Anion halides

In Chapter 4 you learned that carbocations could be captured by halide anions to give alkyl halides In the present chapter a second type of carbocation reaction has been introduced—a carbocation can lose a proton to form an alkene In the next section a third aspect of carbocation behavior will be described the rearrangement of one carbo cation to another... 

The alkyl halide m this case 2 bromo 2 methylbutane ionizes to a carbocation and a halide anion by a heterolytic cleavage of the carbon-halogen bond Like the dissoci ation of an aUcyloxonmm ion to a carbocation this step is rate determining Because the rate determining step is ummolecular—it involves only the alkyl halide and not the base—It is a type of El mechanism... 

Figure 6 4 shows the complementary nature of the electrostatic potentials of an alkene and a hydrogen halide We also know (from Section 4 8) that carbocations when gen erated m the presence of halide anions react with them to form alkyl halides... 

Having gamed one electron the alkyl halide is now negatively chaiged and has an odd numbei of elections It is an anion radical The extra electron occupies an antibondmg oibital This anion radical fragments to an alkyl radical and a halide anion... 

Anion radical Alkyl radical Halide anion... 

Dihalocarbenes are formed when trihalomethanes are treated with a strong base such as potassium tert butoxide The trihalomethyl anion produced on proton abstraction dissociates to a dihalocarbene and a halide anion... 

Step 2 Nucleophilic attack of the halide anion on carbon of the dialkyloxonmm ion This step gives one molecule of an alkyl halide and one molecule of an alcohol... 

The halide anion of quaternary ammonium iodides may be replaced by hydroxide by treatment with an aqueous slurry of silver oxide Silver iodide precipitates and a solu tion of the quaternary ammonium hydroxide is formed... 

Figure 13.5 Siruclures of. some coinplex halide anions of sloichiomeiry MX4...

Figure 13.6 Structures of some complex halide anions of stoichiometry MXj ...

Water-acetone mixtures offer a sufficiently polar medium that certain alkyl halides can dissociate into a halide anion and a carbocation. The latter then reacts with water to give an SnI substitution product. 

With primary alkyl halides 1 the Finkelstein reaction proceeds by a Sn2-mechanism. An alkali halide is used to deliver the nucleophilic halide anion ... 

An a-halosulfone 1 reacts with a base by deprotonation at the a -position to give a carbanionic species 3. An intramolecular nucleophilic substitution reaction, with the halogen substituent taking the part of the leaving group, then leads to formation of an intermediate episulfone 4 and the halide anion. This mechanism is supported by the fact that the episulfone 4 could be isolated. Subsequent extrusion of sulfur dioxide from 4 yields the alkene 2 ... 

The halogens are far too reactive to occur in nature as the free elements. Instead, they are found as halide anions—... 

The tendency of the halogens to form chain-like polyanions that are stabilized by delocalization of the negative charge [15,34] is a basic chemical principle. Donor-acceptor interactions between Lewis-acidic Br2 and halide anions, but also with polyhalides acting as Lewis bases, give rise to the formation of a variety of homo and heteroatomic adducts. The maximum number of atoms in these chains increases with the atomic weights... 

TABLE 8.7 per Mole Cation Enthalpies of Hydration, AWhyd, at 25°C, of Some Halides, Anion in Kilojoules... 

In the halide-assisted method,25 a glycosyl halide (normally bromide) with a nonparticipating 2-substituent and with the thermodynamically more stable axial orientation at C-l is treated with an excess of the corresponding halide anion by the addition of a soluble tetraalkylammonium salt. This sets up an equilibrium between the axial and the (much less stable) equatorial glycosyl halide. The lat-... 

Last, the nickel catalyzed halogen exchange for haloarenes, actually the arylation of halide anions, has been investigated. The equilibrated exchange between the phenyl bromide (60 %) and the phenyliodide (40 %) allows with some... 

The palladium(O) complex undergoes first an oxydative addition of the aryl halide. Then a substitution reaction of the halide anion by the amine occurs at the metal. The resulting amino-complex would lose the imine with simultaneous formation of an hydropalladium. A reductive elimination from this 18-electrons complex would give the aromatic hydrocarbon and regenerate at the same time the initial catalyst. 

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