108-21-4Relevant articles and documents
Kinetics of the esterification of acetic acid with 2-propanol: Impact of different acidic cation exchange resins on reaction mechanism
Ali, Sami H.,Merchant, Sabiha Q.
, p. 593 - 612 (2006)
The kinetics of the esterification of acetic acid with the secondary alcohol, 2-propanol, catalyzed by the cation exchange resins, Dowex 50Wx8-400, Amberlite IR-120, and Amberlyst 15 has been studied at temperatures of 303, 323, and 343 K; acid to alcohol molar ratios of 0.5, 1, and 2; and catalyst loadings of 20, 40, and 60 g/L. The equilibrium constant was experimentally determined, and the reaction was found to be mildly exothermic. External and internal diffusion limitations were absent under the implemented experimental conditions. Systems catalyzed by gel-type resins (Dowex 50Wx8-400 and Amberlite IR-120) exhibit some similarities in their reaction kinetics. Increase in reaction temperature, acid to alcohol ratio, and catalyst loading is found to enhance reaction kinetics for the three catalysts. The pseudohomogeneous (PH), Eley Rideal (ER), Langmuir Hinshelwood (LH), modified Langmuir Hinshelwood (ML), and Poepken (PP) models were found to predict reaction kinetics with mean relative errors of less than 5.4%. However, the ML model was found to be better for predicting reaction kinetics in the systems catalyzed by gel-type resins, while the PP model was better for the system catalyzed by the macroreticular catalyst, Amberlyst 15. The Eact for the forward reaction is found to be 57.0, 59.0, and 64.0 kJ/mole for the systems catalyzed by Dowex 50Wx8-400, Amberlite IR-120, and Amberlyst 15, respectively. For these three catalysts, the adsorption equilibrium constants of the components present in the system increase in the same order as do the solubility parameters of the component. Nonideality in the system is successfully accounted for by the UNIFAC model.
Acetylation of alcohols catalyzed by dodeca-tungsto(molybdo)phosphoric acid
Tayebee, Reza,Alizadeh, Mohammad H.
, p. 1063 - 1069 (2006)
Acetylation of primary, secondary, and tertiary alcohols was carried out in some refluxing alkyl acetates and in two carboxylic acids with the participation of catalytic amounts of H3PW12O 40, H3PMo12O40, and H 14P5W30O110 with good yields and high stereo(regio)specificity under mild reaction condition. H 3PW12O40 and H3PMo 12O40 have also shown excellent reactivity in the formylation of 1-butanol with ethyl formate at room temperature and in short reaction times. Heteropolyacid catalysts could be separated after a simple work up and reused for several times. Springer-Verlag 2006.
Corrigan,Stichweh
, p. 991 (1968)
The heterogenation of melamine and its catalytic activity
Adam, Farook,Hello, Kasim Mohammed,Osman, Hasnah
, p. 115 - 121 (2010)
The immobilization of melamine (Mela) onto silica extracted from rice husk ash (RHA) has been done via 3-chloropropyltriethoxysiline (CPTES). The resulting catalyst was designated as RHAPrMela. The melamine loading on the silica was found to be ca. 65.74%. The 29Si MAS NMR showed the presence of T2, T3, Q3 and Q4 silicon centers. The 13C MAS NMR showed that RHAPrMela had three chemical shifts at 14.83, 31.17 and 52.24 ppm, consistent with the three carbon atoms, and two chemical shifts at 161.52 and 169.67 ppm with double spinning side bands, indicating that the three carbon atoms in melamine ring are not equivalent in RHAPrMela. The catalytic potential of RHAPrMela was tested for the esterification of acetic acid with several alcohols. A conversion of 73% was achieved with 100% selectivity for the respective esters. The catalyst was easily regenerated and could be reused many times without loss of catalytic activity.
Efficient Baeyer-Villiger electro-oxidation of ketones with molecular oxygen using an activated carbon fiber electrode in ionic liquid [bmim][OTf]
Hu, Yu Lin,Xie, Yi Bi,Li, De Jiang
, p. 297 - 306 (2016)
A new and efficient method for the synthesis of lactones and esters involving the application of an molecular oxygen-based electro-catalytic oxidation system and ionic liquid [bmim][OTf] as electrolyte has been developed. The reaction between various ketones with molecular oxygen proceeds in a three-electrode cell under constant current conditions in [bmim][OTf] at room temperature to give the corresponding esters and lactones in good to excellent isolated yield. Additionally, the possible mechanism of Baeyer-Villiger oxidation of ketones in the electro-catalytic system is proposed.
