- Diacidic ionic liquid supported on magnetic-silica nanocomposite: a novel, stable, and reusable catalyst for selective diester production
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Abstract: Supported diacidic ionic liquid on magnetic silica nanoparticles (SDAIL@magnetic nanoSiO2) was successfully prepared through a multi-step approach. 2,2- bis ((3- methylimidazolidin-1-yl) methyl) propane- 1,3- diol bromide salt was immobilized onto the surface of magnetic silica nanoparticles via covalent bonding to prepare a novel powerful acidic catalyst. The synthesized catalyst was characterized by FT-IR, SEM, TGA, VSM, N2 adsorption–desorption measurements and acid-base titration. The catalytic activity of the prepared SDAIL@magnetic nanoSiO2 was investigated for the selective diesterification of alcohols by phthalic anhydride to afford corresponding dialkyl plasticizers under solvent-free conditions. The nature of two acidic counter anions as well as the presence of Lewis acidic species (Fe3O4) on the magnetic nanosilica and high surface area of the nanosilica influenced the behavior of the catalyst. Surperisingly, the high acidic character of the catalyst facilitates the reaction with a short reaction time. Furthermore, TG analysis strongly demonstrates that major content of IL is still stable on the support up to 290?°C, so catalyst has a good thermal stability. Under the optimized conditions, the conversion of phthalic anhydride was 100% and diester plasticizers were obtained with excellent yields (80–100%). The SDAIL@magnetic nanoSiO2 catalyst showed a good reusability and could be easily separated from the reaction mixture using an external magnet thanks to its superparamagnetic behavior and reused for several runs without significant activity loss. An important advantage of the SDAIL@magnetic nanoSiO2 was its high-hydrophilicity resulted in excellent selectivity towards the formation of only diesters which are commonly used plasticizers in different industries. Graphical abstract [Figure not available: see fulltext.].
- Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan,Zekri, Negar
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- Ionic Immobilization of Silicotungstic Acid on Amine-Functionalized Zirconia: A Mesoporous Catalyst for Esterification of Maleic Acid
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Silicotungstic acid (H4SiW12O40) has been immobilized onto the mesopores of amine-functionalized zirconia by exploitation of electrostatic interactions. The ionic grafting of silicotungstic acid was confirmed by XPS, FTIR, UV/Vis-DRS and TGA analysis. The mesoporosity of the material was confirmed through N2 adsorption/desorption analysis. The morphology of the material was established by TEM analysis. The immobilized silicotungstate material was found to be an efficient heterogeneous catalyst for selective esterification of maleic acid with butan-1-ol. A 98 % level of conversion of maleic acid and 82 % selectivity for dibutyl maleate within 5 h at 95 °C was achieved. The catalyst could be reused thrice without loss of activity.
- Ramalingam, Meenakshi,Manickam, Sundar,Srinivasalu, Kutti Rani,Ismail, Mohammed Bilal,Deivanayagam, Easwaramoorthy
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- Role of the succinate skeleton in the disorder-order transition of AOT and its analogous molecules: Detection by infrared absorption spectra of the configurations arising from the difference in torsion angles of the succinate skeleton
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The IR spectra in the 13001450 cm-1 region, which reflect the CH and CH2 deformation vibrational modes of the succinate skeleton, have been investigated in detail for sodium dialkylsulfonates (alkyl groups: Ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, and n-dodecyl) and sodium 1,2-bis(2-ethylhexyl)sulfosuccinate (sodium 1,2-bis(2- ethylhexyloxycarbonyl)ethanesulfonate) (AOT). The results have provided clear evidence that two configurations, arising from the difference in the torsion angles of the succinate skeleton, are preferentially stabilized in aqueous solution as well as in the solid state, depending upon the concentration. Thus, the IR spectra of this region can be used as a powerful tool for elucidation of the mechanism of the disorderorder transition in aggregate systems of AOT or its homologs at the molecular level.
- Okabayashi, Hiro-Fumi,Izawa, Ken-Ichi,Sumiya, Akiko,Eastoe, Julian,O'Connor, Charmian J.
