Reversible chloride migration

Cationic surfactants and protonated polyamines may reverse the direction of the EOF as they impart a positive charge on the capillary wall. This technique is used to prevent wall interactions with cationic proteins. Changing the direction of the EOF is important in anion analysis where comigration of anions and the EOF is required. Otherwise, highly mobile anions such as chloride migrate toward the anode, whereas lower mobility anions are swept by the EOF toward the cathode. 

Scheme 8.10 Reversible formation and cleavage of an Ru-Ir bond upon chloride migration.

Ion 21 can either lose a proton or combine with chloride ion. If it loses a proton, the product is an unsaturated ketone the mechanism is similar to the tetrahedral mechanism of Chapter 10, but with the charges reversed. If it combines with chloride, the product is a 3-halo ketone, which can be isolated, so that the result is addition to the double bond (see 15-45). On the other hand, the p-halo ketone may, under the conditions of the reaction, lose HCl to give the unsaturated ketone, this time by an addition-elimination mechanism. In the case of unsymmetrical alkenes, the attacking ion prefers the position at which there are more hydrogens, following Markovnikov s rule (p. 984). Anhydrides and carboxylic acids (the latter with a proton acid such as anhydrous HF, H2SO4, or polyphosphoric acid as a catalyst) are sometimes used instead of acyl halides. With some substrates and catalysts double-bond migrations are occasionally encountered so that, for example, when 1 -methylcyclohexene was acylated with acetic anhydride and zinc chloride, the major product was 6-acetyl-1-methylcyclohexene. ... 

Adding copper(l) chloride to the molten glass makes the process reversible. When light intensity diminishes, copper ions remove electrons from silver atoms, converting the silver atoms into silver ions. The silver ions then migrate back to the silver chloride crystals. The glass becomes transparent again. 

Xlld does not involve the chiral center, so if the reaction takes place by this pathway, the migration of the alkyl group from sulfur to palladium (with the concomitant or subsequent loss of sulfur dioxide) must take place with inversion of configuration at carbon. Inversion of configuration at carbon has been observed in the reverse-type reaction, the sulfur dioxide insertion into a carbon-iron sigma bond (49). Nucleophilic displacement at carbon in compounds of type Xld is unusually difficult, so the reaction via the sulfite intermediate Xlld would appear to be more likely. Conversion of the tosylate of l-phenyl-2,2,2-trifluoroethanol to the corresponding chloride, a reaction which takes place in the presence of tetra- (n-butyl) ajnmonium chloride with inversion of configuration at carbon, requires 100°C for 24 hrs in dimethylsulfoxide. 

Cell DC-2. Earlier demineralization studies by Lyon (9) employed cell DC-2. This was a sandwich-type cell with Lucite side plates bolted together with two epoxy resin-gasketed graphite electrodes separated by an anion-permeable membrane. The membrane was necessary because a suitable anion-responsive electrode was not then known. The principle of operation is that in the cathode compartment, after several current reversal conditioning cycles, sodium ions are removed by the cathode while chloride ions migrate from the cathode through the membrane to the anion chamber. In the anode chamber, sodium ions, from the previous half cycles, are rejected from the anode. The net result was salt depletion in the cathode chamber and a similar concentration increase in the anode chamber. 

Palladium-catalyzed reaction of dienol 80 in acetone in the presence of acetic acid and benzoquinone resulted in an intramolecular 1,4-oxyacetoxylation (Scheme 8-28) [107], The stereochemistry of the reaction can be controlled via a slight variation of the ligand environment. Thus, under chloride-ion-free conditions, a rrawj-oxyacetoxylation occurs. Usually this reaction is highly stereoselective (>98% tram addition), except m = n = 2 in Scheme 8-28, where the tramlcis ratio is 75 25. When the reaction is run in the presence of a catalytic amount of chloride, the stereochemistry is reversed and now a 1,4-cts-oxyacetoxylation takes place. The effect of the chloride is the same as discussed above, i.e., it blocks the coordination of acetate so that cis migration by acetate cannot occur. 

Propound modification of the structure, with migration of the basic side-chain and reversion to a fully aromatic phenanthrene derivative, occurs when thebaine [i] [1] or codeinone [n] [2] is heated with dilute hydrochloric acid, the product being the phenolic secondary amine thebenine [in], Triacetylthebenine is produced when -codeinone [iv] is heated with acetic anhydride [3], and thebenine-8-methyl ether (methebenine), 8-ethyl ether (ethebenine), and 8-propyl ether (prothe-benine) can be prepared by heating thebaine or codeinone with hydrochloric acid and methyl, ethyl, and propyl alcohol respectively [2, 4]. Methebenine, which can be hydrolysed to thebenine by hot 20 per cent, hydrochloric acid [4], is also obtained by the action of stannous chloride and acetic anhydride on thebaine [5]. 

Many parameters in the medical laboratory are determined from serum or plasma. This should be obtained by removing the blood coagula and corpuscles as soon as possible after the blood sample has been taken. This prevents any analytes from migrating from the solid constituents of the blood into the serum or plasma (e.g. potassium and some enzymes), prevents migration in the reverse direction (e.g. of chloride), and also prevents chemical reactions in vitro from causing increase or decrease of the concentrations of any substances [3]. 

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