol by-product of biodiesel production process. This procedure is an interesting alternative that follows the principles of green chemistry. In this work, triacetin was synthesized using reactions between glycerol and acetic acid, as well as glycerol and acetic anhydride, using homogeneous and heterogeneous acid catalysis. The goal is to use this product as an additive for biodiesel produced from palm oil, which is a fuel with physical properties that require improvement. The products were characterized by Fourier transform infrared spectroscopy (FTIR), 13C nuclear magnetic resonance (NMR) and gas chromatography (GC). The reaction between glycerol and acetic anhydride was the most effective for obtaining the desired product, with an approximate selectivity of 98percent for triacetin. The triacetin was added to diesel fuel oil and biodiesel in proportions from 5 to 10percent v/v, and the mixtures were tested in an electrical generator. In the test, the engine showed no problems during operation, and incorporating the mixtures did not result in significant consumption. Small reductions were detected in CO, O2 and opacity, but no changes were observed in the emissions of NOx and CO2.
An efficient and sustainable production of triacetin from the acetylation of glycerol using magnetic solid acid catalysts under mild conditions
Sun, Jinyan,Tong, Xinli,Yu, Linhao,Wan, Jun
, p. 115 - 122 (2016)
The efficient and selective acetylation of glycerol to produce triacetin is achieved using magnetic solid acids as catalysts. The Fe-based materials including Fe-Sn-Ti (OH)x, Fe-Sn-Ti(SO42-) and Fe-Sn-Ti(SO42-)-t (t represents the temperature for the heating treatment) were successfully prepared and employed in the acetylation of glycerol, respectively. As a result, 100% conversion and 99.0% selectivity for triacetin was obtained in the presence of a catalytic amount of Fe-Sn-Ti(SO42-)-400 at 80 °C for 30 min, which exhibits higher catalytic activity than those of some molecular sieves. The magnetic catalytic materials were respectively characterized by XRD, IR, TG-DTG, BET and NH3-TPD techniques. Moreover, the effects of reaction temperature and reaction time in the glycerol acetylation are investigated in detail. Finally, based on the experimental results and reaction phenomena, a possible mechanism for the catalytic reaction is proposed.
Synthesis of bio-additives: Acetylation of glycerol over zirconia-based solid acid catalysts
Reddy, Padigapati S.,Sudarsanam, Putla,Raju, Gangadhara,Reddy, Benjaram M.
, p. 1224 - 1228 (2010)
Acetylation of glycerol with acetic acid was investigated over ZrO 2, TiO2-ZrO2, WOx/TiO 2-ZrO2 and MoOx/TiO2-ZrO2 solid acid catalysts to synthesize monoacetin, diacetin and triacetin having interesting applications as bio-additives for petroleum fuels. The prepared catalysts were characterized by means of XRD, BET surface area, ammonia-TPD and FT-Raman techniques. The effect of various parameters such as reaction temperature, molar ratio of acetic acid to glycerol, catalyst wt.% and time-on-stream were studied to optimize the reaction conditions. Among various catalysts investigated, the MoOx/TiO2-ZrO2 combination exhibited highest conversion ( ～ 100%) with best product selectivity, and a high time-on-stream stability.
SO42-/SnO2: Efficient, chemoselective, and reusable catalyst for acylation of alcohols, phenols, and amines at room temperature
Satam, Jitendra R.,Gawande, Manoj B.,Deshpande, Sameer S.,Jayaram, Radha V.
, p. 3011 - 3020 (2007)
SO42-/SnO2 was employed for the acylation of a variety of alcohols, phenols, and amines under solvent-free conditions at room temperature. This method showed preferential selectivity for acetylation of the amino group in the presence of a hydroxyl group. The reported method is simple, mild, and environmentally viable, using several other acid anhydrides at room temperature. Copyright Taylor & Francis Group, LLC.