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- Esterification of maleic acid and butanol using cationic exchange resin as catalyst
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Abstract : Dibutyl maleate is a perfumery ester used as an intermediate in the production of paints, adhesives, and copolymers. Esterification of maleic acid and butanol was studied in presence of acidic cation exchange resin as a catalyst. The objective of this work was to test the suitability and efficacy of heterogeneous catalysts such as Indion 225H and Amberlyst-15 in the synthesis of dibutyl maleate. Various parameters deciding the conversion of reaction such as mole ratio, catalyst loading, molecular sieves, speed of agitation and effect of temperature were optimized for the maximum rate and conversion. The activation energy was calculated as 71.5?kcal/mol. Diffusivity value D AB (maleic acid in n-butanol) at 80°C was calculated as 5.08×10-10m2/s and effective diffusivity (D e-A) was calculated as 5.08×10-11m2/s. Solid–liquid mass transfer coefficient (k sl-A) was calculated as 6.77×10-6m/s for the particle size of Amberlyst-15 as 0.5 mm. Graphical Abstract: Synopsis. Synthesis of dibutyl maleate was carried out using ion exchange resin as a catalyst. Effect of various parameters on the conversion of reaction like mole ratio, catalyst loading, molecular sieves, the speed of agitation and effect of temperature was studied. [Figure not available: see fulltext.].
- Mulay, Aarti,Rathod
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- Synthesis and characterization of a new hydroxyl functionalized diacidic ionic liquid as catalyst for the preparation of diester plasticizers
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Two new functionalized diacidic ionic liquids (FDAILs) including hydroxyl functionalized diacidic ionic liquid (HFDAIL) and sulfonated diacidic ionic liquid (SFDAIL) were synthesized and characterized by 1HNMR, 13CNMR and FT-IR. The catalytic activities of these FDAILs were examined in esterification reaction of anhydrides with some alcohols to give corresponding dialkyl plasticizers under solvent-free conditions. The results indicate that HFDAIL, as hydroxyl-bearing catalyst, show better catalytic performance. Under the optimum conditions, using HFDAIL, the conversion of phthalic anhydride was high and diester plasticizers were obtained with good to excellent yields in the presence of only 10?mol% of ionic liquid. All the produced diesters could be easily recovered due to their immiscibility with the ionic liquid. Recycling experiments suggests that these ionic liquids can be reused several times without remarkable loss in their catalytic activity.
- Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan
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- Method for preparing maleate by catalyzing maleic anhydride with ionic liquid
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The invention discloses a method for preparing maleate by catalyzing maleic anhydride with ionic liquid. The preparation method is characterized by comprising the following steps: mixing ionic liquidwith maleic anhydride and fatty alcohol, carrying out heating to 80-140 DEG C, and performing a reaction for 0.5-4 h to obtain maleate, wherein the usage amount of the ionic liquid accounts for 0.1-10% by mol of the maleic anhydride, and a molar ratio of fatty alcohol to maleic anhydride is 2-12. A high-added-value chemical with the completely-esterified maleate as a main product is prepared in the invention. The method is simple in process, mild in conditions, friendly to environment and high in double esterification degree; and the ionic liquid is high in activity, not prone to inactivationand capable of being cyclically used.
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Paragraph 0045; 0048; 0049; 0052
(2020/02/29)
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- Method for preparing succinate by double carbonylation of acetylene
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The invention provides a method for preparing succinate by double carbonylation of acetylene. Acetylene, carbon monoxide and an alcohol compound are used as raw materials and subjected to the double carbonylation reaction in a solvent under the catalysis of a catalyst, and the succinate compound is obtained. The catalyst is composed of a palladium compound, a lithium halide/acid auxiliary agent and a nitrogen-oxygen ligand, wherein the nitrogen-oxygen ligand is one or more of 2-hydroxypyridine, 3-hydroxypyridine and 2-picolinic acid, and the dosage of the catalyst is 0.0001-1.0% of the total weight of the reaction system; in the reaction system, the molar ratio of acetylene to the alcohol compound is 1:(2-16), and the molar ratio of the alcohol compound to the solvent is 1:(7-35). According to the method, the succinate compounds can be produced by a one-pot method, wherein the process is simple, and the investment cost of an industrial device is low; the reaction conditions in the production process are mild, the catalytic activity of the catalyst is high, the stability is high, the service life is long, the yield can reach 90% or above, and the higher technical competitive advantage is achieved.
