Manufacturing process acetates

Acetylation of acetaldehyde to ethyUdene diacetate [542-10-9], a precursor of vinyl acetate, has long been known (7), but the condensation of formaldehyde [50-00-0] and acetic acid vapors to furnish acryflc acid [97-10-7] is more recent (30). These reactions consume relatively more energy than other routes for manufacturing vinyl acetate or acryflc acid, and thus are not likely to be further developed. Vapor-phase methanol—methyl acetate oxidation using simultaneous condensation to yield methyl acrylate is still being developed (28). A vanadium—titania phosphate catalyst is employed in that process. 

Anhydrous Acetic Acid. In the manufacture of acetic acid by direct oxidation of a petroleum-based feedstock, solvent extraction has been used to separate acetic acid [64-19-7] from the aqueous reaction Hquor containing significant quantities of formic and propionic acids. Isoamyl acetate [123-92-2] is used as solvent to extract nearly all the acetic acid, and some water, from the aqueous feed (236). The extract is then dehydrated by azeotropic distillation using isoamyl acetate as water entrainer (see DISTILLATION, AZEOTROPIC AND EXTRACTIVE). It is claimed that the extraction step in this process affords substantial savings in plant capital investment and operating cost (see Acetic acid and derivatives). A detailed description of various extraction processes is available (237). 

Vinyl ethers are prepared in a solution process at 150—200°C with alkaH metal hydroxide catalysts (32—34), although a vapor-phase process has been reported (35). A wide variety of vinyl ethers are produced commercially. Vinyl acetate has been manufactured from acetic acid and acetylene in a vapor-phase process using zinc acetate catalyst (36,37), but ethylene is the currently preferred raw material. Vinyl derivatives of amines, amides, and mercaptans can be made similarly. A/-Vinyl-2-pyrroHdinone is a commercially important monomer prepared by vinylation of 2-pyrroHdinone using a base catalyst. 

Acetic Acid. Methanol carbonylation has become the process of choice for production of this staple of the organic chemical industry, which is used in the manufacture of acetate fibers, acetic anhydride [108-24-7] and terephthaUc acid, and for fermentation (see Acetic acid and derivatives). 

Plastics and Other Synthetic Products. Sulfur is used in the production of a wide range of synthetics, including cellulose acetate, cellophane, rayon, viscose products, fibers, and textiles. These uses may account for 2% of sulfur demand in developed countries. Sulfur intermediates for these manufacturing processes are equally divided between carbon disulfide and sulfuric acid. 

Poly(vinyl alcohol) can be derived from the hydrolysis of a variety of poly(vinyl esters), such as poly(vinyl acetate), poly(vinyl formate), and poly(vinyl ben2oate), and of poly(vinyl ethers). However, all commercially produced poly(vinyl alcohol) is manufactured by the hydrolysis of poly(vinyl acetate). The manufacturing process can be viewed as one segment that deals with the polymeri2ation of vinyl acetate and another that handles the hydrolysis of poly(vinyl acetate) to poly(vinyl alcohol). 

Bendazac Chloride (1 -benzyl-1 H-indazol-3-yl)oxy] acetic acid chloride Manufacturing Process... 

Residual N-bromosuccinimide from the manufacturing process may be identified and/or quantified by making use of its oxidation potential by titration of liberated iodine after addition of potassium iodide in acetic acid (25). 

It is now nearly 40 years since the introduction by Monsanto of a rhodium-catalysed process for the production of acetic acid by carbonylation of methanol [1]. The so-called Monsanto process became the dominant method for manufacture of acetic acid and is one of the most successful examples of the commercial application of homogeneous catalysis. The rhodium-catalysed process was preceded by a cobalt-based system developed by BASF [2,3], which suffered from significantly lower selectivity and the necessity for much harsher conditions of temperature and pressure. Although the rhodium-catalysed system has much better activity and selectivity, the search has continued in recent years for new catalysts which improve efficiency even further. The strategies employed have involved either modifications to the rhodium-based system or the replacement of rhodium by another metal, in particular iridium. This chapter will describe some of the important recent advances in both rhodium- and iridium-catalysed methanol carbonylation. Particular emphasis will be placed on the fundamental organometallic chemistry and mechanistic understanding of these processes. 

