Mono-organotin(IV) compounds as esterification and transesterification catalysts

A series of monoorganotin(IV) compounds has been investigated as transesterification catalysts for the reaction of butyl propionate with methanol. The most active catalysts were found to be those which contain tin-halogen bonds, e.g. monobutyltin trichloride (BuSnCl₃), and the least effective were the coordinatively saturated monoorganotin derivatives. Certain of the mono(2-carboalkoxyethyl)tin compounds were found to undergo a facile autocatalysed transesterification reaction with alcohols. Coordination of the carbonyl group in the ester to the tin catalyst is an important factor influencing its activity. A study of the catalysis of the esterification of propionic acid by BuSnCl₃ is reported.     

Enzyme-catalyzed transesterification of vinyl esters on cellulose solids

Enzyme-catalyzed transesterification of several cellulose solids in organic media have been investigated. Several protease enzymes were made soluble in organic media through ion-paired enzyme–surfactant complexes. Subtilisin Carsberg was found to be catalytically active in the transesterification of cellulose with vinyl propionate and vinyl acrylate in anhydrous pyridine. The ester carbonyl groups in acylated cellulose derivatives were confirmed by Fourier transform infrared spectroscopy. The surfaces of these cellulose derivatives became hydrophobic as demonstrated by increased water-contact angles. The enzyme-catalyzed transesterification was confirmed to regioselectively target the primary hydroxyl group of cellulose by reactions on specifically substituted cellulose. The cellulose esters from enzyme-catalyzed transesterification could be hydrolyzed partially by the same enzyme in aqueous media, and were thus biodegradable. Surface grafting of cellulose acrylate was demonstrated using azobisisobutyronitrile-initiated polymerization of acrylonitrile in dimethylformamide. Polyacrylonitrile (PAN)-g-cellulose shows a different thermal behavior from cellulose, homopolymer PAN, and PAN/cellulose blends. The grafted PAN on PAN-g-cellulose at a 16% grafting add-on is incapable of cyclization. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1931–1939, 2001     

Cross‐linked resins functionalized with triorganotin carboxylates: synthesis,characterization and preliminary catalytic screening in transesterification

Cross‐linked polymers containing triorganotin carboxylate functionalities were synthesized from ionic exchange resins bearing carboxylic groups. The organic tin substituents selected were methyl and butyl in order to ensure different accessibility at the metal centre. The functionalization degree depends on the different substituents and strongly affects the thermal stability of the final product. Catalytic screenings were performed in order to assess the activity of the above resins in transesterification reactions, using ethyl acetate as a substrate, together with differently hindered alcohols. The results obtained point to a negligible role of the bulkiness of tin substituents with a small contribution of the metal atom Lewis acidity in the conversion of the primary alcohol, whereas with secondary and tertiary alcohols the steric hindrance of the reagent strongly affects the conversion of the reacting alcohol. The transesterification process takes place at the liquid–solid interface, so that the catalyst grafted to an insoluble solid support can be completely removed by simple filtration. Copyright © 2005 John Wiley & Sons, Ltd.     

原位ATR红外光谱研究超临界条件下酯交换反应过程与机理

在温度15℃~300℃和压力0.1MPa~25MPa下,采用原位ATR(Attenuated Total Reflectance)红外光谱技术研究高温高压条件下甲醇、乙醇和丙醇的分子间氢键和分子内化学键随温度和压力的变化及亚/超临界甲醇条件下醇油的混合与酯交换反应过程与机理。纯物质的红外光谱研究表明,在压力高于14MPa时,随温度由15℃升高到250℃,甲醇、乙醇和丙醇的分子间氢键减弱,减弱程度最大的温度为75℃~225℃;但温度升高对甲基的振动没有影响,当温度超过225℃后,甲醇的羟基振动峰发生明显分峰,而乙醇和丙醇的羟基振动峰未发现分峰变化;在整个温度和压力范围内,三油酸甘油酯的红外光谱图未发生明显变化。醇油混合与酯交换反应过程的红外研究表明,在14MPa时,当温度超过185℃后甲醇与三油酸甘油酯完全互溶,两者形成均相;当混合体系温度超过220℃时,甲醇与三油酸甘油酯开始发生酯交换反应。因此,超临界甲醇条件下的酯交换是均相反应,而且氢键变化不是导致酯交换反应的主要原因,高温高压条件下C－OH键振动形式的变化,即出现C⁺…O^-…H⁺振动使小分子醇的亲电性和亲核性均增强是导致超临界无催化酯交换反应快速进行的主要原因。     

Non-thermal effects of continuous 2.45 GHz microwaves on Fas-induced apoptosis in human Jurkat T-cell line

Non-thermal effects of microwaves (MWs) are one of the main issues studied for revising standards. The effects of MW exposure on apoptosis at non-thermal level (48 h, 2.45 GHz, 5 mW/cm2) have been studied. Results obtained assess non-thermal MW effects on Fas, but neither on butyrate- nor on ceramide-induced apoptosis in human Jurkat T-cell line. These data show that MW interacts either with Fas pathway between receptor and caspase-3 activation or on membrane proteins (i.e. Fas receptor or neurosphyngomyelinase).     

