Carboxyl group esterification

Poly(y-glutamic acid), an analogue of poly (aspartic acid) with another methylene group in the side chain (12.35), is produced by Bacillus subtilis.188 (Notice that polyglutamic acid made by chemical synthesis involves the other carboxylic group.) Esterification improves the pro cessibility and the solubility in organic solvents. 

Figure 5.8 Cross-linking of HA with BDDE at the carboxylic group (esterification) CH2-CH-R-CH-CH2...

Protecting reagent for carboxyl groups. Esterification reagent for carboxylic acids for hplc or ms. anal. 

Section 19 15 An intramolecular esterification can occur when a molecule contains both a hydroxyl and a carboxyl group Cyclic esters are called lactones and are most stable when the nng is five or six membered... 

Carboxyl groups of ammo acids and peptides are normally protected as esters Methyl and ethyl esters are prepared by Fischer esterification Deprotection of methyl and ethyl esters is accomplished by hydrolysis m base Benzyl esters are a popular choice because they can also be removed by hydrogenolysis Thus a synthetic peptide protected at both... 

Section 27 5 Ammo acids undergo reactions characteristic of the ammo group (e g amide formation) and the carboxyl group (e g esterification) Ammo acid side chains undergo reactions characteristic of the functional groups they contain... 

Suppose the total number of carboxyl groups in the original mixture is 2 mol, of which 1.0% is present as acetic acid to render the resulting polymer inert to subsequent esterification. What value of p would be required to produce the desired polymer in this case, assuming no other stoichiometric imbalance ... 

Acetylation of hydroxyl groups and esterification of carboxyl groups have been observed ia a limited number of cases but, ia geaeral, have ao preparative advantage over chemical methods. By comparison, phosphorylation has been useful ia the preparatioa of modified purine and pyrimidine mononucleotides from their corresponding nucleosides, eg, 6-thioguanosiae [85-31-4] (51) (97). 

Phtha/k anhydride is the most important type of dibasic acid derivative ki alkyd preparation because of its low cost and the excellent overall properties it imparts to the reski. The anhydride stmcture allows a fast esterification to form half-esters at relatively low reaction temperatures without hberatkig water, thereby avoiding the danger of excessive foaming ki the reactor. However, skice the two carboxyl groups of phthaUc anhydride are ki the ortho position to each other on the benzene ring, cycHc stmctures may and do occur ki the reski molecules. 

This procedure is restricted mainly to aminodicarboxyhc acids or diaminocarboxyhc acids. In the case of neutral amino acids, the amino group or carboxyl group must be protected, eg, by A/-acylation, esterification, or amidation. This protection of the racemic amino acid and deprotection of the separated enantiomers add stages to the overall process. Furthermore, this procedure requires a stoichiometric quantity of the resolving agent, which is then difficult to recover efficiendy. Practical examples of resolution by this method have been pubUshed (50,51). 

Esterification, Amidation, and Acid Chloride Formation. Amino acids undergo these common reactions of the carboxyl group with due regard for the need for A/-protection. 

The most important derivatives of the carboxyl group are formed by esterification with monohydric or polyhydric alcohols. Typical alcohols used iaclude methyl alcohol, ethylene glycol, glycerol, and pentaerythritol. These rosia esters have a wide range of softening poiats and compatibiUties. 

Generally, the carboxyl group is not readily reduced. Lithium aluminum hydride is one of the few reagents that can reduce these organic acids to alcohols. The scheme involves the formation of an alkoxide, which is hydroly2ed to the alcohol. Commercially, the alternative to direct reduction involves esterification of the acid followed by the reduction of the ester. 

Chemically Modified Waxes. Hydrocarbon waxes of the microcrystaHine, polyethylene, and polymethylene classes are chemically modified to meet specific market needs. In the vast majority of cases, the first step is air oxidation of the wax with or without catalysts (11). The product has an acid number usuaHy no higher than 30 and a saponification number usuaHy no lower than 25. An alternative step is the reaction of the wax with a polycarboxyHc acid, eg, maleic, at high temperature (12). Through its carboxyl groups, the oxidised wax can be further modified in such reactions as saponification or esterification. Oxidised wax is easily emulsified in water through the use of surfactants or simple soaps, and is widely used in many coating and poHsh appHcations. 

Pectins are subdivided according to their degree of esterification (DE), a designation of the percent of carboxyl groups esterified with methanol. Pectins with DE >50% are high methoxyl pectins (HM pectins) [65546-99-8]-, those with DE <50% are low methoxyl pectins (LM pectins) [9049-34-7]. 

Reactions of the carboxyl group include salt and acid chloride formation, esterification, pyrolysis, reduction, and amide, nitrile, and amine formation. Salt formation occurs when the carboxyUc acid reacts with an alkaline substance (22)... 

Ring closure resulting from attack of a heteroatom on a carboxyl group or its equivalent is merely a case of intramolecular esterification or amide formation. The y-butyrolactones or pyrrolidones obtained from such reactions are usually regarded as the province of aliphatic chemistry, so only a few examples are offered by way of illustration in Scheme 15. 

The chemical inertness of the three-membered ring permitted many conversions of functional groups in diazirines. Esterifications, cleavage of esters and acetals, synthesis of acid chlorides, oxidation of hydroxy groups to carboxyl groups as well as Hofmann alkenation all left the three-membered ring intact (79AHC(24)63). 

See also E. Haslam, Recent Developments in Methods for the Esterification and Protection of the Carboxyl Group, Tetrahedron, 36, 2409-2433 (1980) E. Haslam, Activation and Protection of the Carboxyl Group, Chem. Ind. (London), 610-617 (1979) E. Haslam, Protection of Carboxyl Groups, in Protective Groups in Organic Chemistry, J. F. W. McOmie, Ed., Plenum Press, New York and London, 1973, pp. 183-215. 

The SEM ester was used to protect a carboxyl group where DCC-mediated esterification caused destruction of the substrate. It was formed from the acid and SEM chloride (THF, 0°, 80% yield) and was removed solvolytically. The ease of removal in this case was attributed to anchimeric assistance by the phosphate group. Normally SEM groups are cleaved by treatment with fluoride ion. Note that in this case the SEM group is removed considerably faster than the phenyl groups from the phosphate. ... 

The presenee of free hydroxy and carboxyl groups in lac resin makes it very reactive, in particular to esterification involving either type of group. Of particular interest is the inter-esterification that occurs at elevated temperatures (>70°C) and... 

Esterification. The esterification of rosin provides important commercial products for the adhesive industry. Rosin esters are formed by the reaction of rosins with alcohols at elevated temperatures. Because the carboxyl group of the resin acids is hindered by attachment to a tertiary carbon, esterification with an alcohol can only be accomplished at elevated temperatures. This hindrance is in turn responsible for the high resistance of the resin acid ester linkage to cleavage by water, acid and alkali. 

Treatment of a- or P hydroxyacids with sulfur tetrafluoride leads to conver Sion of the carboxylic group into the tiifluoromethyl group, but the hydroxyl group undergoes either fluorination, fluorosulfination, esterification, or dehydration to form esters, ethers, or alkenes The ratio of the products depends on P substitution [209, 210] (equations 103 and 104)... 

In order to enhance the oral bioavailability of oximonam (104), a prodrug has been made by esterification of the carboxyl group with the t-butyl ester of hydroxyacetic acid (105). The product is prodrug gloximonam (106) [31], Gloximonam is efficiently converted to oximonam in the body by metabolic processes. 

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