Esters and saponification

Resolution of alcohols can be achieved following derivatization with phthalic anhydride. Racemic l-undecyn-3-ol was converted into a phthalic monoester derivative and resolved with (R)-(+)-NEA (eq 2). Liberation of the resolved phthalic ester and saponification yielded (R)-(+)-alcohol in 92% optical purity (eq 2). Similarly, the (S)-(-) alcohol is obtained upon resolution with (S)-(-)-NEA (eq 2). 

Thus, NaOH at these low concentrations is involved in at least two reactions with hardwoods Saponification of uronic esters and saponification of acetates. If these are the only reactions occurring, then the NaOH has the following fates ... 

Acid, ester, and saponification values are determined exactly as described under fats and oils. Instead of expressing the result as saponification value or number, the percentage of ester, calculated in the form of the most important ester present, may be obtained by multiplying the number of c.c. of N/1 alkali absorbed in the saponi-fiication by the molecular weight of the ester. Thus, to find the percentage as linalyl acetate, the number of c.c. absorbed would be multiplied by 0 196 and by 100, and divided by the weight of oil taken. 

Starch has been converted into cold-soluble and cold-swelling derivatives by reaction with ethyl cyanide or by graft polymerization with acrylic esters and saponification. ... 

The introduction of a side chain at C13 was studied by Wilds [186, 188] (Scheme 6). Alkylation of the ketone (53) with bromoac.etic ester and saponification led to the acid (55). The latter was converted into the methyl ketone (58) by condensing its chloride with sodiomalonic ester, hydrolysis. 

It is frequently advisable in the routine examination of an ester, and before any derivatives are considered, to determine the saponification equivalent of the ester. In order to ensure that complete hydrolysis takes place in a comparatively short time, the quantitative saponi fication is conducted with a standardised alcoholic solution of caustic alkali—preferably potassium hydroxide since the potassium salts of organic acids are usuaUy more soluble than the sodium salts. A knowledge of the b.p. and the saponification equivalent of the unknown ester would provide the basis for a fairly accurate approximation of the size of the ester molecule. It must, however, be borne in mind that certain structures may effect the values of the equivalent thus aliphatic halo genated esters may consume alkali because of hydrolysis of part of the halogen during the determination, nitro esters may be reduced by the alkaline hydrolysis medium, etc. 

When the compound for identification fails to respond to test 4 (aldehyde or ketone), the next class reactions to apply are the hydroxatnic acid teat and saponification, i.e., hydrolysis in alkaline solution. These are the class reactions for esters and anhydrides the rarely-encountered lactones react similarly. 

One of the most sensitive tests of the dependence of chemical reactivity on the size of the reacting molecules is the comparison of the rates of reaction for compounds which are members of a homologous series with different chain lengths. Studies by Flory and others on the rates of esterification and saponification of esters were the first investigations conducted to clarify the dependence of reactivity on molecular size. The rate constants for these reactions are observed to converge quite rapidly to a constant value which is independent of molecular size, after an initial dependence on molecular size for small molecules. The effect is reminiscent of the discussion on the uniqueness of end groups in connection with Example 1.1. In the esterification of carboxylic acids, for example, the rate constants are different for acetic, propionic, and butyric acids, but constant for carboxyUc acids with 4-18 carbon atoms. This observation on nonpolymeric compounds has been generalized to apply to polymerization reactions as well. The latter are subject to several complications which are not involved in the study of simple model compounds, but when these complications are properly considered, the independence of reactivity on molecular size has been repeatedly verified. 

Rosin is compatible with many materials because of its polar functionaUty, cycloaUphatic stmcture, and its low molecular weight. It has an acid number of ca 165 and a saponification number of ca 170. It is soluble in aUphatic, aromatic, and chlorinated hydrocarbons, as well as esters and ethers. Because of its solubiUty and compatibiUty characteristics, it is useful for modifying the properties of many polymers. 

A terpene yielding isofenchyl alcohol on hydration, which Wallach considers to be one of the fenchenes, was artificially prepared by converting nopinone into a hydroxy ester by means of bromoacetic ester and zinc-dust. The hydroxy ester is dehydrated by potassium bisulphate, and so yields an unsaturated ester, which on saponification yields an acid from which the terpene results by distillation. This fenchene has the following characters —... 

The enolic esters, on saponification, regenerate the aldehydes. With sodium and alcohol, the saturated alcohol corresponding to the aldehyde is obtained. 