Hydrogenation of Carbon Monoxide to Methanol and Ethylene Glycol by Homogeneous Ruthenium Catalysts
Dombek, B. Duane
, p. 6855 - 6857 (1980)
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Novel double-SO3h functionalized ionic liquid for acetylation
Zhu, Lili,Liang, Xuezheng
, p. 684 - 688 (2012)
Novel double-SO3H functionalized ionic liquid (DFIL) was synthesized and its catalytic activities for acetylation studied. The result showed that the DFIL possess high acidity and was very efficient for the acetylation of alcohols, amines and phenols with good to excellent yields in short reaction times. Operational simplicity, stability to water and air, small amounts needed, low cost, high yields, high acidity, applicability to large-scale reactions and reusability are the key features of the DFIL, which indicated promising applications of DFIL in green chemical processes. Pleiades Publishing, Ltd., 2012.
Continuous synthesis of glycerol acetates in supercritical carbon dioxide using Amberlyst 15
Rezayat, Marzieh,Ghaziaskar, Hassan S.
, p. 710 - 715 (2009)
Continuous esterification of glycerol with acetic acid was investigated in supercritical carbon dioxide (scCO2) using Amberlyst 15 as a heterogeneous catalyst. The effect of pressure at (65-300) bar on the substrate conversion and the reaction yield and selectivity was studied. With increasing pressure, the percent of total yield and conversion remain almost unaffected and the selectivity of monoacetin synthesis increases while the selectivity for triacetin stays relatively unchanged. The effect of temperature on the yield, conversion, and the selectivity at (100-150) °C was also investigated. With increasing temperature from 100 to 140 °C, the selectivity for monoacetin decreases while for tri- and diacetin slightly increases. In contrast, with further increase in temperature, from 140 °C to 150 °C, the selectivity of monoacetin synthesis increases while that of diacetin decreases. By increasing the molar ratio of acetic acid to glycerol to 24, a selectivity of 100% was achieved for 2 h while the yield was 41% for the continuous triacetin synthesis in scCO2. When neat scCO2 as solvent with no catalyst was used, only monoacetin with 29% conversion was synthesized. The catalyst durability was also studied by monitoring the reaction for 25 h. The results show that the catalyst retains its activity even for 25 h but the selectivity for triacetin synthesis declines from 100% to about 60%.
Combining clays and ultrasound irradiation for an o-acetylation reaction of N-glucopyranosyl and other molecules
De Oliveira, Ronaldo N.,De Xavier, Augusto L.,Guimaraes, Bruna M.,Melo, Valentina N. E.,Valena, Wagner O.,Nascimento Do, Wilson S.,Da Costa, Pollyanna L. F.,Camara, Celso A.
, p. 2610 - 2614 (2014)
A convenient, efficient and fast acetylation combining clays and ultrasound irradiation is described. Some molecules from nature or synthetic source, i.e., D-glucose, glycerol, D-mannitol and 1,2,3-triazolic derivatives such as N-glucosyl sugars and 2-substituted 1,4-naphthoquinone structures were acetylated. This kind of chemistry may be classified as eco-friendly because the reactions take a short time and the catalyst is reusable.
Co-production of butyrate methyl ester and triacetylglycerol from tributyrin and methyl acetate
Battistel, Ezio,Calaprice, Chiara,Gualdi, Enrico,Rebesco, Elena,Usai, Elisabetta Maria
, p. 149 - 157 (2011)
The simultaneous synthesis of butyric acid methyl ester, the shortest component of the FAME (fatty acid methyl esters) family, and glycerol triacetate (TAG) from glycerol tributyrate (tributyrin) and methyl acetate was studied as a function of several reaction parameters, such as type of catalyst, temperature and products distribution. The reaction is an interesterification, a multistep consecutive ester interchange catalyzed by either acid or base catalyst. Under optimized conditions, a complete tributyrin conversion and an almost quantitative butyric acid methyl ester accumulation were achieved. The other reaction product, TAG, formed by the complete acetylation of the glycerol moiety, reached almost 70% yield, whereas the mono- and di-acetylated intermediates accumulated in the order of 5-8% and 24-27%, respectively. Similar final conversions and products yields were obtained with either acid or base homogeneous catalysts, suggesting that the final products mixture did not depend on the type of catalysis but might be limited by equilibrium conditions. In spite of similar final yields, base catalysis needed shorter reaction times (minutes instead of hours) and lower temperature (60 °C instead of 130 °C) with respect to the best acid catalyst. On the other hand, unlike heterogeneous basic catalysts, which showed low activity, a heterogeneous acid catalyst almost as active as the homogenous counterpart was found.
