Mechanisms halides

These reactions follow first-order kinetics and proceed with racemisalion if the reaction site is an optically active centre. For alkyl halides nucleophilic substitution proceeds easily primary halides favour Sn2 mechanisms and tertiary halides favour S 1 mechanisms. Aryl halides undergo nucleophilic substitution with difficulty and sometimes involve aryne intermediates. 

In the conversion of alcohols into alkyl halides, the mechanism is probably ... 

Two mechanisms have been proposed for the Wurtz reaction (compare Section III,7) and for the Wurtz-Fittig reaction. According to one, sodium reacts with the alkyl halide to produce a sodium halide and a free radical, which subsequently undergoes coupling, disproportionation, etc. ... 

The mechanism of acylation with acyl halides is usually regarded as involving the acyl cation (acyl carbonium or acylium ion) ... 

I.l.IJ Reactions nitlr 1,2-, 1.3-. ami 1.4-dienes. The reaction of conjugated dienes with aryl and alkenyl halides can be explained by the following mechanism. Insertion of a conjugated 1.3-diene into an aryl or alkenylpalladium bond gives the T-allvlpalladium complex 243 as an intermediate, which reacts further... 

The o-keto ester 513 is formed from a bulky secondary alcohol using tricy-clohexylphosphine or triarylphosphine, but the selectivity is low[367-369]. Alkenyl bromides are less reactive than aryl halides for double carbonyla-tion[367], a-Keto amides are obtained from aryl and alkenyl bromides, but a-keto esters are not obtained by their carbonylation in alcohol[370]. A mechanism for the double carbonylation was proposed[371,372],... 

Lithiation at C2 can also be the starting point for 2-arylatioii or vinylation. The lithiated indoles can be converted to stannanes or zinc reagents which can undergo Pd-catalysed coupling with aryl, vinyl, benzyl and allyl halides or sulfonates. The mechanism of the coupling reaction involves formation of a disubstituted palladium intermediate by a combination of ligand exchange and oxidative addition. Phosphine catalysts and salts are often important reaction components. 

It has been reported that the reactions of 2-aminothiazoles and sulfonyl halides generally afford mono sulfonyl and disulfonyl (171) compounds (Scheme 109) (355-362). Angyal (358) explained this result by a mechanism where in. the first reaction the product would be the cation (172)... 

Many patents and studies are still published in the field of thiazolo dyes because the photographic industrx is always looking for new sensitizing dyes with improved efficiency and eager to know more about the mechanisms of their action on silver halide. 

The use of sensitizing dyes in photography has been the subject of many studies and constitutes. still now. one of the most studied areas in specialized periodic publications (125, 126) or in textbooks (88. 127). It can be ascertained that one hundred years after Vogel s discovery of spectral sensitization, the basic mechanisms of action of dyes on their silver halide support still remain not fully understood. However, the theoretical reasons explaining why among many other dye families practically only cyanine methine dyes appear to be spectral sensitizers (128) are better known. 

While developing the connections between structure reaction and mechanism we will also extend the fundamentals of lUPAC nomenclature to functional group families beginning with alcohols and alkyl halides... 

The procedures to be described m the remainder of this chapter use either an alkane or an alcohol as the starting material for preparing an alkyl halide By knowing how to prepare alkyl halides we can better appreciate the material m later chapters where alkyl halides figure prominently m key chemical transformations The preparation of alkyl halides also serves as a focal point to develop the principles of reaction mechanisms... 

Mechanism of the Reaction of Alcohols with Hydrogen Halides... 

MECHANISM OF THE REACTION OF ALCOHOLS WITH HYDROGEN HALIDES... 

The reaction of an alcohol with a hydrogen halide is a substitution A halogen usually chlorine or bromine replaces a hydroxyl group as a substituent on carbon Calling the reaction a substitution tells us the relationship between the organic reactant and its prod uct but does not reveal the mechanism In developing a mechanistic picture for a par ticular reaction we combine some basic principles of chemical reactivity with experi mental observations to deduce the most likely sequence of steps... 

