Phosphorates synthesis

The future for the use of coordination compounds in phosphors looks very bright indeed. Man s need to illuminate his surroundings, transfer information, and display that information efficiently can only mean an ever more demanding and growing marketplace for materials that emit light. Coordination compounds are, and will remain, in widespread use as both precursors in phosphor synthesis and as major constituents in small molecule OLEDs. 

Vecht, A. Davies, D. A. Smith, D. 1998. A novel method for the preparation of sulfides and selenides and its apphcation for phosphor synthesis. Mat. Res. Innovat. 

A flux often reacts with the starting material, sometimes a melt, when used in small amounts (e.g. less than 10% by weight of the phosphor) and always shows decomposition or evaporation during phosphor synthesis. Frequently used fluxes are NH4CI, NH4Br and AIF3. 

MICHAELIS-ARBUZOV Phosphorate Synthesis Ni catalyzed phosphonate synthesis from phosphites and aryl halides. Reaction of alkyl halides with phosphites proceeds without nickel salts (see 1st edition). 

See also Sodium peroxide 8-hydrate, synthesis 1 Strontium sulfide and sel-enide phosphors, synthesis 4... 

Early catalysts for acrolein synthesis were based on cuprous oxide and other heavy metal oxides deposited on inert siHca or alumina supports (39). Later, catalysts more selective for the oxidation of propylene to acrolein and acrolein to acryHc acid were prepared from bismuth, cobalt, kon, nickel, tin salts, and molybdic, molybdic phosphoric, and molybdic siHcic acids. Preferred second-stage catalysts generally are complex oxides containing molybdenum and vanadium. Other components, such as tungsten, copper, tellurium, and arsenic oxides, have been incorporated to increase low temperature activity and productivity (39,45,46). 

The synthesis of 2,4-dihydroxyacetophenone [89-84-9] (21) by acylation reactions of resorcinol has been extensively studied. The reaction is performed using acetic anhydride (104), acetyl chloride (105), or acetic acid (106). The esterification of resorcinol by acetic anhydride followed by the isomerization of the diacetate intermediate has also been described in the presence of zinc chloride (107). Alkylation of resorcinol can be carried out using ethers (108), olefins (109), or alcohols (110). The catalysts which are generally used include sulfuric acid, phosphoric and polyphosphoric acids, acidic resins, or aluminum and iron derivatives. 2-Chlororesorcinol [6201-65-1] (22) is obtained by a sulfonation—chloration—desulfonation technique (111). 1,2,4-Trihydroxybenzene [533-73-3] (23) is obtained by hydroxylation of resorcinol using hydrogen peroxide (112) or peracids (113). 

Phosphors usually contain activator ions in addition to the host material. These ions are dehberately added in the proper proportion during the synthesis. The activators and their surrounding ions form the active optical centers. Table 1 Hsts some commonly used activator ions. Some soflds, made up of complexes such as calcium tungstate [7790-75-2] CaWO, are self-activated. Also in many photolurninescence phosphors, the primary activator does not efficiently absorb the exciting radiation and a second impurity ion is introduced known as the sensitizer. The sensitizer, which is an activator ion itself, absorbs the exciting radiation and transfers this energy to the primary activator. 

The GdAlgB O QiCe ", Tb " is synthesized by a soHd-state firing of the rare-earth coprecipitated oxide plus boric acid and MgCO at 900° C in a slightly reducing atmosphere. As in the case of the lanthanum phosphate phosphor, a flux is usually used. The synthesis of this phosphor is further comphcated, however, by the fact that it is a ternary system and secondary phases such as gadolinium borate form and must then react to give the final phosphor. 

Most of the phosphoms produced as the element is later converted to high purity phosphoric acid and phosphate compounds the remainder is used in direct chemical synthesis to produce high purity products. In contrast, phosphoric acid produced by the wet process is used in lower purity apphcations, especially in fertiliser and to a lesser degree in animal feed (see Feeds AND FEED ADDITIVES). More recendy, a small portion of wet acid is purified in a second process and then also used in high purity acid and phosphate compound apphcations. 

Synthesis. Hydroxyhydroquiaone is not produced on a large scale, but many uses for it are being developed. The most convenient preparation of hydroxyhydroquiaone is the reaction of -benzoquiaone with acetic anhydride ia the preseace of sulfuric acid or phosphoric acid. The resultant triacetate (29) can be hydrolyzed to hydroxyhydroquiaone (86). 

