Ester contamination

Benzylpenicillin thiomethyl ester (contaminated with some benzylpenicillin) 0.94 ... 

Hasson, D., Limoni-Relis, B., Semiat, R., and Tob, Ph. (1996). Fouling of RO membranes by phtha-late ester contamination. Desalination 105, 13. 

Hie common acrylic ester monomers are combustible liquids. Commercially, acrylic monomers are shipped with DOT red labels in bulk quantities, tank cars, or tank tmcks. Mild steel is the usual material of choice for the constmction of bulk storage facilities for acrylic monomers. Moisture must be excluded to avoid msting of the tanks and contamination of the monomers. Copper or copper alloys must not be allowed to contact acrylic monomers intended for use in polymerization because copper is an inhibitor (67). 

Both the hquid and cured 2-cyanoacryhc esters support combustion. These adhesives should not be used near sparks, heat, or open flame, or ia areas of acute fire ha2ard. Highly exothermic polymerization can occur from direct addition of catalytic substances such as water, alcohols, and bases such as amines, ammonia, or caustics, or from contamination with any of the available surface activator solutions. 

Hydrogen Chloride as By-Product from Chemical Processes. Over 90% of the hydrogen chloride produced in the United States is a by-product from various chemical processes. The cmde HCl generated in these processes is generally contaminated with impurities such as unreacted chlorine, organics, chlorinated organics, and entrained catalyst particles. A wide variety of techniques are employed to treat these HCl streams to obtain either anhydrous HCl or hydrochloric acid. Some of the processes in which HCl is produced as a by-product are the manufacture of chlorofluorohydrocarbons, manufacture of aUphatic and aromatic hydrocarbons, production of high surface area siUca (qv), and the manufacture of phosphoric acid [7664-38-2] and esters of phosphoric acid (see Phosphoric acid and phosphates). 

Three general methods exist for the resolution of enantiomers by Hquid chromatography (qv) (47,48). Conversion of the enantiomers to diastereomers and subsequent column chromatography on an achiral stationary phase with an achiral eluant represents a classical method of resolution (49). Diastereomeric derivatization is problematic in that conversion back to the desired enantiomers can result in partial racemization. For example, (lR,23, 5R)-menthol (R)-mandelate (31) is readily separated from its diastereomer but ester hydrolysis under numerous reaction conditions produces (R)-(-)-mandehc acid (32) which is contaminated with (3)-(+)-mandehc acid (33). 

Other by-products include acetone, carbonaceous material, and polymers of propylene. Minor contaminants arise from impurities in the feed. Ethylene and butylenes can form traces of ethyl alcohol and 2-butanol. Small amounts of / -propyl alcohol carried through into the refined isopropyl alcohol can originate from cyclopropane [75-19-4] in the propylene feed. Acetone, an oxidation product, also forms from thermal decomposition of the intermediate sulfate esters, eg. 

Expect some product contamination if feed components can react with water, eg, ester will be partially hydrolyzed to acid and alcohol fate of reaction product species depends on above rules, eg, methanol from methyl ester hydrolysis probably not stripped out of bottoms stream. 

Polyunsaturated fatty acids in vegetable oils, particularly finolenic esters in soybean oil, are especially sensitive to oxidation. Even a slight degree of oxidation, commonly referred to as flavor reversion, results in undesirable flavors, eg, beany, grassy, painty, or fishy. Oxidation is controlled by the exclusion of metal contaminants, eg, iron and copper addition of metal inactivators such as citric acid minimum exposure to air, protection from light, and selective hydrogenation to decrease the finolenate content to ca 3% (74). Careful quality control is essential for the production of acceptable edible soybean oil products (75). 

Anhydrous sulfonic acids, particularly linear alkylben2enesulfonic acids, are typically stored ia stainless steel containers, preferably type 304 or 316 stainless steel. Use of other metals, such as mild steel, contaminates the acid with iron (qv), causiag a darkening of the acid over time (27). The materials are usually viscous oils which may be stored and handled at 30—35°C for up to two months (27). AH other detergent-grade sulfonic acids, eg, alcohol sulfates, alcohol ether sulfates, alpha-olefin sulfonates, and alpha-sulfomethyl esters, are not stored owiag to iastabiUty. These are neutrali2ed to the desired salt. 

