By Displacement

Copper(I) perchlorate, CUCIO4. Formed in solutions of organic solvents (Et20, C Hf,) by displacement of Ag by Cu. 

The general characteristics of all these elements generally preclude their extraction by any method involving aqueous solution. For the lighter, less volatile metals (Li, Na, Be, Mg, Ca) electrolysis of a fused salt (usually the chloride), or of a mixture of salts, is used. The heavier, more volatile metals in each group can all be similarly obtained by electrolysis, but it is usually more convenient to take advantage of their volatility and obtain them from their oxides or chlorides by displacement, i.e. by general reactions such as... 

Anhydrous hydrogen fluoride (as distinct from an aqueous solution of hydrofluoric acid) does not attack silica or glass. It reacts with metals to give fluorides, for example with heated iron the anhydrous iron(II) fluoride is formed the same product is obtained by displacement of chlorine from iron(II) chloride ... 

Allylic nitro compounds form rr-allylpalladium complexes by displacement of the nitro group and react with nucleophiles, and allylation with the tertiary nitro compound 202 takes place at the more substituted side without rearrangement to give 203[8,9,128]. 

An important method for construction of functionalized 3-alkyl substituents involves introduction of a nucleophilic carbon synthon by displacement of an a-substituent. This corresponds to formation of a benzylic bond but the ability of the indole ring to act as an electron donor strongly influences the reaction pattern. Under many conditions displacement takes place by an elimination-addition sequence[l]. Substituents that are normally poor leaving groups, e.g. alkoxy or dialkylamino, exhibit a convenient level of reactivity. Conversely, the 3-(halomethyl)indoles are too reactive to be synthetically useful unless stabilized by a ring EW substituent. 3-(Dimethylaminomethyl)indoles (gramine derivatives) prepared by Mannich reactions or the derived quaternary salts are often the preferred starting material for the nucleophilic substitution reactions. 

The reaction of alcohols with acyl chlorides is analogous to their reaction with p toluenesulfonyl chloride described earlier (Section 8 14 and Table 15 2) In those reactions a p toluene sulfonate ester was formed by displacement of chloride from the sulfonyl group by the oxygen of the alcohol Carboxylic esters arise by displacement of chlonde from a carbonyl group by the alcohol oxygen... 

Evaluation of pore volume by displacement of mercury and another fluid... 

Steps. A purge-swing cycle usually has two steps, adsorption and purge. Sometimes, a cocurrent purge is added. After the adsorption step has been completed and the less selectively adsorbed components have been recovered, an appreciable amount of product is still stored in the bed. A purge cocurrent to feed can increase recovery by displacing the fluid held in the voids. 

The three types of washing are washing of filter cakes by displacement, washing by reslurrying of cakes or sludges, and washing by successive dilution. 

The filter cake can then be washed either by displacement or by reslurrying. Reslurrying is easily accompHshed using the stirring action of the rotor blades when the rotor is lowered into the cake. The cake may also be dried in situ by the passage of hot air through it, or may be steam distilled for the recovery of solvent. 

Another useful reagent for the 3-aLkylation of indole is the /V,/V-dimethy1foTma1 diminium ion, which forms the useful intermediate gramine [87-52-5] (9). The C-3 substituent can subsequendy be modified by displacement of the dimethylarnino group by a nucleophile. Alternatively, gramine can be converted to its quaternary salt prior to substitution. A variety of carbanions can function as the nucleophile. 

In dmmming and the filling of tank cars and tmcks, where the vessel is initially empty, the amount of material being transferred that could be released by displacement depends on how much evaporates during the filling. Rarely does a material evaporate so quickly that the entire volume of displaced gas is saturated. More likely the initial release at the start of filling contains only a small amount and the concentration increases toward saturation... 

Cementation. A metal can be removed from solution by displacing it with a mote active metal. This simple, inexpensive method has been commonly used to recover copper from dilute (1—3 kg/m ) solution using shredded iron and de-tinned iron cans as reducing agent. 

Hydrolysis and perhydrolysis of diacyl peroxides yields peroxycarboxyhc acids. Carbanions react by displacement on oxygen ... 