Solventless acetylation of alcohols and phenols catalyzed by supported iron oxide nanoparticles
Rajabi, Fatemeh,Luque, Rafael
, p. 129 - 132 (2014)
Supported iron oxide nanoparticles on silicate catalysts were found to be efficient and easily recoverable materials in the acetylation of alcohols and phenols to their corresponding acetyl compounds using acetic anhydride under mild and solvent-less conditions. The supported iron oxide nanoparticles could be easily recovered from the reaction mixture and reused ten times without any loss in activity.
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Sokol'skii,Knunjanz
, (1961)
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A cheap, simple, and versatile method for acetylation of alcohols and phenols and selective deprotection of aromatic acetates under solvent-free condition
Rajabi, Fatemeh,Saidi, Mohammad R.
, p. 483 - 491 (2005)
Acyclic and cyclic acetates of various alcohols and phenols were obtained in excellent yields under mild reaction conditions in the presence of a catalytic amount of sodium hydroxide under solvent-free conditions and microwave irradiation. Selective deprotection of acetate group from the corresponding phenolic compounds was carried out in the presence of LiClO4· 2H2O. Copyright Taylor & Francis, Inc.
Selective Synthesis of Carbonates from Glycerol, CO 2, and Alkyl Halides Using tert -Butyltetramethylguanidine
Mihara, Masatoshi,Moroga, Kaname,Iwasawa, Tetsuo,Nakai, Takeo,Ito, Takatoshi,Ohno, Toshinobu,Mizuno, Takumi
, p. 1759 - 1764 (2018)
Herein, we describe the guanidine-promoted synthesis of carbonates from glycerol, CO 2, and alkyl halides. Specifically, a linear tricarbonate (1,2,3-tri- O -butoxycarbonylglycerol), a dicarbonate [butyl (2-oxo-1,3-dioxolan-4-yl)methyl carbonate] containing a linear and a cyclic moiety, and a cyclic monocarbonate (4-hydroxymethyl-2-oxo-1,3-dioxolan) were selectively obtained in good yields, which were strongly affected by the steric bulkiness of the guanidine group substituents. The developed method exhibits the advantages of high efficiency and mild conditions, thus being a powerful tool for the synthesis of value-added products from industrial by-products.
Highly efficient and versatile acetylation of alcohols catalyzed by cerium(III) triflate
Dalpozzo, Renato,De Nino, Antonio,Maiuolo, Loredana,Procopio, Antonio,Nardi, Monica,Bartoli, Giuseppe,Romeo, Roberto
, p. 5621 - 5624 (2003)
Cerium(III) triflate is a powerful catalyst for the acetylation of alcohols. The reaction works well for a large variety of simple and functionalized alcohols, without isomerisation of chiral centres. Changes of hydroxyl protective groups are possible in a one-pot procedure. The catalyst can be easily recycled.
Sulfamic acid catalysed acetylation of alcohols and phenols with acetic anhydride
Jin, Tong-Shou,Ma, Van-Ran,Zhang, Zhan-Hui,Li, Tong-Shuang
, p. 3173 - 3177 (1998)
An easy acetylation of alcohols and phenols with acetic anhydride has been carried out in excellent yield under catalysis of sulfamic acid.
SbCl3 as a highly efficient catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions
Bhattacharya, Asish K.,Diallo, Mamadou A.,Ganesh, Krishna N.
, p. 1518 - 1526 (2008)
Antimony trichloride has been found to be an efficient and expedient catalyst for the acylation of alcohols, phenols, amines, and sugars with acetic anhydride in high yields and in a short reaction time under solvent-free conditions at room temperature. Also, racemization of chiral alcohols and epimerization of sugars were not observed in any of the substrates. Copyright Taylor & Francis Group, LLC.
