121348-86-5Relevant academic research and scientific papers
A transesterification-acetalization catalytic tandem process for the functionalization of glycerol: The pivotal role of isopropenyl acetate
Calmanti, Roberto,Perosa, Alvise,Rigo, Davide,Selva, Maurizio
, p. 5487 - 5496 (2020/09/23)
At 30 °C, in the presence of Amberlyst-15 as a catalyst, a tandem sequence was implemented by which a pool of innocuous reactants (isopropenyl acetate, acetic acid and acetone) allowed upgrading of glycerol through selective acetylation and acetalization processes. The study provided evidence for the occurrence of multiple concomitant reactions. Isopropenyl acetate acted as a transesterification agent to provide glyceryl esters, and it was concurrently subjected to an acidolysis reaction promoted by AcOH. Both these transformations co-generated acetone which converted glycerol into the corresponding acetals, while acidolysis sourced also acetic anhydride that acted as an acetylation reactant. However, tuning of conditions, mostly by changing the reactant molar ratio and optimizing the reaction time, was successful to steer the set of all reactions towards the synthesis of either a 1?:?1 mixture of acetal acetates (97% of which was solketal acetate) and triacetin, or acetal acetates in up to 91% yield, at complete conversion of glycerol. To the best of our knowledge, a one-pot protocol with such a degree of control on the functionalization of glycerol via transesterification and acetalization reactions has not been previously reported. The procedure was also easily reproduced on a gram scale, thereby proving its efficiency for preparative purposes. Finally, the design of experiments with isotopically labelled reagents, particularly d4-acetic acid and d6-acetone, helped to estimate the contribution of different reaction partners (iPAc/AcOH/acetone) to the formation of final products. This journal is
Method for synthesizing acetone ketal glycerinum acetate from glycerinum
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Paragraph 0018, (2019/12/25)
The invention discloses a method for synthesizing acetone ketal glycerinum acetate from glycerinum. The method comprises the following steps: firstly, putting acetone and a biodiesel byproduct, namelyglycerinum, into a condensation kettle, performing a condensation reaction in the presence of a catalyst A, and performing extraction and distillation after the reaction so as to obtain acetone ketalglycerinum; putting the acetone ketal glycerinum into a reaction/azeotropic distillation device, performing an ester exchange reaction with acetate in the presence of a catalyst B, and performing aftertreatment, so as to obtain a target product, namely the acetone ketal glycerinum acetate. Through condensation and ester exchange reactions, the biodiesel byproduct, namely the glycerinum, is converted into the acetone ketal glycerinum acetate which can be used as a fuel additive, separation is simple, the yield is high, the preparation process is simple, the catalyst is small in equipment corrosion, environment pollution caused by glycerinum wastes can be avoided, the environment can be protected, meanwhile, additional values of products can be increased, and development of the biodiesel industry can be facilitated.
Green Acetylation of Solketal and Glycerol Formal by Heterogeneous Acid Catalysts to Form a Biodiesel Fuel Additive
Dodson, Jennifer R.,Leite, Thays d C. M.,S. Pontes, Nathália,Peres Pinto, Bianca,Mota, Claudio J. A.
, p. 2728 - 2734 (2016/12/23)
A glut of glycerol has formed from the increased production of biodiesel, with the potential to integrate the supply chain by using glycerol additives to improve biodiesel properties. Acetylated acetals show interesting cold flow and viscosity effects. Herein, a solventless heterogeneously catalyzed process for the acetylation of both solketal and glycerol formal to new products is demonstrated. The process is optimized by studying the effect of acetylating reagent (acetic acid and acetic anhydride), reagent molar ratios, and a variety of commercial solid acid catalysts (Amberlyst-15, zeolite Beta, K-10 Montmorillonite, and niobium phosphate) on the conversion and selectivities. High conversions (72–95 %) and selectivities (86–99 %) to the desired products results from using acetic anhydride as the acetylation reagent and a 1:1 molar ratio with all catalysts. Overall, there is a complex interplay between the solid catalyst, reagent ratio, and acetylating agent on the conversion, selectivities, and byproducts formed. The variations are discussed and explained in terms of reactivity, thermodynamics, and reaction mechanisms. An alternative and efficient approach to the formation of 100 % triacetin involves the ring-opening, acid-catalyzed acetylation from solketal or glycerol formal with excesses of acetic anhydride.