Tetrachloroethane (TeCA) was the first chlorinated hydrocarbon solvent produced in large quantities before World War I [371]. It was used as a solvent for cellulose acetate, fat, waxes, greases, rubber, and sulfur. In a few cases, TeCA is used as a carrier or reaction solvent in manufacturing processes for other chemicals and as an analytical reagent for polymers [371]. TeCA was largely replaced by less toxic solvents after 1945. TeCA release in the United States varied from 44,000 pounds in 1988 to 66,000 pounds in 1991 [372]. 

The first successful static firing of plastisol propellant took place late in 1950 as part of a broad program conducted by Atlantic Research Corp. to investigate and evaluate plastisol propellants and methods for their manufacture (16). Major attention was directed to poly (vinyl chloride), cellulose acetate, and nitrocellulose, although other polymers were tested for their suitability (17). Patent applications were filed for plastisol propellant compositions and manufacturing processes, based on poly(vinyl chloride) (PVC) (19) and on nitrocellulose (18). The commercial availability of dispersion grade PVC enabled work with this resin to advance rapidly. The balance of this paper is devoted to a discussion of PVC plastisol propellants and their manufacture. 

Acetic Acid. Although at the time of this writing Monsanto s Rh-catalyzed methanol carbonylation (see Section 7.2.4) is the predominant process in the manufacture of acetic acid, providing about 95% of the world s production, some acetic acid is still produced by the air oxidation of n-butane or light naphtha. n-Butane is used mainly in the United States, whereas light naphtha fractions from petroleum refining are the main feedstock in Europe. 

In the second manufacturing process for copper phthalocyanine, phthalonitrile, copper(II) acetate and ammonium acetate are heated in the presence of a base, with or without a solvent such as pyridine. The mechanism of this has been less studied than that of the phthalic anhydride/urea reaction. It is, however, significant that metal-free phthalocyanine is manufactured by heating phthalonitrile with the sodium derivative of a high-boiling alcohol in an excess of the alcohol. This reaction is believed148 to occur by the route outlined in Scheme 7, which is supported by the isolation of compounds of types (223) and (224). If this or a related mechanism operates in the... 

Industries may emit various pollutants relating to their manufacturing processes— acids (sulfuric, acetic, nitric, and phosphoric), solvents and resins, gases (chlorine and ammonia), and metals (copper, lead, and zinc). 

Related compound (B) has the systematic name methyl-( )-(o-chloro-phenyl)-4,5-dihydrothieno[2,3-c]pyridine-6-(7H)-acetate, hydrogen sulfate salt [2], and is a racemic residue formed during the manufacturing process. This compound may appear as a racemic mixture in samples of bulk drug substance as impurities (la) and (lb) [6, 7]. 

In spite of their record of producing no detectable harm to humans, the phenoxy herbicides 2,4-dichlorophenoxy acetic acid (2,4-D) and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T) have acquired a less than desirable reputation. This reputation has been the result of their association with low levels of impurities. They have commonly been used as a mixture, which contains trace amounts of highly toxic 2,3,7,8-tetrachlorodibenzo-jj-dioxin, a minor product in the manufacturing of 2,4,5-T. In early production of 2,4,5-T a low level of dioxin was retained. Today s manufacturing process produces 2,4,5-T with no more than 0.1 ppm of the 2,3,7,8 tetrachlorodibenzo-]D-dioxin. This association with toxic dioxin and confusion of the public and the media regarding these issues have led to public distrust in the safety of using phenoxys and to the need to establish clearly the extent of human exposure to these compounds as well as the resulting effects of this exposure. 

Bendazac chloride ([(l-benzyl-lH-indazol-3-yl)oxy]acetic acid chloride) Manufacturing Process... 

Manufacturing Process Chenodeoxycholanic acid was dissolved in acetic acid and to this solution ... 

A Wacker catalyst is used in this process, similar to that for the manufacture of acetic acid. Since the acetic acid can also be made from ethylene, the basic raw material is solely ethylene. A liquid-phase process has been replaced by a vapor-phase reaction run at 70 to 140 psi and 175 to 200°C. Catalysts may be (1) carbon-palladium chloride-cupric chloride (C-PdCl2-CuCl2), (2) palladium chloride-alumina (PdCl2-Al203), or (3) palladium-carbon-potassium acetate (Pd-C-KOAc). The product is distilled into water, acetaldehyde that can be recycled to acetic acid, and the pure colorless liquid, which is collected at 72°C. The yield is 95percent. 

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