One important experimental fact is that the rate of reaction of alcohols with hydro gen halides increases m the order methyl < primary < secondary < tertiary This reac tivity order parallels the carbocation stability order and is readily accommodated by the mechanism we have outlined... 

Reaction of Primary Alcohols with Hydrogen Halides The Sn2 Mechanism... 

The SnI mechanism is generally accepted to be correct for the reaction of tertiary and secondary alcohols with hydrogen halides It is almost certainly not correct for methyl alcohol and primary alcohols because methyl and primary carbocations are believed to be much too unstable and the activation energies for their formation much too high for them to be reasonably involved The next section describes how methyl and primary alcohols are converted to their corresponding halides by a mechanism related to but different from S l... 

REACTION OF PRIMARY ALCOHOLS WITH HYDROGEN HALIDES THE Sn2 MECHANISM... 

The first step of this new mechanism is exactly the same as that seen earlier for the reaction of tert butyl alcohol with hydrogen chloride—formation of an alkyloxonmm ion by proton transfer from the hydrogen halide to the alcohol Like the earlier exam pie this IS a rapid reversible Brpnsted acid-base reaction... 

It IS important to note that although methyl and primary alcohols react with hydro gen halides by a mechanism that involves fewer steps than the corresponding reactions of secondary and tertiary alcohols fewer steps do not translate to faster reaction rates Remember the order of reactivity of alcohols with hydrogen halides is tertiary > sec ondary > primary > methyl Reaction rate is governed by the activation energy of the slowest step regardless of how many steps there are... 

Thionyl chloride and phosphorus tribromide are specialized reagents used to bring about particular functional group transformations For this reason we won t present the mechanisms by which they convert alcohols to alkyl halides but instead will limit our selves to those mechanisms that have broad applicability and enhance our knowledge of fundamental principles In those instances you will find that a mechanistic understand mg IS of great help m organizing the reaction types of organic chemistry... 

Chemical reactivity and functional group transformations involving the preparation of alkyl halides from alcohols and from alkanes are the mam themes of this chapter Although the conversions of an alcohol or an alkane to an alkyl halide are both classi tied as substitutions they proceed by very different mechanisms... 

Primary alcohols do not react with hydrogen halides by way of carbo cation intermediates The nucleophilic species (Br for example) attacks the alkyloxonium ion and pushes off a water molecule from carbon m a bimolecular step This step is rate determining and the mechanism is Sn2... 

These common features suggest that carbocations are key intermediates m alcohol dehydra tions just as they are m the reaction of alcohols with hydrogen halides Figure 5 6 portrays a three step mechanism for the acid catalyzed dehydration of tert butyl alcohol Steps 1 and 2 describe the generation of tert butyl cation by a process similar to that which led to its for matron as an intermediate m the reaction of tert butyl alcohol with hydrogen chloride... 

The E2 mechanism is followed whenever an alkyl halide—be it primary second ary or tertiary—undergoes elimination m the presence of a strong base... 

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... 

Typically elimination by the El mechanism is observed only for tertiary and some secondary alkyl halides and then only when the base is weak or m low con centration Unlike eliminations that follow an E2 pathway and exhibit second order kinetic behavior... 

There is a strong similarity between the mechanism shown m Eigure 5 12 and the one shown for alcohol dehydration m Eigure 5 6 The mam difference between the dehy dration of 2 methyl 2 butanol and the dehydrohalogenation of 2 bromo 2 methylbutane IS the source of the carbocation When the alcohol is the substrate it is the correspond mg alkyloxonmm ion that dissociates to form the carbocation The alkyl halide ionizes directly to the carbocation... 

Like alcohol dehydrations El reactions of alkyl halides can be accompanied by carbocation rearrangements Eliminations by the E2 mechanism on the other hand nor mally proceed without rearrangement Consequently if one wishes to prepare an alkene from an alkyl halide conditions favorable to E2 elimination should be chosen In prac tice this simply means carrying out the reaction m the presence of a strong base... 

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