A Methylamino)phenol. This derivative (15) is easily soluble ia ethyl acetate, ethanol, diethyl ether, and benzene. It is also soluble ia hot water, but only spatingly soluble ia cold water. Industrial synthesis is by heating 3-(A/-methylamino)benzenesulfonic acid with sodium hydroxide at 200—220°C (179) or by the reaction of resorciaol with methylamiae ia the presence of aqueous phosphoric acid at 200°C (180). 

Apphcations include ka olin clay dewatering, separation of fish oils from press Hquor, starch and gluten concentration, clarification of wet-process phosphoric acid, tar sands, and concentrations of yeast, bacteria, and fungi from growth media in protein synthesis (14). 

Acid-Gatalyzed Synthesis. The acid-catalysed reaction of alkenes with hydrogen sulfide to prepare thiols can be accompHshed using a strong acid (sulfuric or phosphoric acid) catalyst. Thiols can also be prepared continuously over a variety of soHd acid catalysts, such as seoHtes, sulfonic acid-containing resin catalysts, or aluminas (22). The continuous process is utilised commercially to manufacture the more important thiols (23,24). The acid-catalysed reaction is commonly classed as a Markownikoff addition. Examples of two important industrial processes are 2-methyl-2-propanethiol and 2-propanethiol, given in equations 1 and 2, respectively. 

The Grewe synthesis of /V-methylmorphinan [3882-38-0] (40), which paved the way for the preparation of dextromethorphan and numerous analogues, follows standard reactions to 2-meth5l-l-benzyl-l,2,3,4,5,6,7,8-octahydroisoquinoline. Cyclization of this compound with phosphoric acid gave a mixture of isomers from which /V-methylmorphinan was separated. 

Imidazole-5-thione, 4,4-diphenyl-tautomerism, 5, 368 3 H-Imidazole-2-thione, 1,3-dimethyl-structure, 5, 367 Imidazole-2-thiones acidity, 5, 367 betaines, 5, 372 synthesis, 5, 481 tautomerism, 5, 367 3H-Imidazole-2-thiones synthesis, 5, 473, 6, 992 Imidazolides deacylation, 5, 453 mass spectra, 5, 360 phosphoric acid reactions, 5, 454 reactions, 5, 451-453 Imidazolidine, l-alkyl-3-phenyl-N-oxidation, 5, 427 Imidazolidine, 1,3-benzyl-2-phenyl-oxidation, S, 427... 

A complete synthesis of laudanosine was effected by Pictet and Finkelstein by the condensation of omoveratrylamine (I) with homo-veratroyl chloride (II), giving omoveratroyl omoveratrylamine, which with phosphoric oxide undergoes cyclisation to 3 4-dihydropapaverine (III), which was converted into the methochloride and reduced to laudanosine (IV). 

The synthesis of meconin has been referred to already (p. 201). Cotarnine has been synthesised by Salway from myristicin (I) as a starting-point. This was transformed into jS-3-methoxy-4 5-methylenedioxy-phenylpropionic acid (II), the amide of which was converted by Hofmann s reaction into )S-3-methoxy-4 5-methylenedioxyphenylethylamine, and the phenylacetyl derivative (HI) of this condensed, by heating it in xylene solution with phosphoric oxide, giving rise to the two possible dihydroiso-quinoline derivatives. The first of these substances, 8-methoxy-6 7-methylenedipxy-1-benzyl-3 4-dihydroiioquinoline (IV), on conversion into the methochloride and reduction with tin and hydrochloric acid, gave... 

On treatment of N-methylpapaverine, formed by the lithium aluminum hydride reduction of papaverine methiodide with phosphoric acid, N-methylpavine is formed which is identical with the racemic alkaloid argemonine. This reaction was used for the synthesis of the alkaloid (-h)-coreximine (268) (174) and similar compounds containing the proto-berberine grouping in the molecule (269,270). 

FIGURE 11.15 Formadoii of ADP and ATP by the successive addition of phosphate groups via phosphoric anhydride linkages. Note the removal of equivalents of H9O in these dehydration synthesis reactions. 

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