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Paragraph 0027-0038
(2019/12/02)
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- Photoorganocatalytic synthesis of lactones: Via a selective C-H activation-alkylation of alcohols
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Selective C-H activation is an area of growing importance in modern organic chemistry. Herein, we report our efforts in combining organocatalysis and photocatalysis for the development of a highly efficient and selective visible-light mediated protocol for the C-H activation and addition of various alcohols to a plethora of Michael acceptors, followed by a cyclization reaction leading to lactones, a repeatedly occurring motif in nature. Utilizing phenylglyoxylic acid as the photocatalyst and common household bulbs as the light source, we describe a versatile α-alkylation/lactonization of alcohols with α,β-unsaturated esters leading to products in excellent yields. The reaction mechanism was extensively studied.
- Kaplaneris, Nikolaos,Bisticha, Aikaterini,Papadopoulos, Giorgos N.,Limnios, Dimitris,Kokotos, Christoforos G.
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supporting information
p. 4451 - 4456
(2017/09/29)
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- Expanding the scope of biomass-derived chemicals through tandem reactions based on oxorhenium-catalyzed deoxydehydration
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New modes of DODH: Oxorhenium compounds act as deoxydehydration(DODH)/acid dual-purpose catalysts to transform biomass-derived diol substrates into a variety of commodity chemical precursors. The power of this approach is highlighted by a tandem [1,3]-OH shift/DODH of 2-ene-1,4-diols and 2,4-diene-1,6-diols, and by a DODH/esterification sequence of sugar acids to unsaturated esters for the production of polymers and plasticizers. Copyright
- Shiramizu, Mika,Toste, F. Dean
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supporting information
p. 12905 - 12909
(2014/01/06)
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- Efficient synthesis of symmetrical phthalate and maleate diesters using phosphinite ionic liquids
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Symmetrical dialkyl phthalates and maleates were synthesized using phosphinite ionic liquid as a catalyst and reaction medium. The results indicated that phosphinite ionic liquid shows better catalytic and reusable performance without using any acid or base catalyst. Under the optimum conditions, using 1-methyl-3-(4-phosphinitebutyl) imidazolium chloride as catalyst, the conversion of phthalic and maleic anhydrides to the corresponding diesters of primary and secondary alcohols was occurred in 72-85% yields. The diesters of tertiary alcohols and phenols could not be prepared by this method. A kind of widely used plasticizer, dioctyl phthalate, was prepared in good yield under these conditions. The ionic liquid could be reused three times after easy separation from the products without any disposal. Iranian Chemical Society 2012.
- Valizadeh,Khalili
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p. 529 - 534
(2013/02/22)
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- Reductive coupling of aldehydes by H2S in aqueous solutions, a C-C bond forming reaction of prebiotic interest
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We report here a novel reductive coupling reaction of conjugated, non- or poorly enolizable aldehydes induced by H2S and operative in aqueous solutions under prebiotically relevant conditions. This reaction leads from retinal to β-carotene, and from benzylic aldehydes to the corresponding diarylethylenes. This novel reaction also opens a new potentially prebiotic pathway leading from glyoxylic acid to various compounds that are involved in the reductive tricarboxylic acid cycle. This C-C bond forming reaction of prebiotic interest might have been operative, notably, in the sulfide-rich environments of hydrothermal vents, which have been postulated as possible sites for the first steps of organic chemical evolution.
- Kajjout, Mohammed,Hebting, Yanek,Albrecht, Pierre,Adam, Pierre
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experimental part
p. 714 - 726
(2012/07/14)
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- Highly chemo- and stereoselective intermolecular coupling of diazoacetates to give cis-olefins by using Grubbs second-generation catalyst
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Highly stereoselective formation of cis-2-ene-1,4-diesters by homo- and heterocoupling of α-diazoacetates in the presence of Grubbs second-generation catalyst is demonstrated. The dual reactivity of the catalyst in alkene metathesis and diazocoupling has been exploited in the synthesis of 12-26-membered macrocyclic dienyl dilactones by one-pot carbene dimerisation/ring-closing metathesis.
