556-52-5Relevant articles and documents
Synthesis of glycidol from glycerol and dimethyl carbonate using ionic liquid as a catalyst
Gade, Swapna M.,Munshi, Mudassir K.,Chherawalla, Batul M.,Rane, Vilas H.,Kelkar, Ashutosh A.
, p. 184 - 188 (2012)
Transesterification of dimethyl carbonate with glycerol has been investigated using various ionic liquids as catalysts. Synthesis of glycidol with high selectivity (78%) has been achieved using tetramethylammonium hydroxide ([TMA][OH]) as a catalyst at 80°C. Effect of various reaction conditions on the activity and selectivity was investigated and catalyst concentration had a significant influence on conversion as well as selectivity to glycidol. Activity as well as selectivity of the catalyst decreased significantly with increase in moisture content. Recycle experiment indicated slight drop in glycerol conversion and selectivity to glycidol because of dilution of reaction mixture and also the presence of products from the initial experiment.
Fluorinated Mg–Al Hydrotalcites Derived Basic Catalysts for Transesterification of Glycerol with Dimethyl Carbonate
Zhang, Xuelan,Wang, Dengfeng,Ma, Jie,Wei, Wei
, p. 1181 - 1196 (2017)
Abstract: A series of fluorinated Mg–Al hydrotalcite-like (HTl) compounds were prepared by introduction of different amount of (AlF6)3? into HTl sheets via co-precipitation method. The fluorine-modified Mg–Al mixed oxides (CHT-F) with mesoporous structure were then acquired by thermal decomposition of as-prepared HTl precursors. The influence of fluorine modifier on the physicochemical properties of CHT-F samples was studied in detail and the results demonstrated that their structure and basicity were strongly related to the fluorine content. Simultaneously, the CHT-F samples were test for the glycerol carbonate (GC) production via transesterification between glycerol and dimethyl carbonate without organic solvent. For these catalysts, the role of basic sites was examined based on reactant conversion and product selectivities in overall reaction as well as in side reaction identified in this work. The catalytic results showed that the activity of CHT-F catalysts depended on the total number of surface basic sites. However, further study demonstrated that the undesired product was catalyzed by strong basic sites, resulting in decrease of GC selectivity. Thus, the introduction of appropriate amount of (AlF6)3? into the HTl structure can promote the production of GC, and the best catalytic performance was obtained over the catalyst with F:Al = 1.0. Besides, various parameters including reaction time, reaction temperature and catalyst amount were investigated to optimize the reaction conditions. Furthermore, these CHT-F catalysts possessed high stability on the basis of reusability test and catalyst characterization. Graphical Abstract: [Figure not available: see fulltext.].
Reaction of glycidyl methacrylate at the hydroxyl and carboxylic groups of poly(vinyl alcohol) and poly(acrylic acid): Is this reaction mechanism still unclear?
Reis, Adriano V.,Fajardo, Andre R.,Schuquel, Ivania T. A.,Guilherme, Marcos R.,Vidotti, Gentil Jose,Rubira, Adley F.,Muniz, Edvani C.
, p. 3750 - 3757 (2009)
(Chemical Equation Presented) Transesterification and epoxide ring-opening reactions are two mechanism routes that explain chemical modifications of macromolecules by glycidyl methacrylate (GMA). Although the coupling reaction of the GMA with macromolecul
Facile one-pot synthesis of glycidol from glycerol and dimethyl carbonate catalyzed by tetraethylammonium amino acid ionic liquids
Zhou, Yan,Ouyang, Fan,Song, Zhi-Bin,Yang, Zhen,Tao, Duan-Jian
, p. 25 - 29 (2015)
Four tetraethylammonium amino acid ionic liquids (TAAILs) were prepared and used as catalysts for facile one-pot synthesis of glycidol from glycerol and dimethyl carbonate. The results indicate that tetraethylammonium pipecolinate ([N2222][Pipe]) exhibits the best catalytic activity compared with other three TAAILs, and catalyzes the reaction to reach a glycerol conversion of 96% and a glycidol yield of 79% under optimum conditions. Moreover, DFT calculated results further manifest that such excellent performance originates from the carboxyl group in [N2222][Pipe], which enables [N2222][Pipe] to activate the substrates effectively.
Aerobic oxidation of methyl p-Tolyl sulfide catalyzed by a remarkably labile heteroscorpionate Ru(II)-aqua complex, fac-[RuII(H2O)(dpp)(tppm)]2+
Huynh, My Hang V.,Witham, Laura M.,Lasker, Joanne M.,Wetzler, Modi,Mort, Brendan,Jameson, Donald L.,White, Peter S.,Takeuchi, Kenneth J.
, p. 308 - 309 (2003)
fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large (40)-Ru (1)-N(51) of 96.95(14)° The remarkably short distance between O (40) of H 2O and H (45a) of dpp confirms the heteroscorpionate ligand effect fo dpp H 2O [2B] 2+ aerobically catalyzes methl p-toyl sulfide to methyl p-toyl sulfoxide in 1,2 dichlorobenzene at 25.0 ± 0.1 ° C under 11.4 psi of O2.Experimental facts in support of this aerobic sulfide oxidation are the absence of H 2O2 and the oxidative readctive of the putative Ru(IV)-oxo intermediate toward methl p-tolyl Sulfide, 2- propanol, and allyl alcohal This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru (III)- aqua complex without the formation of a highly reactive peroxide as an intemediate. Copyright
Efficient synthesis of glycerol carbonate/glycidol using 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) based ionic liquids as catalyst
Munshi, Mudassir K.,Biradar, Pradeep S.,Gade, Swapna M.,Rane, Vilas H.,Kelkar, Ashutosh A.