苯乙酮酸薄荷醇酯的合成及其不对称Henry反应

在四乙氧基钛催化下,用天然丰产的薄荷醇为手性源与非手性苯乙酮酸乙酯进行酯交换得到含手性基团的苯乙酮酸薄荷醇酯,经手性基团的立体选择性控制让其与硝基甲烷缩合,主要得到2s-2-羟基-2-苯基-3-硝基丙酸薄荷醇酯,用IR、1H NMR、13C NMR确认了合成物结构。并用高效液相色谱法分析了诱导不对称Henry缩合反应效果。     

Studies on the formation of PEN. I. Kinetic aspects of catalyzed reaction in transesterification of dimethylnaphthalate with ethylene glycol

The transesterification of dimethyl naphthalate (DMN) with ethylene glycol (EG) was kinetically investigated in the presence of various catalysts at 185°C. The transesterification was assumed to obey first-order kinetics with respect to DMN and EG, and a rate equation was derived. The rate constant of transesterification which was calculated from the quantity of methanol which distilled from the reaction vessel was used to evaluate the activity of each metal compound. The first-order dependence on the catalyst concentration is valid below a critical concentration which was found to be dependent on the catalyst type. The order of decreasing catalytic activity of various metal ions was found to be: Pb ≥ Zn > Co > Mg > Ni ≥ Sb, but in the case of highly basic metal salts, the rate constants were found to be extremely large at the initial stage of the reaction, and then rapidly decreased with the progress of the reaction. Effects of reaction temperature were also discussed. The activation energies for zinc acetate and lead acetate were 97.84 and 108.8 kJ/mol, respectively, which were calculated from the Arrhenius equation. © 1994 John Wiley & Sons, Inc.     

Miscibility and transesterification in blends of liquid crystalline copolyesters and polyarylate

Blends of poly(oxybenzoate-p-ethylene terephthalate) (POB-PET) and polyarylate were confirmed to be a partially miscible system by differential scanning calorimetry. When 60/40 POB-PET/PAr blend was annealed at high temperature (above 270°C) for several minutes, the ester–ester interchange (transesterification) in the blend took place immediately, as evidenced by Fourier Transformed infrared analyses. The analysis of the blend annealed at 290°C by ¹H-¹³C nuclear magnetic resonance disclosed that there were four new diads appearing in 15 min and an additional one produced in 60 min during the heat treatment. The miscibility between POB-PET and polyarylate increased with the mol concentration of these new diads judging from differential scanning calorimetry. The evolution of the concentration of the diad ethylene glycol-isophthalate during the annealing can be described by a second-order reaction. The activation energy of forming the diad ethylene glycol-isophthalate was 26.5 kcal/mol, and the preexponential factor for the transesterification reaction is 3.7 × 10⁸ min⁻¹. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1959–1969, 1998     

Transesterification and esterification with subcritical methanol. Synthesis of biodiesel

Benzoic acid esterification and ethyl benzoate transesterification with subcritical methanol were carried out at 220 °C without any catalyst. A procedure for biodiesel production from vegetable oil under indicated conditions was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 102–104, January, 2008.     

Studies on the transesterification of glycerides: I. The methanolysis of tripalmitin catalysed by diorganotin(IV) compounds

The potential of diorganotin compounds, in particular alkoxides and phenoxides, to function as neutral and non‐corrosive catalysts in the methanolysis of tripalmitin (the main triglyceride in palm oil) to methyl palmitate has been investigated. The compounds reveal a strong dependence of catalytic activity on the nature of the organic moiety on tin, the ring‐borne substituent on the phenoxyl group and the chain length of the alkoxyl fragment, as well as the ring size in cyclic alkoxides derived from bifunctional ligands such as diethanolamine. Kinetic studies, based on detailed compositional analysis of the reaction mixture by gas chromatography, were performed typically at 70.0 ± 0.1 °C in mixed methanol–tetrahydrofuran (3:2, v/v) medium and at 1.0 mol% catalyst concentration with respect to tripalmitin. The catalysts used for the kinetic studies were dibutyl bis( p‐chlorophenoxyl)tin 1, dibutyl bis(phenoxyl)tin 2, 1,1‐dibutyl‐5‐aza‐2,8‐dioxo‐1‐stannacyclo‐octane 3, 2,2‐dibutyl‐2‐stanna‐1,3‐benzdioxane 4 and dioctyltin oxide 5. The methanolysis was shown to proceed by a consecutive reaction pathway. Numerical analysis of the rate data yielded values of the three rate constants k₁, k₂ and k₃ corresponding to the respective conversions, tripalmitin → dipalmitin → monopalmitin → glycerol. Based on t values ranging from 7.2 to 22.3 h⁻¹, the following order of catalytic activity was established: 1 > 2 > 3 ≫ 5 ≫ 4; for catalyst 4 the t value was close to that of the uncatalysed reaction. A six‐fold increase in rate was observed when the catalyst concentration was raised from 1.0 to 3.0 mol% for 3. ¹¹⁹Sn NMR analysis of the chloroform extracts of the pot residue following solvent removal at the end of 24 h of the transesterification reaction revealed that the catalysts 1 and 3 essentially retained their chemical integrity. Copyright © 2000 John Wiley & Sons, Ltd.     