- Hodgson, David M.,Angrish, Deepshikha
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p. 3470 - 3479
(2008/02/08)
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- Homobimetallic ruthenium-N-heterocyclic carbene complexes: Synthesis, characterization, and catalytic applications
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Two new homobimetallic ruthenium-arene complexes [(p-cymene)Ru(μ-Cl) 3RuCl(η2-C2H4)(L)], where L = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (3a) or 1,3-bis(2,4,6- trimethylphenyl)-4,5-dichloroimidazolin-2-ylidene (3b), were isolated in high yields upon heating a toluene solution of [RuCl2 (p-cymene)] 2 with 1 equivalent of carbene ligand under an ethylene atmosphere. They were characterized by NMR and TGA. Their catalytic activity was investigated in the atom transfer radical polymerization of vinyl monomers. In the polymerization of methyl methacrylate, complex 3a displayed faster reaction rates than 3b and the related phosphine-based complex 2a (L = tricyclohexylphosphine), although control was more effective with the latter catalyst. When n-butyl acrylate or styrene served as monomer, a major shift of reactivity was observed between complex 2a that promoted controlled radical polymerization, and complexes 3a or 3b that favored metathetical coupling. Further homocoupling experiments with various styrene derivatives confirmed the outstanding aptitude of complex 3a (and to a lesser extent of 3b) to catalyze olefin metathesis reactions. Contrary to monometallic ruthenium-arene complexes of the [RuCl2(p-cymene)(L)] type, the new homobimetallic species did not require the addition of a diazo compound or visible light illumination to initiate the ring-opening metathesis of norbornene or cyclooctene. When α,ω-dienes were exposed to 3a or 3b, a mixture of cycloisomerization and ring-closing metathesis products was obtained in a non-selective way. Addition of a terminal alkyne co-catalyst enhanced the metathetical activity while completely repressing the cycloisomerization process. Thus, quantitative conversions of diethyl 2,2-diallylmalonate and N,N-diallyltosylamide were achieved within 2 h at room temperature using 2 mol% of catalyst precursor 3 a and 6 mol % of phenylacetylene.
- Sauvage, Xavier,Borguet, Yannick,Noels, Alfred F.,Delaude, Lionel,Demonceau, Albert
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p. 255 - 265
(2008/02/03)
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- Solubility and phase behaviors of AOT analogue surfactants in 1,1,1,2-tetrafluoroethane and supercritical carbon dioxide
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A series of AOT (aerosol-OT) analogue surfactants (sodium salt of dibutyl-2-sulfosuccinate, sodium salt of dipentyl-2-sulfosuccinate, sodium salt of dihexyl-2-sulfosuccinate, and sodium salt of dioctyl-2-sulfosuccinate) were synthesized and characterized by 1H NMR and elemental analysis. A static method coupled with gravimetric analysis is developed to measure the solubility of the surfactants in 1,1,1,2-tetrafluoroethane (HFC-134a) and supercritical CO2 (scCO2). The solubilities of the surfactants in HFC-134a and scCO2 are affected by the temperature, pressure, and carbon atom number of the surfactant. The solubility of the same surfactant in HFC-134a solvent is approximately two times that in the most commonly used supercritical solvent CO2. The pressure-temperature phase diagrams for water/MFC-134a microemulsions stabilized by the surfactants were determined using cloud-point measurements for a concentration range of the surfactant from (1.85 × 10-3 to 5.60 × 10-3) M, temperature up to 338 K, and pressure up to 40 MPa in a high-pressure vessel. At a fixed temperature, the cloud-point pressure increased with increasing water-to-surfactant molar ratio (Wo). At a fixed Wo, the cloudpoint pressure decreased with increasing temperature. The surfactant with the longest hydrocarbon chain has the highest cloud-point pressure even at lower surfactant concentrations.
- Liu, Zhao-Tie,Liu, Ling,Wu, Jin,Song, Liping,Gao, Ziwei,Dong, Wensheng,Lu, Jian
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p. 2045 - 2050
(2007/10/03)
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- Solubilities of AOT analogues surfactants in supercritical CO2 and HFC-134a fluids
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A series of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) analogue surfactants [sodium dibutyl sulfosuccinate (DBSS), sodium dipentyl sulfosuccinate (DPSS), sodium dihexyl sulfosuccinate (DHSS), and sodium dioctyl sulfosuccinate (DOSS)] were synthesized and characterized with 1H NMR and elemental analysis. The solubilities of surfactants in supercritical CO2 (scCO2) and supercritical 1,1,1,2-tetrafluoroethane (HFC-134a) fluids at a temperature range from (308 to 338) K and under pressures of (10 to 30) MPa were measured using a static method coupled with gravimetric analysis. The solubilities of these surfactants are much higher in HFC-134a fluid as compared with that in scCO2. The solubilities increased with increasing temperature and pressure for both scCO2 and HFC-134a fluids. The solubilities in scCO2 increased with increasing carbon atom number of surfactant, whereas they decreased with increasing carbon atom number of surfactant in HFC-134a. The density of scCO2 was simulated with the Peng-Robinson (P-R) equation. The experimental data were used to validate the accuracy of the P-R equation.