Pheromone synthesis. Part 255: Synthesis and GC-MS analysis of pheromonal triacylglycerols of male Drosophila fruit flies
Mori, Kenji
, p. 5752 - 5762 (2015/03/30)
Pheromonal triacylglycerols and their analogs, 1A, 1B, 2A, 2B, 3A, 3B, and 3C, of male Drosophila fruit flies were synthesized and analyzed by GC-MS. Their GC retention times were found to be a reliable measure to analyze and identify these triacylglycerols with acetyl, oleoyl and tigloyl groups, although the stereo- and regioisomers of 1 (1A and 1B), 2 (2A and 2B), and 3 (3A, 3B, and 3C) could not be distinguished from each other by MS alone.
A basic germanodecatungstate with a - 7 charge: Efficient chemoselective acylation of primary alcohols
Sugahara, Kosei,Satake, Naoto,Kamata, Keigo,Nakajima, Takahito,Mizuno, Noritaka
supporting information, p. 13248 - 13252 (2015/01/09)
The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ-Keggin germanodecatungstate, [γ-HGeW10O36]7- (A), having a -7 charge was, for the first time, successfully synthesized by the reaction of [γ-H2GeW10O36]6- with one equivalent of [(n-C4H9)4N]OH under non-aqueous conditions. The activities of germanodecatungstates for base-catalyzed reactions dramatically increased with increase in the number negative charges from -6 to -7. In the presence of A, various combinations of acylating agents and primary alcohols including those with acid-sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions.
Selective esterifications of primary alcohols in a water-containing solvent
Wang, Yong,Aleiwi, Bilal A.,Wang, Qinghui,Kurosu, Michio
supporting information, p. 4910 - 4913,4 (2012/12/12)
Oxyma and an oxyma derivative, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl 2-cyano-2-(hydroxyimino)acetate (5b), displayed a remarkable effect on selective esterifications of primary alcohols. A wide range of carboxylic acids could be esterified with primary alcohols by using EDCI, NaHCO3, and Oxyma or Oxyma derivative 5b in 5% H2O-CH3CN. Oxyma derivative 5b is particularly useful, since it could be removed after the reaction via a simple basic or an acidic aqueous workup procedure.
Selective esterifications of primary alcohols in a water-containing solvent
Wang, Yong,Aleiwi, Bilal A.,Wang, Qinghui,Kurosu, Michio
supporting information, p. 4910 - 4913 (2013/01/15)
Oxyma and an oxyma derivative, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl 2-cyano-2-(hydroxyimino)acetate (5b), displayed a remarkable effect on selective esterifications of primary alcohols. A wide range of carboxylic acids could be esterified with primary alcohols by using EDCI, NaHCO3, and Oxyma or Oxyma derivative 5b in 5% H2O-CH3CN. Oxyma derivative 5b is particularly useful, since it could be removed after the reaction via a simple basic or an acidic aqueous workup procedure.
New approach to the synthesis of 1,3-dioxolanes
Vol'Eva,Belostotskaya,Malkova,Komissarova,Kurkovskaya,Usachev,Makarov
experimental part, p. 638 - 641 (2012/10/18)
Application of ethanol to the synthesis of 1,3-dioxolanes by the condensation of carbonyl compounds with vicinal diols results in a high yield of the reaction product and considerably reduces the duration of the process. It is assumed that the effect of the ethanol is caused by the adduct formation with carbonyl compounds (hemiacetals) which behave as active intermediates of the condensation. A cyclic ketal of acetone with glycerol obtained with the help of ethanol was used as a basis component in the synthesis of a series of ketals substituting diol or carbonyl components by transketalyzation mechanism proceeding without water liberation.
A mild and efficient acetylation of alcohols, phenols and amines with acetic anhydride using La(NO3)3·6H2O as a catalyst under solvent-free conditions
Reddy, T. Srikanth,Narasimhulu,Suryakiran,Mahesh, K. Chinni,Ashalatha,Venkateswarlu
, p. 6825 - 6829 (2007/10/03)
A wide variety of alcohols, phenols and amines are efficiently and selectively converted into the corresponding acetates by treatment with acetic anhydride in the presence of catalytic amounts of La(NO3)3·6H2O under solvent-free conditions at room temperature. The method is compatible with acid sensitive hydroxyl protecting groups such as TBDMS, THP, OBz, OBn, Boc and some isopropylidenes and offers excellent yields of the mono acetates of 1,3-, 1,4- and 1,5-diols.