Chemical Conversions using Sheet Silicates: Facile Ester Synthesis by Direct Addition of Acids to Alkenes
Ballantine, James A.,Davies, Mary,Purnell, Howard,Rayanakorn, Mongkon,Thomas, John M.,Williams, Kevin J.
, p. 8 - 9 (1981)
Ethene and acetic acid react in the interlamellar regions of certain cation (e.g.Al3+)-exchanged montmorillonites to yield ethyl acetate as the sole product, and a variety of carboxylic acids readily add to C2-C8 alkenes at temperatures above 100 deg C to yield the corresponding esters in high and selective yields.
Hydroxide-promoted selective C(α)-C(β) bond activation of aliphatic ethers by rhodium(III) porphyrins
Lee, Siu Yin,Lai, Tsz Ho,Hui, Ying Ying,Chan, Kin Shing
, p. 88 - 93 (2014)
The selective aliphatic C(α)-C(β) bond activation (CCA) of ethers by rhodium(III) porphyrin halides in the presence of KOH was achieved to give Rh-C(β) alkyls up to 88% yield. The addition of H2O and a phase transfer agent Ph4PBr improved the homogeneity of the reaction mixture and significantly brought down the reaction temperature to 60 °C. At this mild temperature, the C(α) co-product was oxidized to the corresponding esters in up to 89% yield. KOH promotes the bond activation by transferring the hydroxyl group to rhodium porphyrin to generate the key intermediate RhIII(ttp)OH (ttp = 5,10,15,20-tetratolylporphyrinate dianion).
Homogeneous Metal-Complex Catalyst Systems in the Partial Oxidation of Propane with Oxygen
Chepaikin, E. G.,Menchikova, G. N.,Pomogailo, S. I.
, (2020)
Abstract: The effect of copper compounds and phosphorus–molybdenum–vanadium heteropoly acids (HPAs) H5PMo10V2O40 and H7PMo8V4O40 used as cocatalysts in the cooxidation
Direct catalytic oxidation of lower alkanes in ionic liquid media
Chepaikin,Bezruchko,Menchikova,Moiseeva,Gekhman
, p. 374 - 381 (2014)
Immobilization of rhodium (palladium)-copper-chloride catalytic systems in ionic liquids as high-boiling-point solvents affects the distribution of propane oxidation products: the acetone yield increases and the yield of alcohols decreases. Propane is oxidized to acetone, bypassing the isopropanol formation step. Methane is oxidized under more severe conditions than propane, giving methyl trifluoroacetate as the main product. Mechanisms of action of the catalytic systems based on rhodium and palladium are close to each other and likely include oxo or peroxo complexes as intermediates.
A potential “green” organotin: Bis-(methylthiopropyl)tin dichloride, [MeS (CH2)3]2SnCl2
Vargas, Diana Gabriela,Metta-Maga?a, Alejandro,Sharma, Hemant K.,Whalen, Margaret M.,Gilbert, Thomas M.,Pannell, Keith H.
, p. 125 - 130 (2017)
The tetravalent organotin compound [MeS(CH2)3]2SnCl2, 1, has been synthesized in high yield and structurally characterized as being hexa-coordinate at tin with two intramolecular Sn-S bonds. The specific structure has been shown by theoretical calculations to be the low energy geometric structure available, and the differences associated with the experimental and calculated Sn-S bond lengths ascribed to crystal packing issues. The intramolecular Sn-S bonding produces a benign organotin compound with respect to its interactions with human natural killer cells; however, this blocking of coordination sites at Sn does not reduce its capacity to act as an efficient esterification catalyst.
-
Sowa,Nieuwland
, p. 5052 (1933)
-
-
Dorris,Sowa
, p. 358 (1938)
-
-
Gierut,Sowa,Nieuwland
, p. 786 (1936)
-
-
Baum,K.,Beard,C.D.
, p. 81 - 85 (1975)
-
-
Kharasch et al.
, p. 905,906,910 (1952)
-
-
Juenge et al.