Sulphuric acid-functionalized siliceous zirconia as an efficient and reusable catalyst for the synthesis of glycerol triacetate
Abida, Km,Ali, Amjad
, p. 3627 - 3639 (2020)
In the present study, a sulphated siliceous zirconia catalyst (SSZ-550) has been prepared and characterized by XRD and FTIR analysis to indicate the incorporation of sulphate group over the matrix. X-ray photoelectron spectroscopy also revealed that sulphur group was incorporated over the matrix to impart the Br?nsted acidity to the catalyst which is vital for the acetylation activity. To optimize the reaction parameters, viz. reagent molar ratios (3–12; glycerol/acetic acid), catalyst amount (1–5?wt%; catalyst/glycerol), reaction duration (20–50?min) and reaction temperature (30–100?°C) have been varied to obtain the optimum catalyst activity for the maximum glycerol triacetate yield. Finally, under the optimized reaction parameters of 9:1 glycerol/acetic acid molar ratio, 3?wt% catalyst, 80?°C reaction temperature and 40?min of reaction duration, a 93% glycerol triacetate yield was obtained. The catalyst was recovered from the reaction mixture and reused during six consecutive reaction runs while retaining 50% glycerol triacetate selectivity in the last cycle. A plausible mechanism suggests the heterogeneous catalyst-assisted protonation of carbonyl group of acetic acid to initiate the stepwise esterification of the hydroxyl groups of glycerol.
Chemical transformation of embelin through dimerization during preparation of a decoction
Kiuchi, Fumiyuki,Suzuki, Noriko,Fukumoto, Yumiko,Goto, Yoshihisa,Mitsui, Mariko,Tsuda, Yoshisuke
, p. 1225 - 1128 (1998)
Embelin, a major constituent of Embelia ribes BURM. (Myrsinaceae) was transformed into different types of compounds through dimerization during preparation of a decoction. Two of the products are proposed to have furanylidene benzofuranone and 1,4-dibenzofurandione skeletons on the basis of spectroscopic means. The transformation of embelin in boiling water is markedly accelerated by the presence of fatty acids.
Ordered mesoporous zirconium silicates as a catalyst for biofuel precursors synthesis
Bu, Quan,Cai, Jin,Mao, Hanping,Vasudevan, Srinivasan Vinju
, (2021/11/16)
Zirconium incorporated three-dimensional ordered mesoporous silica (FDU-5) catalysts with different Si/Zr (100, 50 and 25) ratios were synthesized using an Evaporation Induced Self Assembly (EISA) method to maximize the incorporation of zirconium sites in the silica framework. The physicochemical properties of the synthesized materials were characterized by several techniques such as XRD, N2 sorption, diffuse reflectance UV–Vis, TEM, ammonia TPD, ICP-OES and pyridine adsorbed FT-IR. The catalytic activity was evaluated in acid-catalyzed esterification of glycerol with acetic acid. The effects of different reaction parameters were studied to optimize the maximum yields, such as reaction temperature, catalyst loading, acid/alcohol molar ratio, and reaction time. Esterification of glycerol with levulinic acid and levulinic acid with ethanol was also performed to synthesize fuel precursors. Reaction results showed that the prepared Zr-FDU-5(25) material was a very high catalytic activity, which depended mostly on the zirconium species' availability on the surfaces and framework. This zirconium containing FDU-5 material was very active in the esterification reaction and selective product formation at certain reaction conditions. The selected catalyst was recycled five times without significant loss in its activity.
ZWITTERIONIC CATALYSTS FOR (TRANS)ESTERIFICATION: APPLICATION IN FLUOROINDOLE-DERIVATIVES AND BIODIESEL SYNTHESIS
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Paragraph 0011; 0027, (2021/01/29)
An amide/iminium zwitterion catalyst has a catalyst pocket size that promotes transesterification and dehydrative esterification. The amide/iminium zwitterions are easily prepared by reacting aziridines with aminopyridines. The reaction can be applied a wide variety of esterification processes including the large-scale synthesis of biodiesel. The amide/iminium zwitterions allow the avoidance of strongly basic or acidic condition and avoidance of metal contamination in the products. Reactions are carried out at ambient or only modestly elevated temperatures. The amide/iminium zwitterion catalyst is easily recycled and reactions proceed in high to quantitative yields.
