Acidic by-products

Mix intimately in a mortar 100 g. of sodium laevulinate, 250 g. of phosphorus sulphide (1) and 50 g. of clean dry sand. Place the mixture in a flask fitted with a condenser for distillation and a receiver (2). Heat the flask with a free flame until the reaction commences, and then remove the flame. When the reaction subsides, continue the heating until distillation ceases. Wash the distillate with 10 per cent, sodium hydroxide solution to remove acidic by-products and steam distil. Separate the crude 2-methyltliiophene from the steam distillate, dry over anhydrous calcium sulphate, and distil from a little sodium. Collect the pure compound at 113° the yield is 30 g. 

In order to control the concentration of lower dibasic acid by-products in the system, a portion of the mother liquor stream is diverted to a purge treatment process. Following removal of nitric acid by distillation (Fig. 3, K), copper and vanadium catalyst are recovered by ion-exchange treatment (Fig. 

Additional phosphonic acid is derived from by-product streams. In the manufacture of acid chlorides from carboxyUc acids and PCl, phosphonic acid or pyrophosphonic acid is produced, frequentiy with copious quantities of yellow polymeric LOOP. Such mixtures slowly evolve phosphine, particularly on heating, and formerly were a disposal problem. However, purification of this cmde mixture affords commercial phosphonic acid. By-product acid is also derived from the precipitate of calcium salts in the manufacture of phosphinic acid. As a consequence of the treatments of the salt with sulfuric acid, carbonate is Hberated as CO2 and phosphonic acid goes into solution. 

Yields are best in the case of aromatic metallic reagents. Use of aUphatic reagents favors low molecular weight products. Products often are recovered by water addition, followed by separation and distillation of the organic layer. Such procedures inevitably lead to acidic by-products when there is incomplete replacement of the halogens on phosphoms. A modification of the Wurt2 reaction sometimes is used. 

Phosphoric acid [7664-38-2] and its derivatives are effective catalysts for this reaction (60). Reverse alcoholysis and acidolysis can, in principle, also be used to produce polyamides, and the conversion of esters to polyamides through their reaction within diamines, reverse alcoholysis, has been demonstrated (61). In the case of reverse acidolysis, the acid by-product is usually less volatile than the diamine starting material. Thus, this route to the formation of polyamide is not likely to yield a high molecular weight polymer. 

The pelargonic acid by-product is already a useful item of commerce, making the overall process a commercial possibiUty. The 13-carbon polyamides appear to have many of the properties of nylon-11, nylon-12, or nylon-12,12 toughness, moisture resistance, dimensional stabiUty, increased resistance to hydrolysis, moderate melt point, and melt processibiUty. Thus, these nylons could be useful in similar markets, eg, automotive parts, coatings, fibers, or films. Properties for nylon-13,13 are = 56 (7 and = 183 (7 (179). 

Bisamides. Methylenebisamides are prepared by the reaction of the primary fatty amide and formaldehyde in the presence of an acid catalyst. AijAT-Methylenebisoleamide has been made via this route without the use of refluxing solvent (55). Polymethylenebisamides can be made from fatty acid, esters, or acid haUdes with diamines while producing water, alcohol, or mineral acid by-products. Eatty acids and diamines, typically ethylenediamine, have been condensed in the presence of NaBH and NaH2P02 to yield bisamides (56). When stearic acid, ethylenediamine, and methyl acetate react for 6 h at... 

Until the 1970s, the main production countries of sulfamic acid were the United States, several European countries, and Japan. The large amounts of dilute sulfuric acid by-product generated led to the difficult situation of by-product acid disposal. Concomitandy, the start of chemical production in developing Asian countries caused successional sulfamic acid production withdrawal in the 1980s. As of the mid-1990s production countries are Japan, Taiwan, Indonesia, India, and China. The 1995 wodd production capacity was ca 96,000 metric tons. 

Benzyl Chloride. Benzyl chloride is manufactured by high temperature free-radical chlorination of toluene. The yield of benzyl chloride is maximized by use of excess toluene in the feed. More than half of the benzyl chloride produced is converted by butyl benzyl phthalate by reaction with monosodium butyl phthalate. The remainder is hydrolyzed to benzyl alcohol, which is converted to ahphatic esters for use in soaps, perfume, and davors. Benzyl salicylate is used as a sunscreen in lotions and creams. By-product benzal chloride can be converted to benzaldehyde, which is also produced directiy by oxidation of toluene and as a by-product during formation of benzoic acid. By-product ben zotrichl oride is not hydrolyzed to make benzoic acid but is allowed to react with benzoic acid to yield benzoyl chloride. 

The gas distribution system can be composed of a network of perforated pipe, slotted or vented concrete block, or metal grating. When there are no space hmitations, single-level filters are used. In regions where footprint space is hmited, hke Japan, multiple-deck filter beds have become commonplace. If inorganic compounds are being treated, corrosion-resistant materials of construc tion are used due to the acidic by-products of the bioreaction. 

In the production process an acidic by-product, called vianesse, largely consisting of organic and amino acids, is produced at a level of over ten times the amount of ethanol produced. This material has a high COD and BOD, and poses significant problems if it finds its way into the water course. 

The human body generates a steady flow of acidic by-products during its normal metabolic processes. Foremost among these is carbon dioxide, which is a major product of the reactions the body uses to produce energy (see Section 14-). An average person produces from 10 to 20 mol (440 to 880 g) of CO2 every day. Blood carries CO2 from the cells to the lungs to be exhaled. In aqueous solution, dissolved CO2 is in equilibrium with carbonic acid H2 O + CO2 H2 CO3... 

The residue from a large scale atmospheric pressure distillation of trimethyl phosphate exploded violently. This was attributed to rapid decomposition of the ester, catalysed by the acidic degradation products, with evolution of gaseous hydrocarbons. It is recommended that only small batches of alkyl phosphates should be vacuum distilled and in presence of magnesium oxide to neutralise any acid by-products, and to suppress the acid catalysed reaction. 

These agents are readily destroyed by high pH (i.e., basic solutions). Use an aqueous caustic solution (minimum of 10% by weight sodium hydroxide or sodium carbonate) containing 20% alcohol or use undiluted household bleach. However, hydrolysis of GV-series agents produces acidic by-products therefore, a large excess of base will be needed to ensure... 

Hindered nonnucleophilic bases are typically added to sulfoxide glycosylations to buffer the acidic by-products. Classically, the 2,6-di-tert-butylpyridines have been employed for this purpose [86], but the more highly crystalline and easily handled 2,4,6-tri-fert-butylpyrimidine is finding increasing favor in this regard [356]. 

Treatment with alkali removes the various acidic by-products and their salts (acetate, sulfinate, and formate) and also serves to hydrolyze and remove unreacted starting materials. 

For small-scale work the chlorination is also conveniently carried out by N-chlorosuccinimide (Kenner, Todd and Weymouth, J. Chem. Soc. 1952, p. 3575). In this case no acid by-product is obtained. This modification is discussed in Chapter iv. 

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