Terpinyl acetate in the absence of esters of high molecular weight, or ethyl esters of the fatty acids of coconut oil, is indicated by a difference to be observed in the apparent ester value by different times of saponification. This ester is far more resistant to the action of caustic alkali than is linalyl acetate, and requires two hours at least for complete saponification. Hence, if the oil shows a difference in the saponification value in thirty minutes and in two hours, which amounts to more than from 1 to 2, terpinyl acetate is almost certainly present. The following table shows the effect of this partial-saponrfication on the two esters and on adulterated oils —... 

You will note that the oxygen atoms attached to carbons 5 and 12 in 43 reside in proximity to the C-9 ketone carbonyl. Under sufficiently acidic conditions, it is conceivable that removal of the triethylsilyl protecting groups would be attended by a thermodynamically controlled spiroketalization reaction.30 Indeed, after hydro-genolysis of the C-26 benzyl ether in 43, subjection of the organic residue to the action of para-toluenesulfonic acid in a mixture of methylene chloride, ether, and water accomplishes the desired processes outlined above and provides monensin methyl ester. Finally, saponification of the methyl ester with aqueous sodium hydroxide in methanol furnishes the sodium salt of (+)-monensin [(+)-1], Still s elegant synthesis of monensin is now complete.13... 

Although these Boc derivatives underwent methylation with poor selectivity (compared to 3-amino-N-benzoyl butanoates [106] and Z-protected methyl 4-phen-yl-3-aminobutanoate [107]), epimers were succesfully separated by preparative HPLC or by flash chromatography. However, saponification of the methyl ester caused partial epimerization of the a-stereocenter and a two-step (epimerization free) procedure involving titanate-mediated transesterification to the corresponding benzyl esters and hydrogenation was used instead to recover the required Boc-y9 -amino acids in enantiomerically pure form [104, 105]. N-Boc-protected amino acids 19 and 20 for incorporation into water-soluble /9-peptides were pre-... 

Alkaline hydrolysis (saponification) has been used to remove contaminating lipids from fat-rich samples (e.g., pahn oil) and hydrolyze chlorophyll (e.g., green vegetables) and carotenoid esters (e.g., fruits). Xanthophylls, both free and with different degrees of esterification with a mixture of different fatty acids, are typically found in fruits, and saponification allows easier chromatographic separation, identification, and quantification. For this reason, most methods for quantitative carotenoid analysis include a saponification step. 

Chromatographic methods were developed for the systematic determination of five classes of additives in PE for food packaging [170]. In Soxhlet extractions phenolic AOs and acid amides were determined by HPLC and CGC, respectively. Thiodipropionic acid esters were determined by HRGC as higher alcohols obtained after saponification of the extracts with KOH. Glycerol fatty acid esters and stearates were determined... 

The reaction takes place in aqueous solution. Equimolal concentrations of the ester and the phenolate are used. These concentrations are equal to 30 moles/m3. By the time the samples are brought to thermal equilibrium in the reactor and efforts made to obtain data on ester concentrations as a function of time, some saponification has occurred. At this time the concentration of ester remaining is 26.29 moles/m3, and the concentration of phenol present in the reactant mixture is 7.42 moles/m3. The rate expression for the reaction is believed to be of the form... 

The stereoselective total synthesis of (+)-epiquinamide 301 has been achieved starting from the amino acid L-allysine ethylene acetal, which was converted into piperidine 298 by standard protocols. Allylation of 297 via an. V-acyliminium ion gave 298, which underwent RCM to provide 299 and the quinolizidine 300, with the wrong stereochemistry at the C-l stereocenter. This was corrected by mesylation of the alcohol, followed by Sn2 reaction with sodium azide to give 301, which, upon saponification of the methyl ester and decarboxylation through the Barton procedure followed by reduction and N-acylation, gave the desired natural product (Scheme 66) <20050L4005>. 

Treatment of A8(9)-dehydro-D-homoestradiol (39, R = H) (or its 3-methyl ether, R = Me) with Et3SiH/TFA followed by saponification of the trifluoroac-etate ester intermediate leads to D-homoestradiol (40) (or its 3-methyl ether) containing 2-15% D-homoequilenol (41) (or its 3-methyl ether).240 By contrast, reduction and saponification of 3,17-diacetyl-A8(9)-dehydro-D-homoestradiol (39, R = AcO) gives a 60% yield of D-homoestradiol without the presence of any D-homoequilenol (Eq. 87).240... 

Ester saponifaction was a favoured reaction for this type of study, because the hydrophobicity of the acyl moiety could easily be controlled by increasing the length of an n-alkyl group, and saponification of p-nitrophenyl n-alkanoates could be followed with very dilute substrate. Substrate concentration is an important factor, because provided that it is kept low it is reasonable to assume that the micelle structure is relatively unperturbed. 

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