Hydrolysis, acetal ester

One approach called enzymatic resolution, involves treating a racemic mixture with an enzyme that catalyzes the reaction of only one of the enantiomers Some of the most commonly used ones are lipases and esterases enzymes that catalyze the hydrol ysis of esters In a typical procedure one enantiomer of the acetate ester of a racemic alcohol undergoes hydrolysis and the other is left unchanged when hydrolyzed m the presence of an esterase from hog liver... 

Acetal resins are generally stable in mildly alkaline environments. However, bases can catalyse hydrolysis of ester end groups, resulting in less thermally stable polymer. 

Esters of cinnamic acid are used more extensively than the acid itself, and can be converted to the acid by standard hydrolysis protocols. The Claisen condensation between benzaldehyde and the appropriate acetate ester provides a direct, high yield route to the simple esters. 

Optically Active Alcohols and Esters. In addition to the hydrolysis of esters formed by simple alcohols described above, Hpases and esterases also catalyze the hydrolysis of a wide range of esters based on more complex and synthetically useful cycHc and acycHc alcohols (Table 5). Although the hydrolysis of acetates often gives the desirable resolution, to achieve maximum selectivity and reaction efficiency, comparison of various esters is recommended. 

The adamantoate ester is formed selectively from a primary hydroxyl group (e.g., from the 5 -OH in a ribonucleoside) by reaction with adamantoyl chloride, Pyr (20°, 16 h). It is cleaved by alkaline hydrolysis (0.25 N NaOH, 20 min), but is stable to milder alkaline hydrolysis (e.g., NH3, MeOH), conditions that cleave an acetate ester. ... 

Many functional groups are stable to alkaline hydrogen peroxide. Acetate esters are usually hydrolyzed under the reaction conditions although methods have been developed to prevent hydrolysis.For the preparation of the 4,5-oxiranes of desoxycorticosterone, hydrocortisone, and cortisone, the alkali-sensitive ketol side chains must be protected with a base-resistant group, e.g., the tetrahydropyranyl ether or the ethylene ketal derivative. Sodium carbonate has been used successfully as a base with unprotected ketol side chains, but it should be noted that some ketols are sensitive to sodium carbonate in the absence of hydrogen peroxide. The spiroketal side chain of the sapogenins is stable to the basic reaction conditions. 

Hydrolysis of the acetate ester with alkali, e.g., sodium methoxide in methanol, affords the free alcohol, 16/3-methyl-1,4,9( 11 )-pregnatriene-17o, 21-diol-3,20-dione. To a suspension of 3 grams of 16/3-methyl-1,4,9(11)-pregnatriene-17o,21-diol-3,20-dione-21-acetate in 40 ml of acetone is added at 0°C with stirring 2 grams of N-chlorosuccinimide and then 7 ml of a perchloric acid solution prepared by dissolving 0.548 ml of 70% perchloric acid in 33 ml of water. The resulting reaction mixture is stirred at 0°C for about 4 hours 45 minutes. 

Digestion (Section 29.1) The first stage of catabolism, in which food is broken down by hydrolysis of ester, glycoside (acetal), and peptide (amide) bonds to yield fatty acids, simple sugars, and amino acids. 

Parallel reactions. In water 2.4-ditrophenyl acetate (= ester) undergoes parallel hydrolysis and amination reactions (am = triethylenediamine = R NH ) according to the scheme shown. The rate constants are hyd = 2.10 X HP5 s 1 and k.m = 1.61 x... 

Esterases form a wide family of enzymes that catalyze the hydrolysis of ester bonds. They are ubiquitously expressed in all tissues including the intestine, and are found in both microsomal and cytosolic fractions. Prueksaritonont et al. [6] have studied the metabolism of both p-nitrophenol acetate and acetylsalicylic acid by esterases from human intestinal microsomal and cytosolic systems, and the activity values were 2.76 pmol min-1 mg-1 and 0.96 nmol min-1 mg-1, respectively. Thus, the activity for the hydrolysis of p-nitrophenol acetate in human intestine approaches that in the liver. 

The hydrolysis of esters by the nickel derivative (271) provided an early example of the use of a metal-capped cyclodextrin as a catalyst (shown here as its p-nitrophenyl acetate inclusion complex) (Breslow Overman, 1970 Breslow, 1971). The synthesis of this host involves the following steps (i) covalent binding of the pyridine dicarboxylic acid moiety to cyclodextrin, (ii) coordination of Ni(n) to this species, and (iii)... 

Marans and Preckel " synthesized both the mononitrate (95) and the dinitrate (92) esters of metriol by using a similar strategy to that used for pentaerythritol trinitrate. Thus, nitration of both the mono- (90) and the di- (93) acetate esters of metriol, followed by selective hydrolysis of the acetate groups, yields (92) and (95) respectively the latter could be useful as a monomer for the synthesis of energetic polyurethane polymers. 

This enzyme [EC 3.1.1.7], also known as true cholinesterase, choline esterase I, and cholinesterase, catalyzes the hydrolysis of acetylcholine to produce choline and acetate. The enzyme will also act on a number of acetate esters as well as catalyze some transacetylations. 

As in the case of hydrocortisone acetate, where hydrocortisone might be expeeted to occur as a result of hydrolysis of the acetate ester, tests for the presenee of known impurities are based on the known manufacturing sequence or on likely degradation pathways. For example, the tests carried out on clotrimazole are based on the last step in its manufacture as shown in Figure 13.8. Unreacted imidazole is an obvious impurity and chlorotritanol would be readily formed from unreacted chlorotrityl bromide by hydrolysis, which would occur when the clotrimazole is extracted from the reaction mixture. 

Another strategy for the preparation of the core structure of palmarumycin or preussomerin commenced with acetate esters, such as trichloroacetate 221. Hydrolysis of the ester group of compound 221 with LiOH gave the anion 222, which cyclizes to bridged bis-l,3-dioxane 223 (Scheme 106) <19990L3>. It was calculated that bis-1,3-dioxane 223 and the protonated form of anion 222 are in thermodynamic equilibrium with a preference for 223 of almost 8 kcalmoP <2002JOC2735>. 

By the hydrolysis of esters 81a-c, the corresponding acids 83a-c were formed. The 2-[3-(trifluoromethyl)phenyl]-4//-furo[3,2-7]pyrrole-5-carboxylic acid 83a was decarboxylated in acetic anhydride to 4-acetyl-2-[3-(trifluoromethyl)-phenyl]furo[3,2-7]pyrrole 84 (see 10.01.05.1.2, Scheme 7). 

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