Bayer acid

The first product formed by the actio of concentrated sulfuric acid on/3-naphthol is 2-naphthol-l-sulfonic acid (page 199). This compound, however, is very unstable and rearranges, even in the cold, in the presence of excess sulfuric acid, to form 2-naphthol-8-sulfonic acid (Bayer acid, croceine acid), and this in turn rearranges, only partially in the cold but completely at higher temperatures, into 2-naphthol-6-sulfonic acid (Schaeffer acid). 

The utility of acid-base titrimetry improved when NaOH was first introduced as a strong base titrant in 1846. In addition, progress in synthesizing organic dyes led to the development of many new indicators. Phenolphthalein was first synthesized by Bayer in 1871 and used as a visual indicator for acid-base titrations in 1877. Other indicators, such as methyl orange, soon followed. Despite the increasing availability of indicators, the absence of a theory of acid-base reactivity made selecting a proper indicator difficult. 

Xanthenes date from 1871 when von Bayer synthesized fluorescein (5) by the condensation of two moles of resorcinol with one mole of phthaUc anhydride in the presence of concentrated sulfuric acid (1). 

Starch is a polysaccharide found in many plant species. Com and potatoes are two common sources of industrial starch. The composition of starch varies somewhat in terms of the amount of branching of the polymer chains (11). Its principal use as a flocculant is in the Bayer process for extracting aluminum from bauxite ore. The digestion of bauxite in sodium hydroxide solution produces a suspension of finely divided iron minerals and siUcates, called red mud, in a highly alkaline Hquor. Starch is used to settle the red mud so that relatively pure alumina can be produced from the clarified Hquor. It has been largely replaced by acryHc acid and acrylamide-based (11,12) polymers, although a number of plants stiH add some starch in addition to synthetic polymers to reduce the level of residual suspended soHds in the Hquor. Starch [9005-25-8] can be modified with various reagents to produce semisynthetic polymers. The principal one of these is cationic starch, which is used as a retention aid in paper production as a component of a dual system (13,14) or a microparticle system (15). 

There are several processes available for the manufacture of cryoHte. The choice is mainly dictated by the cost and quaUty of the available sources of soda, alumina, and fluoriae. Starting materials iaclude sodium aluminate from Bayer s alumina process hydrogen fluoride from kiln gases or aqueous hydrofluoric acid sodium fluoride ammonium bifluoride, fluorosiUcic acid, fluoroboric acid, sodium fluosiUcate, and aluminum fluorosiUcate aluminum oxide, aluminum sulfate, aluminum chloride, alumina hydrate and sodium hydroxide, sodium carbonate, sodium chloride, and sodium aluminate. 

The manufacture of cryoHte is commonly iategrated with the production of alumina hydrate and aluminum trifluoride. The iatermediate stream of sodium aluminate from the Bayer alumina hydrate process can be used along with aqueous hydrofluoric acid, hydrogen fluoride kiln gases, or hydrogen fluoride-rich effluent from dry-process aluminum trifluoride manufacture. 

Acids are usually the end products of ketone oxidations (41,42,44) but vicinal diketones and hydroperoxyketones are apparent intermediates (45). Acids are readily produced from vicinal diketones, perhaps through anhydrides (via, eg, a Bayer-ViUiger reaction) (46,47). The hydroperoxyketones reportedly decompose to diketones as well as to aldehydes and acids (45). Similar products are expected from radical— radical reactions of the corresponding peroxy radical precursors. 

Earlier reports have indicated that esters can form before significant amounts of acids accumulate (16). The Bayer-ViUiger oxidations of ketones with intermediate hydroperoxides and/or peracids have been suggested as ester forming mechanisms (34,56). However, the reactions of simple aUphatic ketones with peracetic acid are probably too slow to support this mechanism (57,58). Very early proposals for ester formation, although imaginative, appear improbable (59). 

Cryolite. Cryofite [15096-52-3] Na AlF, is the primary constituent of the HaH-Hfiroult cell electrolyte. High purity, natural cryofite is found in Greenland, but its rarity and cost have caused the aluminum industry to substitute synthetic cryofite. The latter is produced by the reaction of hydrofluoric acid [7664-39-3] HE, with sodium aluminate [1302-42-7] NaA102, from the Bayer process... 

Thus operating cells need aluminum fluoride [7784-18-17, AIF., rather than cryoHte. Much aluminum fluoride is produced in a fluidized bed by the reaction of hydrofluoric acid gas and activated alumina made by partially calcining the alumina hydrate from the Bayer process... 

Aluminum fluoride is also made by the reaction of fluosiUcic acid [16961 -83-4] H2SiFg, a by-product from phosphoric acid production (see Phosphoric ACID AND THE PHOSPHATES), and aluminum hydroxide from the Bayer process. 

In high caustic Bayer Hquor, Al(OH) 4 ions exist because there is not enough water to hydrate them. Aluminum hydroxide is capable of reacting as either an acid or a base (18). 