Fast esterification of fatty acids with alkyl chloroformates. Optimization and application in gas chromatography

Alkyl chloroformates with methyl, ethyl, and 2-chloroethyl substituents can instantaneously esterify fatty acids under proper reaction conditions. Apart from the formation of the corresponding alkyl esters, even the alkoxycarbonyl esters can be prepared. These derivatives are useful for the analysis of short-chain fatty acids. As alkoxycarbonyl ester, even acetic acid can already be separated from the solvent peak. The reaction conditions were examined, and the Influence of solvent polarity and reagent concentration on the conversion was studied. Quantitative conversion of acids to their easters was achieved in non-aqueous solutions, but even in the presence of water the yields were acceptable.     

Kinetics of the transesterification of para-nitrophenyl esters of phosphorus acids in water and aqueous hexamethylphosphorotriamide

The rate constants for the substitution of the para-nitrophenoxide ion by the phenoxide and hydroxide ions in phosphates and phosphonates are enhanced upon the addition of hexamethylphosphorotriamide (HMPTA) to water. The lack of alkaline hydrolysis of the esters in 90% aqueous HMPTA containing PhONa is a consequence of the formation of the PhOH... OH complex, which is nonreactive.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 456–459, February, 1992.     

Kinetic model of transesterification of diphenyl carbonate and 1, 4-butyldiol

The transesterification of diphenyl carbonate(DPC)with 1,4-butyldiol(BD)was kinetically investigated in the presence of lithium acetate catalyst at 465K.The reaction was followed by the measurement of the quantity of phenol which was distilled from the reactor.The experiments supported the assumption that the phenyl ester groups in DPC and phenyl hdroxybutyl carbonate(PHBH)had the same reactivity,and the transesterification obeyed first-order kinetics with respect to DPC and BD,and a rate equation was derived.The reaction rate was found to be first order with respect to the catalyst concentration as well.When those data were incorporated in the rate equation,excellent agreement between calculated values and the observed ones was recognized over a wide range.     

Mechanism of transesterification and cyclization of epoxy–polycarbonate blends catalyzed by quarternary ammonium salt

The reaction of oxirane with carbonate using quarternary ammonium salts as catalyst has been studied. Curing is caused by the transesterification reaction of the oxirane cycle with the carbonate group that proceeds by an “insertion” mechanism in the stoichiometric system. The ratio of the reactants is two oxirane groups to one carbonate group. In the nonstoichiometric system, the epoxide content is more than the stoichiometric quantity required. A cyclization reaction is followed by the transesterification reaction. To identify the finished products, a model reaction was proposed using diphenyl carbonate and phenyl glycidyl ether which results in the formation of 4-phenoxymethyl-1,3-dioxolane-2-one (PMD). The mechanism of forming the cyclic structure is assumed to proceed through the chain scission of the network in which the molecular chain crosslinked with carbonate group by a transesterification reaction. © 1996 John Wiley & Sons, Inc.     

Increased enantioselectivity and remarkable acceleration of lipase-catalyzed transesterification by using an imidazolium PEG-alkyl sulfate ionic liquid

Several types of imidazolium salt ionic liquids were prepared derived from poly(oxyethylene)alkyl sulfate and used as an additive or coating material for lipase-catalyzed transesterification in an organic solvent. A remarkably increased enantioselectivity was obtained when the salt was added at 3-10 mol % versus substrate in the Burkholderia cepacia lipase (lipase PS-C)-catalyzed transesterification of 1-phenylethanol by using vinyl acetate in diisopropyl ether or a hexane solvent system. In particular, a remarkable acceleration was accomplished by the ionic liquid coating with lipase PS in an iPr(2)O solvent system while maintaining excellent enantioselectivity; it reached approximately 500- to 1000-fold acceleration for some substrates with excellent enantioselectivity. A similar acceleration was also observed for IL 1-coated Candida rugosa lipase. MALDI-TOF mass spectrometry experiments of the ionic-liquid-coated lipase PS suggest that ionic liquid binds with lipase protein.     

