Esters of, with organic acids

Hydrolysis.—These esters of the organic acids react as those of the inorganic acids. The most important reaction is their decomposition with water by which the alcohol and the acid are reformed. As the reaction involves simply the taking up of the elements of water it is termed an action of hydrolysis. 

In contrast to anionic ROP, cationic ROP represents another class of polymerization where electrophilic reagents are used as initiators. A general mechanism for cationic ROP is described in Scheme 2.5, where the initiators with an electrophilic nature most often involve Br0nsted acid, Lewis acid and alkyl esters of strong organic acids such as sulfonic acid. 

Cellulose esters are commonly derived from natural cellulose by reaction with organic acids, anhydrides, or acid chlorides. Cellulose esters of almost any organic acid can be prepared, but because of practical limitations esters of acids containing more than four carbon atoms have not achieved commercial significance. 

Unsaturated Hydrocarbons. Olefins from ethylene through octene have been converted into esters via acid-catalyzed nucleophilic addition. With ethylene and propjiene, only a single ester is produced using acetic acid, ethyl acetate and isopropyl acetate, respectively. With the butylenes, two products are possible j -butyl esters result from 1- and 2-butylenes, whereas tert-huty esters are obtained from isobutjiene. The C5 olefins give rise to three j iC-amyl esters and one /-amyl ester. As the carbon chain is lengthened, the reactivity of the olefin with organic acids increases. 

A s/cr.s possess a fruity smell and usually distil without decomposition. Boil with refltiK for 5 minutes on the water-btith a few c.c. of the licpiid with 3 to 4 volumes of a ten pei cent, solution of ctLListic potash in methyl alcohol and pour into water. Notice if the liquid dissolves and has lost the odour of the ester. An ester will be completely hydrolysed, and if the alcohol is soluble in water a clear solution will be obtained. If the alcohol is vol.atile and the solution neiitialised w ith sulphuric acid. and evaporated on the water-bath, the alkali salt of the organic acid mixed with pottissium sulphate will be left and the acid may be investigated as desciibed under 1. If it is required to. ascertain the nature of the alcohol in the ester, hydrolysis must fig effected with a strong aqueous solution of caustic potash... 

Figure 15.8 Multidimensional GC-MS separation of urinary acids after derivatization with methyl chloroformate (a) pre-column cliromatogram after splitless injection (h) Main-column selected ion monitoring cliromatogram (mass 84) of pyroglutamic acid methyl ester. Adapted from Journal of Chromatography, B 714, M. Heil et ai, Enantioselective multidimensional gas chromatography-mass spectrometry in the analysis of urinary organic acids , pp. 119-126, copyright 1998, with permission from Elsevier Science.

A reaction which has proved to be of much use in synthetic organic chemistry is the formation of the ortho and/or the para isomers of a hydroxyketone (CVI and CVTI) by treatment of a phenolic ester (CV) with an acid catalyst, viz. 

The solubility of several salts of alkyl esters of a-sulfopalmitic acid and a-sulfostearic acid was measured by Stirton et al. [30]. The aqueous solubility of the a-sulfopalmitates is better than the solubility of the a-sulfostearates and it also increases with increasing molecular weight of the alcohol. The same dependency is found in organic solvents, such as chloroform ethanol, petroleum ether diethyl ether, and mineral oil. They also showed that esters of secondary and branched chain alcohols are more soluble than esters of normal primary alcohols. 

Phosphonous acid diesters undergo the Arbusov reaction with a wide variety of organic halides, giving esters of secondary phosphinic acids, as is demonstrated in Eq. (88) ... 

An alternative to the extraction of intact PHA polymer is the isolation of PHA monomers, oligomers, or various derivatives such as esters [74]. PH As are composed of stereo-chemically pure P-3-hydroxyacids, and therefore can be used as a source of optically pure organic substrates for the chemical and pharmaceutical industry [79]. In this protocol, the defatted cake containing PHA polymer would be chemically treated to obtain the PHA derivatives. For example, transesterification of the meal with methanol would give rise to methyl esters of 3-hydroxyalkanoic acids. The PHA derivatives would then be separated from the meal with appropriate solvents. One potential disadvantage of this method is the potential alteration of the quality of the residual meal if the harsh chemical treatments required for the production of PHA derivatives lead to protein or amino acid breakdown. 

Quite often, we find nonsystematic nomenclature used in the literature dealing with organophosphorus compounds. This results in unnecessary confusion, as systematic nomenclature is easy to use and understand. Nomenclature based on the oxidation state of the phosphorus center eliminates the confusion and helps to promote understanding of the chemistry as well as to facilitate communication. Table 1.1 shows structures for tricoordinate and tetracoordinate phosphorus compounds related to oxyacids with their English general names. Also noted are the names for simple esters of the parent acids. They are organized based on oxidation state and the number of bonds of the carbon-phosphorus type. 

Activated esters of A-alkoxycarbonylamino acids are prepared by two approaches, activation of the acid followed by reaction with the hydroxy compound, and trans-esterification. Most of the products are stable enough to be purified by washing a solution of the ester in an organic solvent with aqueous solutions. A few that are not crystalline are purified by passage through a column of silica. The commonly used method for their preparation is addition of dicyclohexylcarbodiimide to a cold mixture of the reactants in dimethylformamide or ethyl acetate. The first Boc-amino acid nitrophenyl esters were obtained using pyridine as solvent. Pyridine generates the nitrophenoxide ion that is more reactive. For one type of ester, 2-hydroxypyridino... 

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