Esterification and transesterification

Rea.ctlons, The chemistry of butanediol is deterrnined by the two primary hydroxyls. Esterification is normal. It is advisable to use nonacidic catalysts for esterification and transesterification (122) to avoid cycHc dehydration. When carbonate esters are prepared at high dilutions, some cycHc ester is formed more concentrated solutions give a polymeric product (123). With excess phosgene the usefiil bischloroformate can be prepared (124). 

Esterification and Transesterification to Produce Alkyl Mercaptopropionates. The other methods used to produce many of the... 

Stannous oxalate is used as an esterification and transesterification catalyst for the preparation of alkyds, esters, and polyesters (172,173). In esterification reactions, it limits the undeskable side reactions responsible for the degradation of esters at preparation temperatures. The U.S. Bureau of Mines conducted research on the use of stannous oxalate as a catalyst in the hydrogenation of coal (174) (see Coal). 

Amino alcohols can be resolved by a number of pathways including hydrolysis, esterification, and transesterification. For example, hydrolysis of Ai,0-diacet5l-2-amino-l-butanol with PPL followed by recrystallization results in (80a) with 95% ee (108). Hydrolysis of racemic acetates or butyrates of 2-[(aLkoxycarbonyl)amino]-l-aLkanols with PFL gives (R)-alcohol (81) with 95% ee (109). (3)-(81) can be obtained by transesterification of the racemic (81) with ethyl acetate which also serves as the reaction medium (109). 

Aqueous solutions are not suitable solvents for esterifications and transesterifications, and these reactions are carried out in organic solvents of low polarity [9-12]. However, enzymes are surrounded by a hydration shell or bound water that is required for the retention of structure and catalytic activity [13]. Polar hydrophilic solvents such as DMF, DMSO, acetone, and alcohols (log P<0, where P is the partition coefficient between octanol and water) are incompatible and lead to rapid denaturation. Common solvents for esterifications and transesterifications include alkanes (hexane/log P=3.5), aromatics (toluene/2.5, benzene/2), haloalkanes (CHCI3/2, CH2CI2/I.4), and ethers (diisopropyl ether/1.9, terf-butylmethyl ether/ 0.94, diethyl ether/0.85). Exceptionally stable enzymes such as Candida antarctica lipase B (CAL-B) have been used in more polar solvents (tetrahydrofuran/0.49, acetonitrile/—0.33). Room-temperature ionic liquids [14—17] and supercritical fluids [18] are also good media for a wide range of biotransformations. 

Organotin compounds such as monobutyltin oxide, the main substance used, accounting for 70% of consumption, dibutyltin oxide, monooctyltin oxide, and dioctyltin oxide are used in certain esterification and transesterification reactions, at concentrations between 0.001% and 0.5% by weight. They are used in the production of substances such as phthalates, polyesters, alkyd resins, fatty acid esters, and adipates and in trans-esterifications. These substances are in turn used as plasticizers, synthetic lubricants, and coatings. Organo-tins are used as catalysts to reduce the formation of unwanted by-products and also provide the required colour properties (ETICA, 2002). 

Cutinase is a hydrolytic enzyme that degrades cutin, the cuticular polymer of higher plants [4], Unlike the oflier lipolytic enzymes, such lipases and esterases, cutinase does not require interfacial activation for substrate binding and activity. Cutinases have been largely exploited for esterification and transesterification in chemical synthesis [5] and have also been applied in laundry or dishwashing detergent [6]. 

Lipase is an enzyme which catalyzes the hydrolysis of fatty acid esters normally in an aqueous environment in living systems. However, hpases are sometimes stable in organic solvents and can be used as catalyst for esterifications and transesterifications. By utihzing such catalytic specificities of lipase, functional aliphatic polyesters have been synthesized by various polymerization modes. Typical reaction types of hpase-catalyzed polymerization leading to polyesters are summarized in Scheme 1. Lipase-catalyzed polymerizations also produced polycarbonates and polyphosphates. 

S (2)-hydroxy-3-butenenitrile from acrolein and HCN trans hydrocyanation using, for instance, acetone cyanohydrin Hydrolysis of nitriles to amides, e.g. acrylonitrile to acrylamide Isomerization of glucose to fructose Esterifications and transesterifications Interesterify positions 1 and 3 of natural glycerides Oxidation of glucose to gluconic acid, glycolic acid to glyoxalic acid... 

Syntheses of aliphatic polyesters by fermentation and chemical processes have been extensively studied from the viewpoint of biodegradable materials science. Recently, another approach to their production has been made by using an isolated lipase or esterase as catalyst via non-biosynthetic pathways under mild reaction conditions. Lipase and esterase are enzymes which catalyze hydrolysis of esters in an aqueous environment in living systems. Some of them can act as catalyst for the reverse reactions, esterifications and transesterifications, in organic media [1-5]. These catalytic actions have been expanded to... 