, p. 2671 (1971)
-
Acetic Anhydride as an Oxygen Donor in the Non-Hydrolytic Sol–Gel Synthesis of Mesoporous TiO2 with High Electrochemical Lithium Storage Performances
Wang, Yanhui,Kim, Sanghoon,Louvain, Nicolas,Alauzun, Johan G.,Mutin, P. Hubert
, p. 4767 - 4774 (2019)
An original, halide-free non-hydrolytic sol–gel route to mesoporous anatase TiO2 with hierarchical porosity and high specific surface area is reported. This route is based on the reaction at 200 °C of titanium(IV) isopropoxide with acetic anhydride, in the absence of a catalyst or solvent. NMR spectroscopic studies indicate that this method provides an efficient, truly non-hydrolytic and aprotic route to TiO2. Formation of the oxide involves successive acetoxylation and condensation reactions, both with ester elimination. The resulting TiO2 materials were nanocrystalline, even before calcination. Small (about 10 nm) anatase nanocrystals spontaneously aggregated to form mesoporous micron-sized particles with high specific surface area (240 m2 g?1 before calcination). Evaluation of the lithium storage performances shows a high reversible specific capacity, particularly for the non-calcined sample with the highest specific surface area favouring pseudo-capacitive storage: 253 mAh g?1 at 0.1 C and 218 mAh g?1 at 1 C (C=336 mA g?1). This sample also shows good cyclability (92 % retention after 200 cycles at 336 mA g?1) with a high coulombic efficiency (99.8 %). Synthesis in the presence of a solvent (toluene or squalane) offers the possibility to tune the morphology and texture of the TiO2 nanomaterials.
-
Friess et al.
, p. 1305,1306 (1952)
-
Sowa
, p. 654 ()
Substituent and Solvent Effects in the Kinetics of N-Alkylimidazole-Catalyzed Reaction of Acetic Anhydride with Isopropyl Alcohol
Pandit, Nivedita K.,Obaseki, Andrew O.,Connors, Kenneth A.
, p. 1678 - 1679 (1980)
The overall rate of the N-alkylimidazole-catalyzed reaction of acetic anhydride with isopropyl alcohol is rather insensitive to solvent polarity.Of the nine solvents studied, N,N-dimethylformamide is the best for analytical use.A series of N-alkyl substituted imidazoles was investigated as catalysts in this reaction.The most effective catalyst was N-n-pentylimidazole, which is about 60percent more reactive than N-methylimidazole.
A Pyridine-Acetylene-Aniline Oligomer: Saccharide Recognition and Influence of this Recognition Array on the Activity as Acylation Catalyst
Ohishi, Yuki,Takata, Toshikazu,Inouye, Masahiko
, p. 2565 - 2569 (2020)
In order to create new functions of foldamer-type hosts, various kinds of recognition arrays are expected to be developed. Here, a pyridine-acetylene-aniline unit is presented as a new class of a saccharide recognition array. The conformational stabilities of this array were analyzed by DFT calculation, and suggested that a pyridine-acetylene-aniline oligomer tends to form a helical structure. An oligomer of this array was synthesized, and its association for octyl β-D-glucopyranoside was confirmed by 1H NMR measurements. UV/Vis, circular dichroism, and fluorescence titration experiments revealed its high affinity for octyl glycosides in apolar solvents (Ka=104 to 105 M?1). This oligomer was relatively stable under basic conditions, and therefore this array was expected to be applied to the derivatization of saccharides. A 4-(dialkylamino)pyridine attached pyridine-acetylene-aniline oligomer proved to catalyze the acylation of the octyl glucoside.
Oxidation of Propane: Influence of the Nature of Catalyst, Cocatalyst, and Coreductant
Chepaikin, E. G.,Menchikova, G. N.,Pomogailo, S. I.
, p. 781 - 786 (2021/08/03)
Abstract: Variation of the nature of the components of the catalytic systems comprisinga catalyst [Pd/C, Pd(α,α-bipy)Cl2,RhCl3] and a cocatalyst(FeSO4, CuSO4), as well as acoreductant (H2, CO), allows exerting some control overthe selectivity of the process of propane oxidation with oxygen. In particular,the yield of carbonyl compounds such as acetone and propanal in the presence ofthe Pd/C–FeSO4–H2catalytic systemreached 90%, and that of propyl esters in the presence ofRhCl3–CuSO4–CO catalyticsystem was 64.5%. These differences are supposedly attributable to the changesin the process mechanism depending on the composition of the catalyticsystems. [Figure not available: see fulltext.]