- Liu, Zhao-Tie,Wu, Jin,Liu, Ling,Sun, Changan,Song, Liping,Gao, Ziwei,Dong, Wensheng,Lu, Jian
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p. 1761 - 1768
(2007/10/03)
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- Raman and IR spectroscopic studies of the interaction between counterion and polar group in self-assembled systems of AOT-homologous 'sodium dialkyl sulfosuccinates'
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Headgroup-counterion interactions have been studied for a homologous series of sodium dialkyl sulfosuccinates (SDAS) with propyl, butyl, hexyl, octyl, decyl, undecyl and dodecyl chains as Aerosol-OT analogues. Raman scattering and IR absorption spectra were recorded and compared with those for dimethyl sulfosuccinate monohydrate, diethyl sulfosuccinate trihydrate and diheptyl sulfosuccinate dihydrate, whose crystal structures are known. The spectral features of the C=O and SO3- stretch modes directly reflect the interaction between the polar group and the Na+ ion and depend strongly upon the environment of hydration. The results may be summarized as follows. For the SDAS monohydrates in the solid state, there exists a strong interaction between the β C=O group and the Na+ ion, as a consequence of coordination of the β C=O to the Na+ ion, resulting in splitting of the C=O stretch modes. In particular, the common Raman (IR) bands observed at 1705- 1707 (1706-1708) and 1730-1732 (1732-1733) cm-1 may be assigned to the β C=O group coordinated to the Na+ counterion and the hydrated α C=O group, respectively. The extent of splitting of these bands is a measure of the strength of this C=O···Na+ interaction. Coordination of the β C=O to the Na+ ion also affects the C=O deformation modes of the O-C=O linkage. An increased hydration number and longer hydrocarbon chains induce a weak interaction between the C=O group and the Na+ ion. The SO3-···Na6+ interaction reflects the SO3- stretch modes, depending upon the extent of hydration. Furthermore, for the SDAS samples in the organic and aqueous microphases, Raman (IR) bands characteristic of the C=O and SO3-1 groups have been used successfully to account for the interaction between the polar group and the Na+ ion.
- Nagasoe, Yasuyuki,Ichiyanagi, Naoki,Okabayashi, Hirofumi,Nave, Sandrine,Eastoe, Julian,O'Connor, Charmian J.
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p. 4395 - 4407
(2007/10/03)
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- Selective monoesterification of dicarboxylic acids catalysed by ion-exchange resins
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Symmetrical dicarboxylic acids with 4-14 carbon atoms gave selectively the corresponding monoesters in high yields in the transesterification catalysed by strongly acidic ion-exchange resins in ester-hydrocarbon mixtures. It was found that the rate of the esterification of the dicarboxylic acids is much higher than that of the monocarboxylic acids formed. This result can explain the high selectivity for the monoester formation and can also be explained by the existence of an aqueous layer on the surface of the resins. This method of selective esterification is quite simple and practical. The Royal Society of Chemistry 1999.
- Nishiguchi, Takeshi,Ishii, Yasuhiro,Fujisaki, Shizuo
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p. 3023 - 3027
(2007/10/03)
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- KINETICS OF ESTERIFICATION OF MONOBUTYL MALEATE WITH n-BUTANOL.
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The purpose of the present work was to study the kinetics of monobutyl maleate esterification with n-butanol in the absence of catalysts. It is found that the rate of dibutyl maleate formation from monobutyl maleate and n-butanol conforms to an equation of overall third order, of the second order with respect to monobutyl maleate, and of the first order with respect to n-butanol. Our theoretical data are in agreement with the mechanism postulated for the conversion of substituted succinate monoesters into the diester.
- Timofeev,Sushchenko,Tereshchenko,Golubkov
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p. 1534 - 1537
(2007/10/02)
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- Preparation of aconitic acid
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Novel methods for preparing polycarboxylic compounds which are useful as metal sequestrants and food acidulants are disclosed. These compounds are aconitic and a mixture of aconitic acid, and the lactones of isocitric acid and alloisocitric acid. The compounds can be neutralized to the corresponding salts which, in turn, are metal sequestering agents. The novel methods include chlorination of propane-1,1,2,3-tetracarboxyalic tetraesters.
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