Acetylsalicylic acid [50-78-2] (i9-acetyoxyben2oic acid) was first synthesized in 1853 by reaction of acetyl chloride with sodium saUcylate. As a dmg, acetylsahcyhc acid was introduced in Germany in 1899 and into the United States in 1900. The first U.S. patent (35) for the manufacture of acetylsaUcyhc acid expired in 1917. Aspirin is a registered trademark of Bayer in many nations, but in the United States and the United Kingdom, aspirin is accepted as the generic name for acetylsahcyhc acid (36). 

Sulfonic Acid-Based Dyestuffs. Sulfonic acid-derived dyes are utilized industrially in the areas of textiles (qv), paper, cosmetics (qv), foods, detergents, soaps, leather, and inks, both as reactive and disperse dyes. Of the principal classes of dyes, sulfonic acid derivatives find utiUty in the areas of acid, azoic, direct, disperse, and fiber-reactive dyes. In 1994, 120,930 t of synthetic dyes were manufactured in the United States, of which 5,600 t were acidic (74). The three largest manufacturers of sulfonic acid-based dyes for use in the United States are BASF, Bayer, and Ciba-Geigy. 

Several promising antibacterial compounds are available and may be considered for use in U.S. aquaculture. In addition to sarafloxacin, other quinolones, flumequine and oxolinic acid, are already registered in Europe. However, resistance to both of these compounds developed in bacteria in just a few years (20). Enrofloxacin, [95106-60-6], C22H22FN2O2, a quinolone product of Bayer A.G. (Germany), is also a candidate for aquaculture registration in Europe and may be considered for registration in the United States. 

A process to convert butenes to acetic acid has been developed by Farbenfabriken Bayer AG (137) and could be of particular interest to Europe and Japan where butylenes have only fuel value. In this process a butane—butylene stream from which butadiene and isobutylene have been removed reacts with acetic acid in the presence of acid ion-exchange resin at 100—120°C and 1500—2000 kPa (about 15—20 atm) (see Acetic acid and its derivatives, acetic acid). Both butenes react to yield j -butyl acetate which is then oxidized at about 200°C and 6 MPa (about 60 atm) without catalyst to yield acetic acid. 

The two oxidoreductase systems most frequentiy used for preparation of chiral synthons include baker s yeast and horse hver alcohol dehydrogenase (HLAD). The use of baker s yeast has been recendy reviewed in great detail (6,163) and therefore will not be coveted here. The emphasis here is on dehydrogenase-catalyzed oxidation and reduction of alcohols, ketones, and keto acid, oxidations at unsaturated carbon, and Bayer-Vidiger oxidations. 

Some 50 years later, in the 1990s Bayer produced their BAK polyesteramides by co-reacting either hexamethylene diamine or e-caprolactam with adipic acid and butane glycol. These materials do have sufficient regularity to be crystallisable and are of interest as biodegradable plastics and are discussed further in Chapter 31. 

Carothers also produced a number of aliphatic linear polyesters but these did not fulfil his requirements for a fibre-forming polymer which were eventually met by the polyamide, nylon 66. As a consequence the polyesters were discarded by Carothers. However, in 1941 Whinfield and Dickson working at the Calico Printers Association in England announced the discovery of a fibre from poly(ethylene terephthalate). Prompted by the success of such a polymer, Farbenfabriken Bayer initiated a programme in search of other useful polymers containing aromatic rings in the main chain. Carbonic acid derivatives were reacted with many dihydroxy compounds and one of these, bis-phenol A, produced a polymer of immediate promise. 

One such material is the copolymer first marketed by the Japanese company Unitika in 1974 as U-Polymer and more recently by the Belgian company Solvay as Arylef and Union Carbide as Ardel. (Around 1986 the Union Carbide interest in Ardel, as well as in polysulphones, was taken over by Amoco.) Similar polyarylates have since been marketed by Hooker (Durel), Bayer (APE) and DuPont (Arylon). This is a copolyester of terephthalic acid, isophthalic acid and bis-phenol A in the ratio 1 1 2 Figure 25.23). 

A further approach is used by Bayer with their polyesteramide BAK resins. A film grade, with mechanical and thermal properties similar to those of polyethylene is marketed as BAK 1095. Based on caprolactam, adipic acid and butane diol it may be considered as a nylon 6-co-polyester. An injection moulding grade, BAK 2195, with a higher melting point and faster crystallisation is referred to as a nylon 66-co-polyester and thus presumably based on hexamethylene diamine, adipic acid and butane diol. 

Erank H, G. J. Nicholson and E. Bayer, Rapid gas cliromatographic separation of amino acid enantiomers with a novel cliiral stationary phase , J. Chromatogr. Sci. 15 174-176(1977). 

C. Wang, E. Haitmut, G. Wang, L. Zhou, E. Bayer and P. Lu, Determination of amino acid enantiomers by two-column gas cliromatography with valveless column switching , J. Chromatogr. 262 352-359 (1983). 

Bayer and Henrich have prepared a bisnitrosopulegone, which is very useful for the identification of the ketone. A solution of 2 c.c. of pulegone in 2 c.c. of petroleum ether is cooled in a freezing mixture and 1 c.c. of amyl nitrite and a trace of hydrochloric acid are added. Fine needles of the bisnitroso compound quickly separate, which, when dried on a porous plate and washed with petroleum ether, melt at 81 5°. 

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