The use of a catalytic quantity of alkah equivalent to only a small fraction of the acetate has the advantage that contamination of the poly(vinyl alcohol) with salts, which are difficult to remove, is minimized. A variant of the process is the use of a mixture of alcohol with the acetate ester produced by the alcoholysis as the alcoholyzing agent. This provides a means of controlling the completeness of removal of the acetate groups from the poly(vinyl acetate) (111). 

In a number of cases the intermediate oxime has been isolated in the reaction of hydroxylamine and /3-keto esters. The reaction of ethyl acetoacetate with hydroxylamine generated an oxime which cyclized on base treatment (Scheme 144) (70MI41600). Likewise, treatment of an analogous amide with hydroxylamine generated a ring opened material which cyclized on treatment with HCl (Scheme 144) (67T831). The presence of a minor contaminant in the standard reaction of ethyl acetoacetate with hydroxylamine was discovered and identified as an isomeric isoxazolin-3-one. The mechanism of product formation has been discussed (70BSF2685). 

Solid esters are easily crystallisable materials. It is important to note that esters of alcohols must be recrystallised either from non-hydroxylic solvents (e.g. toluene) or from the alcohol from which the ester is derived. Thus methyl esters should be crystallised from methanol or methanol/toluene, but not from ethanol, n-butanol or other alcohols, in order to avoid alcohol exchange and contamination of the ester with a second ester. Useful solvents for crystallisation are the corresponding alcohols or aqueous alcohols, toluene, toluene/petroleum ether, and chloroform (ethanol-free)/toluene. Esters of carboxylic acid derived from phenols... 

Medium reactivity contaminants alcohols, ketones, organic acids, esters, alkyl-substituted aromatics, nitro-substituted aromatics, carbohydrates. 

Kunlze finds that the precipitate of silver sulphide, which is formed hy both melhods under Ihc same conditions, is always contaminated wilh more or less silver salt of allyl-ihiocarbamiuic acid ester. 

Pyrethrolone and cinerolone make up the keto alcohol moiety of the pyrethrins. Both of these keto alcohols have one asymmetric carbon at the 4-position and a double bond in the side chain which is capable of cis-trans isomerism in the 2-position. It is possible, therefore, to have four stereoisomers for each keto alcohol. Katsuda et al. (22) show that only the ( + ) form occurs in the natural esters. Elliott (8) has shown recently, by a new procedure developed to obtain pure ( + ) pyrethrolone, that the hitherto unidentified prye-throlone C is in reality pyrethrolone contaminated with thermally isomerized material. (+) Pyrethrolone forms a crystalline monohydrate from which the pure alcohol is obtained. The natural configurations of the keto alcohols in the esters are insecticidally more active, as is the case with the acid moiety. 

Di- and mono-esters of phthalic acid, an ortho-dicarboxylic acid derivative of benzene. These compounds are widely used as industrial plasticizers to coat polyvinylchloride surfaces of plastics used in food packaging and medical devices (iv drip bags, blood storage bags, etc.) and are common environmental contaminants. Several phthalate mono-esters are peroxisome proliferator chemicals and can activate the peroxisome proliferator-activated receptor PPAR. 

Occasionally the product is contaminated with an impurity (1-2%), which appears as tiny red needles. This material has been tentatively identified as diethyl azobenzene-4,4 -dicarboxylate [Benzoic acid, 4,4 -azobis-, diethyl ester],... 

The method used is described by Drysdale, Stevenson, and Sharkey.4 The methyl ester of butadienoic acid has not been described previously, but the free acid contaminated by 2-bu-tynoic acid has been prepared by Wotiz, Matthews, and Lieb 5 by carbonation of propargylmagncsium bromide. Ethyl butadienoate has been prepared by Eglinton, Jones, Mansfield, and Whiting by alkali-catalyzed isomerization of ethyl 3-butynoate prepared from 3-butynol by chromic acid oxidation and esterification. 

Many impurities are present in commercial caprolactam which pass into the liquid wastes from PCA manufacture from which caprolactam monomer may be recovered. Also, the products of die thermal degradation of PCA, dyes, lubricants, and other PCA fillers may be contained in the regenerated CL. Identification of die contaminants by IR spectroscopy has led to the detection of lower carboxylic acids, secondary amines, ketones, and esters. Aldehydes and hydroperoxides have been identified by polarography and thin-layer chromatography. 

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