Halogen Displacement. Poly(phenylene oxide)s can also be prepared from 4-halo-2,6-disubstituted phenols by displacement of the halogen to form the ether linkage (48). A trace of an oxidizing agent or free radical initiates the displacement reaction. With 4-bromo-2,6-dimethylphenol, the reaction can be represented as in equation 10 ... 

Ephedrine, which is not a catecholamine, has weak oral activity as a bronchodilator and although it has some direct action at adrenergic receptors, its predominant mode of action is by displacing norepinephrine from storage vesicules. 2"Agonists which are in use or are under investigation are the result of quests for improved selectivity, retention of potency, oral activity, and longer duration of action. 

Pyrrole is a colorless, slightly hygroscopic Hquid which, if fresh, emits an odor like that of chloroform. However, it darkens on exposure to air and eventually produces a dark brown resin. It can be preserved by excluding air from the storage container, preferably by displacement with ammonia to prevent acid-catalyzed polymerization. A review of the physical and theoretical aspects of pyrrole is found in Reference 4. Some physical properties of pyrrole are Hsted in Table 1. 

Halosilanes can also be produced by displacement of amines with a hydrogen hahde (173). 

Using any of the carrier proteins available in highly purified form, eg, TBG or TBPA, a convenient and accurate quantitative determination of and is possible by displacement of radioiodinated or T. This procedure enables their quick determination at low concentrations even in the presence of coundess other substances that occur in body duids (31). In a similar fashion, intact cell nuclei or solubilized proteins from rat fiver cell nuclei, which display high affinities for thyroid hormones, especially T, have been used to establish relative binding affinities of many thyromimetic compounds (7). 

The capability of zinc to reduce the ions of many metals to theh metallic state is the basis of important appHcations. However, metals are removed from zinc solutions by displacement with finely divided zinc before winning by electrolysis. Gold and silver are displaced from cyanide leach solutions with zinc and the following metals are similarly recovered from various solutions platinum group, cadmium, indium, thallium, and sometimes copper. 

Mod.ifica.tion of Intact Penems. Functional group modification has been used by a number of researchers (123—125) to synthesize a wide range of 2-substituted penems. For example, activation of the hydroxyl group of (84, R = OH) followed by displacement reactions provided 2-heterocyclylthiomethyl-penems (84, R = (3)-heterocyclyl) (125) and 2-(quaternary ammonio)methyl-penems (84, R = (1 )-... 

The calcium form of EDTA instead of free EDTA is used in many food preparations to stabilize against such deleterious effects as rancidity, loss of ascorbic acid, loss of flavor, development of cloudiness, and discoloration. The causative metal ions are sequestered by displacing calcium from the chelate, and possible problems, such as depletion of body calcium from ingestion of any excess of the free chelant, had it been used, are avoided. 

In the treatment of poisoning by lead or other metal ions, higher concentrations of chelant can be safely obtained in humans by administering Na2CaEDTA rather than Na EDTA. The metal ion is bound by displacing small amounts of Ca " that the body can tolerate. Use of Na EDTA would result in calcium chelation and thus serious depletion of calcium in the body fluids (44). Removal of iron in Cooley s anemia is accompHshed by using chelants that are relatively specific for iron (45). 

This was first demonstrated ia 1862 by Berthelot and Saint-Gibes (32), who found that when equivalent quantities of ethyl alcohol and acetic acid were abowed to react, the esterification stopped when two-thirds of the acid had reacted. Sinularly, when equal molar proportions of ethyl acetate and water were heated together, hydrolysis of the ester stopped when about one-third of the ester was hydroly2ed. By varyiag the molar ratios of alcohol to acid, yields of ester >66% were obtained by displacement of the equbibrium. The results of these tests were ia accordance with the mass action law shown ia equation 5. 

A second practical route to AT-unsubstituted amides is by the controlled hydrolysis of nitriles, which can often be made (in the 5-position) by primary synthesis or (elsewhere) by displacement of an ammonio grouping. Thus 4,6-dimethylpyrimidine-2-carbonitrile (798 R = CN) in warm aqueous ammonia gives the amide (798 R = CONH2) in good yield... 

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