The Salt-Oxide Method

A suspension of the oxide of the divalent cation is prepared, vigorously stirred and mixed with an aqueous solution of the trivalent metal cation in excess above the pursued stoichiometry of the LDH, during several days 

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The nature of the reagents leads us to name this synthesis the "salt-oxide method."... 

When one of the two acids is used in excess and the pk -values of the two acids differ strongly, the salt deficit method should be used with caution. Formic add, acetic acid, propionic acid, and trifluoroacetic acid have been electrolyzed competitively in mixtures of pairs. Formic acid and trifluoroacetic acid are comparable in case of electrolysis, both are more readily electrolyzed than acetic and propionic adds. Deviations are rationalized on the basis of differences in ionization [147]. It might 1 useful in such cases to neutralize both acids completely. Sometimes one of the two acids, although being the minor component, is more favorably oxidized possibly due to preferential adsorption or its higher acidity [148]. In this case the continuous addition of the more acidic add to an excess of the weaker acid may lead to successful cross-coupling [149], The chain length of the two acids should be chosen in such a... 

A second major route to metal-metal complexes, related to the salt-elimination method described above, is elimination of neutral molecules with concurrent formation of metal-metal bonded complexes. Transihon metal hydrides readily undergo these dinuclear reductive elimination reactions. The oxidative addition/reductive elimination see Oxidative Addition and Reductive Elimination) reaction of molecular hydrogen is a key reachon in this area (equation 47). 

The mechanism involves initial formation of an acetylated or phosphorylated cation, which reacts with a carbanion to form a salt that is strongly acidic because of its substituent electron-withdrawing groups. This salt is hence readily converted into an ylide by loss of a proton, whose removal is assisted by the acetic anhydride or triethylamine (see equation 27). As with method B the arsine oxide method is limited to the preparation of stable ylides, since its success depends upon the acidity of the methylene compound. Almost all examples of this method have utilized triphenylarsine oxide tri-w-butylarsine oxide has been used in triethylamine but gave only intractable products in acetic anhydride In a modification of this method, an ylide has been prepared by reaction of acetoacetanilide with diacetoxytriphenylarsorane, the latter compound having been prepared from triphenylarsine and lead tetra-acetate. ... 

The readily available 2,3,4,6-fefra-O-benzyl-D-glucopyranose (11) can be used for the synthesis of both nojirimycin (1) and 1-deoxynojirimycin (2) (Schemed).It was treated with EtSH to furnish 12, which was oxidized to the corresponding ketone 13 using TPAP, while the Swern oxidation method failed to produce 13. Treatment of 13 with mercury(ll) salts in the presence of methanol followed by treatment with hydroxylamine hydrochloride in the presence of pyridine afforded the oxime 14 in 73% yield. Treatment of 14 with LiAlH4 in diethyl ether followed by N-protection of the resulting diastereomeric mixture of amines with di-rert-butyl dicarbonate furnished 15 and 16 in 65 and 15% yield, respectively. Pearlman s catalytic hydrogenation of 15 over palladium hydroxide in ethanol followed by treatment of the resulting tetrol with SO2 in water furnished the sulfonic acid 17 in 80% yield. Conversion of 17 into 1 was accomplished by treatment with Dowex 1X2 (OH ) resin. 

Closely related to the salt infiltration method discussed above is the utilization of metal alkoxide precursors in a sol-gel process to fill the interstitial sites in an opal template. The template is first infiltrated with an alkoxide (neat or as solution), then the hydrolysis and condensation reaction following the infiltration transforms the alkoxides into an extended network of the corresponding metal oxide. By this method Ti02 networks besides other oxides were initially prepared with a strong focus on their optical properties as photonic crystals [30,50]. For this purpose a high refractive index material is desired, which would be the rutile modification of titania with the highest refractive index. Nevertheless, the sol-gel procedure provides an amorphous or anatase modification with lower refractive index. By calcination of the anatase... 

Cu-Cr-Q] This compound had never been prepared previously by the coprecipitation method and the alternative salt-oxide method was successfully used to synthesized it. The reaction proceeds at a nearly constant pH, contrary to what is observed in the former cases.The pH drops from 6.8 rfter the first addition of CrCls, and then remains constant at ca. 4.5. The disappearance of CuO on diffractograms (Figure 7-14) occms at a Cu/Cr ratio near 2, and the phase is characterized by the chemical formula Cu2Cr(0H)6Cl.nH20. 