In lipase-catalyzed esterifications and transesterifications, esters of halo-genated alcohols, typically 2-chloroethanol, 2,2,2-trifluoroethanol, and 2,2,2-... 

Esterification and transesterification using TiIV compounds are useful methods for functionalization of ester moieties under mild conditions. In the transformation of carboxylic acids to esters, a catalytic amount of TiCl(OTf)3 is effective (Scheme 30).110 Titanium alkoxides, such as Ti(OEt)4 or Ti(0 Pr)4, easily promote transesterification of alkoxy groups to other ones—even to more hindered groups.111 Anomerization of glycosides to Q-isomers using a Tilv-bascd Lewis acid is an important method for controlling the product structure.112... 

Esterification is the first step in PET synthesis but also occurs during melt-phase polycondensation, SSP, and extrusion processes due to the significant formation of carboxyl end groups by polymer degradation. As an equilibrium reaction, esterification is always accompanied by the reverse reaction being hydrolysis. In industrial esterification reactors, esterification and transesterification proceed simultaneously, and thus a complex reaction scheme with parallel and serial equilibrium reactions has to be considered. In addition, the esterification process involves three phases, i.e. solid TPA, a homogeneous liquid phase and the gas phase. The respective phase equilibria will be discussed below in Section 3.1. 

An extensive review on titanium catalysts for esterification and transesterification has been published by Siling and Laricheva [40],... 

The production of PET is a well-known industrial process. Early patents on PET synthesis refer to the 1940s. Esterification and transesterification reactions have been investigated since the end of the 19th century. PET production plants have been optimized over the last few decades based on well-established production know-how . PET is now a commodity product with unusually rapid growth and further nearly unlimited future growth perspectives. 

However, in contrast to the production know-how , the scientific knowledge on the details of phase equilibria, kinetics, mechanisms, catalysis and mass-transport phenomena involved in polycondensation is rather unsatisfactory. Thus, engineering calculations are based on limited scientific fundamentals. Only a few high-quality papers on the details of esterification and transesterification in PET synthesis have been published in the last 45 years. The kinetic data available in the public domain are scattered over a wide range, and for some aspects the publications even offer contradicting data. 

As mentioned above, esterification and transesterification are the two main reactions responsible for the molecular weight increase in PET. Both reactions are considered to be second-order and their rates are given as follows [12] ... 

Generally, two to three preheater sections are used for the product heat-up by using nitrogen, and two to three sections are required to reach the final viscosity. Cooling is carried out either in an additional compartment or with a fluid bed. Typically, for a viscosity increase from 0.60 up to 1.0, the crystallinity increases to ca. 62 vol%, and the carboxyl end group concentration decreases by approximately 10-15 mol/t. This equates to both esterification and transesterification contributing half of the IV increase if side reactions are neglected. 

The understanding of the SSP process is based on the mechanism of polyester synthesis. Polycondensation in the molten (melt) state (MPPC) is a chemical equilibrium reaction governed by classical kinetic and thermodynamic parameters. Rapid removal of volatile side products as well as the influence of temperature, time and catalysts are of essential importance. In the later stages of polycondensation, the increase in the degree of polymerization (DP) is restricted by the diffusion of volatile reaction products. Additionally, competing reactions such as inter- and intramolecular esterification and transesterification put a limit to the DP (Figure 5.1). 

There are a few reported cases of esterases that catalyze not only hydrolysis but also the reverse reaction of ester formation, in analogy with the global reaction described for serine peptidases (Fig. 3.4). Thus, cholesterol esterase can catalyze the esterification of oleic acid with cholesterol and, more importantly in our context, that of fatty acids with haloethanols [54], Esterification and transesterification reactions are also mediated by carboxyleste-rases, as discussed in greater detail in Sect. 7.4. 

Reactions with anhydrides and acid chlorides are more rapid and can occur in an essentially nonreversible fashion. But, anhydrides and acid chlorides are considered high-energy reactants since they often involve additional energy-requiring steps in their production, and are thus less suitable for large-scale production of materials. The activity energies for direct esterification and transesterification are on the order of 30 kcal/mol (120 kJ/mol) while the activation energies for anhydride and acid chloride reaction with alcohols are on the order of 15-20 kcal/mol (60-80 kJ/mol). 

In this chapter, we report just a few selected examples of heterogeneous catalytic systems for the esterification of fatty acids and for the simultaneous esterification and transesterification of acidic oils and fats, and we discuss the use of selective hydrogenation as a tool for the production of high-quality biodiesel from non-edible raw materials. 