, p. 17124 - 17128 (2014)
Transesterification of dimethyl carbonate with glycerol to glycerol carbonate has been catalyzed efficiently using basic ionic liquids as catalysts. Activity of all the ILs tested is very high and the best result (96% conversion with 82% selectivity to glycerol carbonate and 18% selectivity to glycidol) was obtained using IL1 as catalyst. The effect of catalyst loading has significant influence on the selectivity pattern. The higher activity of the ionic liquid is explained with a plausible mechanism based on the co-operative effect of both cation and anion.
A novel titanosilicate with MWW structure III. Highly efficient and selective production of glycidol through epoxidation of allyl alcohol with H2O2
Wu, Peng,Tatsumi, Takashi
, p. 317 - 326 (2003)
The catalytic properties of Ti-MWW in the epoxidation of allyl alcohol (AAL) with hydrogen peroxide to glycidol (GLY) have been studied in detail by a comparison with those of TS-1 and pure silica Ti-Beta, and mechanical considerations have been given to the relation between the catalytic performance and the structural, acidic, and hydrophilic/hydrophobic nature of titanosilicates. Ti-MWW catalyzed the AAL epoxidation more actively and selectively than TS-1 and Ti-Beta in the presence of H2O or MeCN, and exhibited a conversion of 95% for AAL and a selectivity of 99% for GLY when the AAL epoxidation was carried out at 333 K for 30 min and at 12 wt% of catalyst to substrate. Ti-MWW proved to be a reusable and sustainable catalyst as it stood up to Ti leaching and maintained the catalytic activity and the product selectivity in the reaction-regeneration cycles. The acidic character due to the boron framework was very weak, and thus contributed negligibly to the solvolysis of GLY. The AAL epoxidation proceeded mainly within the intralayer sinusoid 10-MR channels which supplied more steric fitness to the substrate molecules than the tunnel-like channels of TS-1 ad Ti-Beta. Ti-MWW was more hydrophilic than TS-1, but much more hydrophobic than Ti-Beta. The hydrophilicity of Ti-MWW was presumed to derive mainly from the defect sites due to the incomplete dehydroxylation between the layers and partially as a result of deboronation. The sinusoidal 10-MR channels serving as the reaction space for the AAL epoxidation were considered to be hydrophobic, thus rendering the Ti-MWW catalyst applicable to the substrates and solvents, both of a polar nature.
1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU): A highly efficient catalyst in glycerol carbonate synthesis
Munshi, Mudassir K.,Gade, Swapna M.,Mane, Manoj V.,Mishra, Deepti,Pal, Sourav,Vanka, Kumar,Rane, Vilas H.,Kelkar, Ashutosh A.
, p. 144 - 149 (2014)
Transesterification of dimethyl carbonate (DMC) with glycerol (GLY) was investigated using various amines as catalysts. Amidines like 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) were found to be the best catalysts for this reaction. Best results: 98% conversion of GLY with 96% selectivity to GC (TON: 9408), were obtained with DBU as a catalyst. Effect of various reaction conditions on activity and selectivity were investigated using DBU as catalyst. The mechanism of the reaction was investigated with the help of 1H, 13C and 15N NMR analysis and DFT calculations.
Synthesis of glycerol carbonate by transesterification of glycerol and dimethyl carbonate over KF/γ-Al2O3 catalyst
Liu, Zhenmin,Wang, Junwei,Kang, Maoqing,Yin, Ning,Wang, Xinkui,Tan, Yisheng,Zhu, Yulei
, p. 152 - 160 (2014)
Series of KF/γ-Al2O3 solid base catalysts were prepared by a wet impregnation method and applied to the synthesis of glycerol carbonate (GC) from glycerol and dimethyl carbonate. The influences of KF loading and calcination temperature of catalyst on the synthesis were investigated. The results showed that KF/γ-A12O3 catalysts could promote glycerol conversion to GC efficiently. The structure and properties of the catalysts were studied by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N2-adsorption, CO2-temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and Hammett indicator method. It was found that several types of basic centers such as KF, KAlO2, KOH and possibly coordinately unsaturated F-ion existed on the catalysts. The strong basic centers could not only accelerate the conversion of glycerol, but also enhance the formation of glycidol from the decomposition of GC. The recycling of KF/γ-A1 2O3 revealed that deactivation of catalyst was strengthened with the reuse times, which was mainly caused by the partial leaching of active potassium species. High calcination temperature favored the transformation of KF to KAlO2 and alleviated the deactivation of the catalyst. Based on the product distribution and obtained results, a possible reaction mechanism on reaction of glycerol with dimethyl carbonate was proposed.
Role of cation-anion cooperation in the selective synthesis of glycidol from glycerol using DABCO-DMC ionic liquid as catalyst
Munshi, Mudassir K.,Gade, Swapna M.,Rane, Vilas H.,Kelkar, Ashutosh A.
, p. 32127 - 32133 (2014)
Transesterification of dimethyl carbonate with glycerol has been investigated using 1,4-diazabicyclo [2.2.2] octane (DABCO) based ionic liquid as a catalyst. DABCO reacted with dimethyl carbonate to form ionic liquid as the reaction progressed. Though the basicity of DABCO based ionic liquid was lower than that of DABCO, the catalytic activity and selectivity to glycidol was higher with DABCO based ionic liquid as a catalyst, indicating that basicity may not be the only criterion in deciding activity and selectivity of the reaction. The cooperative effect of the cation and anion of the ionic liquid is responsible for the observed results. The best results (97% glycerol conversion with 83% selectivity to glycidol and 17% selectivity to glycerol carbonate) were obtained using DABCO based ionic liquid as a catalyst. A plausible mechanism involving the role of both the cation and anion of the ionic liquid has been proposed. the Partner Organisations 2014.
