Esterification experimental procedures

Other examples of esterification with trialkyloxonium salts have been reported.7,8 The present procedure offers the advantages that the reactive carboxylate ion is generated in sitv and that a low-boiling, nonaqueous solvent is employed, whereby the experimental procedure is considerably simplified. A related method has been reported which utilizes a hindered amine wdth dimethyl sulfate [Sulfuric acid, dimethyl csterj as the alkylating agent.9 The present procedure is carried out under somewhat milder conditions and avoids the use of highly toxic reagents. 

Experimental procedure for the enzymatic esterification of oleic acid with... 

Transesterification under strongly basic reaction conditions has been used to acy-late support-bound alcohols with alkyl esters (Entry 10, Table 13.12). For sensitive acids, the Mitsunobu reaction is a particularly mild method of esterification. This reaction gives high yields with support-bound primary aliphatic alcohols and proceeds under essentially neutral reaction conditions (Experimental Procedure 13.4). Mitsunobu esterification of PEG with /V-Fmoc amino acids has also been reported [172]. 

Standard solid-phase peptide synthesis requires the first (C-terminal) amino acid to be esterified with a polymeric alcohol. Partial racemization can occur during the esterification of N-protected amino acids with Wang resin or hydroxymethyl polystyrene [200,201]. /V-Fmoc amino acids are particularly problematic because the bases required to catalyze the acylation of alcohols can also lead to deprotection. A comparative study of various esterification methods for the attachment of Fmoc amino acids to Wang resin [202] showed that the highest loadings with minimal racemization can be achieved under Mitsunobu conditions or by activation with 2,6-dichloroben-zoyl chloride (Experimental Procedure 13.5). iV-Fmoc amino acid fluorides in the presence of DMAP also proved suitable for the racemization-free esterification of Wang resin (Entry 1, Table 13.13). The most extensive racemization was observed when DMF or THF was used as solvent, whereas little or no racemization occurred in toluene or DCM [203]. 

Experimental Procedure 13.5 Esterification of Wane resin with Fraoc amino acids... 

Scheme 44 summarizes an addition reaction by the Barton method. Thiohydroxamate esters (32) are readily prepared and isolated, but, more typically, they are generated in situ. Experimental procedures have been described in detail148151 and often entail the slow addition of an acid chloride to a refluxing chlorobenzene solution of the readily available sodium salt (31), dimethylaminopyridine (DMAP, to catalyze the esterification), and excess alkene. The products are usually isolated by standard aqueous work-up and chromatographic purification. 

By varying reaction condititnis, the optimum extent of esterification was obtained for each kind of proteins. Table 1 shows the highest esterification values obtained from an experimental design. Sunflower proteins underwent esterification in a larger extent than wheat gluten proteins. Only 25 % of the carboxyl groups of wheat gluten could be esterified with this experimental procedure. The different structure of proteins may account for this difference. 

Likewise the acid or base catalyzed reaction of an alcohol and an acid anhydride is a regular method of esterification [4]. For many acids the most convenient experimental procedure is to form a mixed anhydride in situ by reaction with trifluoroacetic anhydride [23, 24] or the reagents listed above (method A). Cyclic anhydrides of dibasic acids yield monoesters with alcohols and this reaction is utilized in the preparation of glutamine (11) from glutamic acid (10) and in a similar synthesis of asparagine [35, 36]. 

Two separate series of experiments were carried out in order to study the reactivity of EPR-g-SA towards low Mw diols with or without the addition of a tertiary amine as catalyst, and the reactivity of EPR-g-SA towards a long-chain hydroxyl-terminated polybutadiene (HTPB). For both of them, the same experimental procedure was followed to ensure an intimate mixing of the reactants, they were all dissolved in a common solvent at room temperature and in a certain stoichiometric amount (in solution, the kinetics of esterification is very slow, thus the degree of reaction is negligible). Subsequently, the solvent is quickly removed by evaporation under vacuum at room temperature directly onto KBr disks to obtain a film which is used for IR analysis. 

The Overman esterification is a palladium-catalyzed formation of enantioenriched allyl esters from carboxylic esters with primary allyl imidates. From a mechanistic point of view, it is related to the Tsuji-Trost reaction. It proceeds under quite mild conditions with high enantiomerically access if the COP ([Ti -(5)-2-(4-methylethyl)-oxazolinylcyclo-pentadienyl]-(T] -tetraphenylcyclobutadiene)cobalt) complex is used. For example, Kirsch and co-workers used the Pd-catalyzed Overman esterification " in their approach to 1,3-polyols starting from (Z)-allylic trichloroacetimidates to build up the stereogenic centers. By choice of the required enantiomer of COP-OAc catalyst, every possible diastereoisomer is accessible in high stereoselectivity (Experimental Procedure below). 

The variety of enzyme-catalyzed kinetic resolutions of enantiomers reported ia recent years is enormous. Similar to asymmetric synthesis, enantioselective resolutions are carried out ia either hydrolytic or esterification—transesterification modes. Both modes have advantages and disadvantages. Hydrolytic resolutions that are carried out ia a predominantiy aqueous medium are usually faster and, as a consequence, require smaller quantities of enzymes. On the other hand, esterifications ia organic solvents are experimentally simpler procedures, aHowiag easy product isolation and reuse of the enzyme without immobilization. 

Here, we report the application of this procedure for immobilizing Mucor miehei lipase. A catalytic test was aimed at producing esters by direct esterification reactions with a large range of carboxylic acids (from C4 to C16), and a diversity of alcohols (from C4 to C8). Several reaction model systems are analyzed in order to illustrate the kind of products that can be made by using an experimental preparation of lipase immobilized on POS-PVA particles. 

First of all, we collected the main techniques used in the kinetic studies of the reaction (reaction procedures, analytical methods, treatment of experimental data). In fact, unambiguous results can be obtained only if some basic conditions are observed. The survey of the literature shows a great diversity of the catalysts used in epoxy-carboxy esterifications or polyesterifications however, at least in the case of kinetic studies, tertiary amines and ammonium salts are largely predominant. From the fundamental studies carried out with organic models, and mostly in solution, several mechanisms were proposed involving the formation of a complex which can be cyclic or not. 

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