However, acids can simultaneously catalyze both esterification and transesterification, therefore they can directly produce biodiesel from low-cost lipid feedstocks. 

Catalysts able to promote both transesterification of triglycerides and esterification of FFAs in an oil or fat are still rare and up to now none of them have found a commercial application. Thus far it seems that a moderate to high concentration of strongly acidic sites and a hydrophobic surface are mandatory to achieve good conversions in simultaneous esterification and transesterification reactions, but more research and creative thinking are still needed in this area. 

Many types of solid catalysts have been tested in esterification and transesterification reactions of fatty acids, TG feedstock and simple esters. Nonetheless, it is possible to group most catalysts in three general categories metal, base, and acid catalysts. The following sections deal with these three groups accordingly. 

Perhaps, a more important reason for the little research in this particular area is the slow reaction rate associated with acid catalysis in general. However, the ability of solid acids to catalyze both esterification and transesterification reactions simultaneously and the possibility for employing catalysts that are reusable and green, meaning that they do not pose a great environmental threat, are attractive aspects that make the study of these materials imperative. 

Many publications advocate the use of solid acid resins in esterification reactions. A comprehensive review of organic reactions catalyzed by resins is that of Harmer and Sun. However, thermal-stability above 140°C and lack of structural integrity at high pressures severely limit the applicability of organic resins as catalysts for esterification and transesterification. 

Lipase-catalysed esterification and transesterification reactions have a wide range of applications in the synthesis of aroma compounds. 

Biphasic systems have been effectively used in several enzyme-catalyzed reactions, including peptide and alkyl glycosides synthesis, esterification and transesterification, alcoholysis, hydrolysis, and enantiomeric resolution [2, 24, 60]. Although application of this particular bioconversion system has been used for final products, it is mostly used in the production of intermediate compounds, particularly optically active ones, that can be used as building blocks in the pharmaceutical and food sectors [61-64]. Updated reviews have addressed this matter [2, 4, 24, 60-63], and examples of some representative recent applications of this methodology are given in Table 8.1). 

With one exception [447], only sulphonated resins were used as catalysts in kinetic studies of esterification and transesterification, the resins being almost exclusively styrene—divinylbenzene copolymers in one case, a sulphonated phenol—formaldehyde resin was also used [433]. The main factors determining the catalytic activity are (i) the concentration of functional groups in protonated form (— S03H groups) and (ii) the degree of crosslinking of the copolymer (characterised by the divinylbenzene content). 

A more general scheme with both reactants adsorbed is that represented by scheme (g). It was considered probable in the liquid phase transesterification in a non-polar solvent (cyclohexane) [435] and it may correspond to all vapour phase esterifications and transesterifications where the rate equations from the kinetic analysis (see eqns. (27) and (29) suggested the involvement of dual- or triple-sites. 

Resolution of Racemic Amines and Amino Acids. Acvlases (EC 3.5.1.14) are the most commonly used enzymes for the resolution of amino acids. Porcine kidney acylase (PKA) and the fungal Aspergillus acylasc (AA) are commercially available, inexpensive, and stable. Amino alcohols can be resolved by a number of pathways, including hydrolysis, esterification, and transesterification. 

Capewell et al. (1992) Batch Hydrolysis, esterification, and transesterification of p-hydroxycarbonic esters and acids Lipase PS... 

Fontes et al. (1998b) studied the enantioselectivity of cutinase and found that it was very selective toward one enantiomer with an enantiomeric excess of almost 100%. They found that the enantioselectivity was very sensitive to changes in water content. Bornscheuer et al. (1992) studied hydrolysis, esterification, and transesterification in carbon dioxide to try to find the best method for producing enantiomerically pure substances in carbon dioxide. They found that the thermodynamically favored hydrolysis led to higher enantiomeric excess with less enzyme in the shortest time. Michor et al. (1996b) also examined more than one system to determine a better route to product and found that while the transesterification of -menthol was fast and resulted in high enantiomeric excess, resolution of -citronellol was not feasible. The reaction rate for the reaction of -citronellol was 10-20 times of that of -menthol, but was not selective. 

Arylpropionic acids are important class of non-steroidal anti-inflammatory drugs (NSAID). Their pharmacological activity is mainly in one of both enantiomers. Thus, efforts had been made to access to the enantiomerically pure substance. The kinetic resolution of racemic 2-(2-fluoro-4-biphenyl) propanoic acid 56 and 2(4-isobutylphenyl) propanoic acid 59 (Ibuprofen) was performed via enzymatic esterification and transesterification using an alcohol and vinyl acetate, respectively in a membrane reactor. The unreacted acid is obtained in highly enantiomerically enriched form. A consecutive approach consisting of the enzymatic hydrolysis of the resulted esters is needed to achieve the alcohol in optically pure form.77... 

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