We have already pointed out that the [Zn-Cr-C1]3R phase prepared by the so-called "salt-oxide" method displays a constant ratio Zn2+/Cr3+ = 2.0, suggesting a probable ordering of the divalent and trivalent cations never proved so far. If the mixed... 

The studied compounds are generally prepared as [M -M -Q] by the "salt+base" or "salt+oxide" methods followed by an... 

The sulfite oxidation method, however, can be expected to give approximately correct results even in rather heterogeneous dispersions because of the low gas phase conversions involved (8,9). Furthermore, the reaction kinetics is almost unaffected by CMC (10,11,12). The photographic method, on the other hand, has been shown to overestimate the interfacial area in sulfite solutions both with and without CMC (8,9). Therefore, in this study, the sulfite oxidation method is used for interfacial area determination. The influence of the added salt (0.8 mole l lNa2S03) is checked by additional kj a measurements in a CMC solution containing 0.8 mole l Na2S04. 

The first patent on ammonia oxidation wras issued to Khulman in 1839 in this case platinum was used as a catalyst to oxidize ammonia with air. The ammonia-oxidation method using a platinum catalyst qn a commercial scale, developed by Oswald and Brauer and first operated in Germany about 1908, is at present the principal industrial method of nitric acid producticxi. The main use for nitric acid is in fertiDzer production, mainly for ammonium nitrate as such or in compound fertilizers, nitrogen solutions, or mixed salts. About 75% of total nitric acid production is consumed for nitrate fertilizers, mainly as 509 5% concentration acid. Smaller fertilizer uses are for calcium and potassium nitrates. A primary use is in addulation of phosphate rock for production of nitrophosphates. Plant capacities for weak nitric acid i Bed for fertilizer production are in the range of 35 to 1,380 tpd althoi h capacities of 2,000 tpd have been designed. 

Hydrazine [302-01-2] (diamide), N2H4, a colorless liquid having an ammoniacal odor, is the simplest diamine and unique in its class because of the N—N bond. It was first prepared in 1887 by Curtius as the sulfate salt from diazoacetic ester. Thiele (1893) suggested that the oxidation of ammonia (qv) with hypochlorite should yield hydrazine and in 1906 Raschig demonstrated this process, variations of which constitute the chief commercial methods of manufacture in the 1990s. 

Lithium Niobate. Lithium niobate [12031 -64-9], LiNbO, is normally formed by reaction of lithium hydroxide and niobium oxide. The salt has important uses in switches for optical fiber communication systems and is the material of choice in many electrooptic appHcations including waveguide modulators and sound acoustic wave devices. Crystals of lithium niobate ate usually grown by the Czochralski method foUowed by infiltration of wafers by metal vapor to adjust the index of refraction. 

Diacetone-L-sorbose (DAS) is oxidized at elevated temperatures in dilute sodium hydroxide in the presence of a catalyst (nickel chloride for bleach or palladium on carbon for air) or by electrolytic methods. After completion of the reaction, the mixture is worked up by acidification to 2,3 4,6-bis-0-isoptopyhdene-2-oxo-L-gulonic acid (2,3 4,6-diacetone-2-keto-L-gulonic acid) (DAG), which is isolated through filtration, washing, and drying. With sodium hypochlorite/nickel chloride, the reported DAG yields ate >90% (65). The oxidation with air has been reported, and a practical process was developed with palladium—carbon or platinum—carbon as catalyst (66,67). The electrolytic oxidation with nickel salts as the catalyst has also... 

In this method, a metal oxide or hydroxide is slurried in an organic solvent, neodecanoic acid is slowly added, and the mixture is refluxed to remove the water. Salts that are basic can be prepared by using less than stoichiometric amounts of acid. This method has been used in the preparation of metal salts of silver (80) and vanadium (81). The third method of preparation is similar to the fusion process, the difference is the use of finely divided metal as the starting material instead of the metal oxide or hydroxide. This method has been appHed to the preparation of cobalt neodecanoate (82). Salts of tin (83) and antimony (84) have been prepared by the fusion method, starting with lower carboxyHc acids, then replacing these acids with neodecanoic acid. 

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