Lanthanum nitrate as an efficient and recoverable homogeneous catalyst for the transesterification of dimethyl carbonate with ethanol

Lanthanum nitrate was an efficient and recoverable homogeneous catalyst for the transesterification of dimethyl carbonate (DMC) with ethanol. It was reused 5 times for the transesterification without loss of its catalytic activity.     

Synthesis and characterization of polycarbonates based on bisphenol S by melt transesterification

Several sulfone-containing polycarbonates, having inherent viscosity 0.25–0.30 dL g⁻¹ in N,N-dimethylformamide (DMF), were prepared by melt polycondensation of diphenyl carbonate (DPC) with various aromatic and aliphatic diols, in the presence of zinc acetate as transesterification catalyst. The polycarbonates were examined with IR spectra, inherent viscosity, solubility, tensile strength, contact angle, DSC and TGA. Almost all polymers were soluble in DMF, pyridine, N-methyl pyrrolidinone (NMP), THF, phenol and dimethylsulfoxide (DMSO), partially soluble in nitrobenzene, but insoluble in acetone. Polycarbonate with introduced ether linkages leads to enhanced flexibility and elongation strength. The contact angle of the polycarbonate based on bisphenol S was found in the range 42–80°, smaller than that of polycarbonates based on bisphenol AF and bisphenol A. The wettability of polycarbonate films based on bisphenol S remarkably increased with increasing oxyethylene unit in polymer chain. The smaller values of T_d of PC-3-PC-7 than of PC-1 is attributed to the flexible ether linkage. The thermal stability of a brominated aromatic polycarbonate (PC-2) is less than that of the unbrominated one (PC-1). The brominated aromatic polycarbonate (PC-2) has good flame retardency, as indicated by the large limiting oxygen index 56. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2453–2460, 1997     

Investigation on deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate by transesterification

The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol has been investigated.X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),infrared spectroscopy (IR),thermogravimetry analysis (TG),atomic absorption spectroscopy and elementary analysis are employed for the catalyst characterizaton.The results show that,the formation of Pb40(OC6H5)6 through the reaction of phenol and lead species in the catalyst leads to the crystal phase change of active component and serious leaching of lead,which is the cause of the catalyst deactivation.In addition,the composition of the leached lead is ascertained to be a mixture of Pb40(OC6H5)6 and PbO with the weight percentage of 62.7% and 37.3%,respectively.     

复合磁性MgAl水滑石制备及其酯交换性能的研究

使用共沉淀法制备磁性Fe_3O_4粒子,并以此为原料制备出Fe_3O_4/M g Al-LDH,将其焙烧产物Fe_3O_4/M g(Al)O作为微藻油脂和甲醇发生酯交换反应的催化剂,利用产物生物柴油产率作为评价催化剂的活性指标,探究其酯交换活性。通过TGDTG、XRD、SEM、EDS、TEM、N2吸附-脱附、VSM等表征手段对所制备样品进行表征。结果表明,Mg Al-LDH、Mg(Al)O在Fe_3O_4表面生长,并具有一定的磁响应能力。在反应时间为4 h、醇油物质的量比为13∶1的条件下,生物柴油产率高达90%。经过三次使用后,仍具有一定活性。在外磁场的作用下可完成催化剂与反应物的分离。     

Density estimated physicochemical properties of alanine-based ionic liquid [C7mim][Ala] and its application in selective transesterification of soybean oil

Amino acid ionic liquid (AAIL) based on alanine, 1-n-heptyl-3-methylimidazolium alanine ([C7mim][Ala]), has been prepared and characterized. Since the IL can form strong hydrogen bonds with water, trace amount of water is a problematic impurity in the IL. Using the standard addition method (SAM), the densities were measured in the temperature range from 293.15 to 343.15±0.05 K. On the basis of the experimental data of density, the surface tension , molar volume, and the molecular volume Vm, molar enthalpy of vaporization lgHm0, and the thermal expansion coefficients , for [C7mim][Ala] were estimated using semi-empirical methods. Also the interstice model has been verified with good accordance. Then the [C7mim][Ala] was taken as catalyst in the transesterification reaction with fatty acid, where soybean oil was used as raw material and methanol as reactant. The amount of catalyst, alcohol consumption, reaction time, temperature and other factors of the reaction were investigated. Using GC determination, the conversions were calculated by the internal standard method. The main ingredients of the products were identified by GC-MS as palm methyl ester and linoleic acid methyl ester only, which showed high selectivity in palmitic acid and linoleic acid.