Chloride ion loss

It is found that decarboxylation of dichlorofluoroacetate [49] gives about 70% of CCI2FH via competitive abstraction of a proton from solvent by the intermediate CCl2F anion, whereas chlorodifluoroacetate [50] gives very little CCIF2H, suggesting either that chloride ion loss in this case is faster than protonation, or that the process is concerted. Decarboxylation procedures have been widely used, mainly for the preparation of fluorocyclopropyl derivatives as illustrated in Figure 6.36 [51, 52]. 

Reductive Chloride Ion Loss and Electropolymerization Techniques in Preparing Metallopolymer Films on Electrode Surfaces... 

During multiple scans (ca. 10-50) into the 0sIII/0s11 reduction the chloride ion loss and pyridine coordination reaction occurred as schematically illustrated in Figure 2. The re-oxidation of surface-bound osmium (eq. 12) proved to be a convenient method to monitor the amount of metal incorporation by the pyridine coordination sites. 

A 1,32 -azaphosphinine was prepared by condensation of diethyl phenylethynylphosphonite (78) with the nitrile ylide formed by deprotonation and chloride ion loss from (79). Cyclization and proto tropic isomerization of an intermediate ethynyl-1,4-dipole (80) led to the product (81) (Scheme... 

The reaction may be performed in one stage by preparing the trichloro-methylsulfenamido heterocycle in situ in the presence of an aromatic amine l,2,4-thiadiazolo[4,3-a]pyridine derivatives (152), for example, have been produced in this way.139 Suitable enolate ions, e.g., acetylacetone or diethyl malonate, give rise to compounds of type 155,140 probably by the successive displacement (from 151) of a chloride ion, loss of hydrogen chloride, and cyclization of the resulting a,/)-unsaturated intermediate 154 by a Michael-... 

Loss of a proton and of chloride ion from the tetrahedral intermediate yields the mixed anhydride... 

It would appear that this type of addition may not be confined to the addition of NH2 in liquid ammonia, since it has been observed that treatment of 2-chloro-3-dichloromethyl-pyrazine with an excess of methoxide results in the introduction of a methoxy group into the 6-position of the pyrazine ring (Scheme 9) (68TL5931). This reaction is best rationalized in terms of addition of the methoxide ion at the 6-position, followed by loss of chloride ion from the dichloromethyl side chain. 

Benzimidazole 3-oxides, e.g. (189), react with phosphorus oxychloride or sulfuryl chloride to form the corresponding 2-chlorobenzimidazoles. The reaction sequence involves first formation of a nucleophilic complex (190), then attack of chloride ions on the complex, followed by rearomatization involving loss of the fV-oxide oxygen (191 -> 192). 

Figure 2-11 shows weight loss rate-potential curves for aluminum in neutral saline solution under cathodic protection [36,39]. Aluminum and its alloys are passive in neutral waters but can suffer pitting corrosion in the presence of chloride ions which can be prevented by cathodic protection [10, 40-42]. In alkaline media which arise by cathodic polarization according to Eq. (2-19), the passivating oxide films are soluble ... 

During the next fifty years the interest in derivatives of divalent carbon was mainly confined to methylene (CHg) and substituted methylenes obtained by decomposition of the corresponding diazo compounds this phase has been fully reviewed by Huisgen. The first convincing evidence for the formation of dichlorocarbene from chloroform was presented by Hine in 1950. Kinetic studies of the basic hydrolysis of chloroform in aqueous dioxane led to the suggestion that the rate-determining step was loss of chloride ion from the tri-chloromethyl anion which is formed in a rapid pre-equilibrium with hydroxide ions ... 

Interest in this reaction was revived when the relevance of a carbene mechanism was realized, particularly following the demonstration (cf. SectionI,B) of a similar ring expansion of indene to 2-chloro-naphthalene by dichlorocarbene via the cyclopropane adduct. Indeed, at this time Nakazaki suggested that these reactions occurred by the addition of dichlorocarbene to the indolyl anion and subsequent rearrangement to the indolenine and, with loss of chloride ion, to the quinoline [Eq. (12)]. The preference of dichlorocarbene for... 

A Bronsted-Lowry acid is a substance that donates a proton (H+), and a Bronsted-Lowry base is a substance that accepts a proton. (The name proton is often used as a synonym for hydrogen ion, H+, because loss of the valence electron from a neutral hydrogen atom leaves only the hydrogen nucleus— a proton.) When gaseous hydrogen chloride dissolves in water, for example, a polar HC1 molecule acts as an acid and donates a proton, while a water molecule acts as a base and accepts the proton, yielding hydronium ion (H30+) and chloride ion (Cl-). 

Spontaneous loss of chloride ion then yields the neutral dichlorocarbene. 

The ion Fe2+ is converted into ion Fe3+ (oxidation), and the neutral chlorine molecule into negatively charged chloride ions Cl" (reduction) the conversion of Fez+ into Fe3+ requires the loss of one electron, and the transformation of the neutral chlorine molecule into chloride ions necessitates the gain of two electrons. This leads to the view that, for reactions in solutions, oxidation is a process involving a loss of electrons, as in... 

Goering and coworkers201 studied the kinetics of base-promoted dehydrohalogenation of several series of cis- or frans-2-chlorocycloalkyl aryl sulfones. For the trans-2-chlorocyclohexyl series reacting with sodium hydroxide in 80% ethanol at 0 °C the p value was 1.42. The mechanism was considered to involve rate-determining carbanion formation, with the subsequent loss of chloride ion in a fast step. 

Copolymers of mainly acrylic acid and 2% to 20% by weight of itaconic acid are described as fluid loss additives for aqueous drilling fluids [138]. The polymers have an average molecular weight between 100,000 and 500,000 Dalton and are water dispersible. The polymers are advantageous when used with muds containing soluble calcium and muds containing chloride ions, such as seawater muds. 

Deactivation can be understood in terms of the mechanism based on adsorption of the anions. Although a lower current density would need a less positive potential if for example, chloride ions stayed at the surface, as soon as the potential shifts negative, desorption of chloride should take place, with a corresponding loss of activity. 

Spatial electrochromism has been demonstrated in metallopolymeric films.28 Photolysis of poly-[Run(L10)2(py)2]Cl2 thin films on ITO glass in the presence of chloride ions leads to photochemical loss of the photolabile pyridine ligands, and sequential formation of po/y-[RuII(Llt))2(py)Cl]Cl and po/y-[Run(L10)2Cl2] (Scheme 1). 

Smith [117] discussed the determination of tin in water. In the determination of low concentrations of the order of 40 ng of trialkyltin chlorides in sea water it has been observed that these compounds are very volatile and are easily lost upon evaporation with acid. Quantitative recovery of tin is, however, obtained in the absence of chloride ion during evaporation with acid. Preliminary removal of chlorides from sea water by passage down a column of IRA 400 resin before digestion with acid completely overcame loss of tin on subsequent evaporation, with acid giving a tin recovery of 90%. 

In the late 1970s and early 1980s there was a flurry of interest in precipitation techniques as a method of keeping ions in their in vivo locations, and thus avoid the problems mentioned in Subheading 3.1. The idea was simply to add a precipitant to the fixative, which reacted with the ion in question, and hopefully kept it where it was in the tissue. The most popular technique was to use a silver salt to precipitate chloride ions (35). Two problems emerged loss of ions was not totally prevented (36) and quantification was not possible. This led to the almost complete... 

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