By protonation

Acids often generate hydride complexes by oxidative addition. The starting material in Equation 3.107, Mn(CO)5 , is Mn(-I), d , whereas the product, HMn(CO)j is Mn(I), d . 

When the starting materal is cationic and the acid is HX, X may coordinate before protonation. The mechanism shown in Equation 3.108 was deduced from kinetic data and confirmed by isolation of the neutral intermediate.  

Some metal-hydrides react with acidic reagents. For example, the HMn(CO)j formed by the protonation of Mn(CO)j evolves when dissolved in pure CF3SO3H (in Equation 

Hydride ligands often undergo protonation faster than the metal center.  

One reagent that is effective for the clean monoprotonation of reactive anions is ferf-butyl chloride (Equation 3.110), which is not acidic but undergoes a facile E2 elimination when attacked by strong bases. 

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MarkownikofT s rule The rule states that in the addition of hydrogen halides to an ethyl-enic double bond, the halogen attaches itself to the carbon atom united to the smaller number of hydrogen atoms. The rule may generally be relied on to predict the major product of such an addition and may be easily understood by considering the relative stabilities of the alternative carbenium ions produced by protonation of the alkene in some cases some of the alternative compound is formed. The rule usually breaks down for hydrogen bromide addition reactions if traces of peroxides are present (anti-MarkownikofT addition). 

Thus, the values calculated for effective polarizability at the nitrogen atom for a series of 49 amines carrying only alkyl groups was correlated directly with their proton affinities, a reaction that introduces a positive charge on the nitrogen atom by protonation (Figure 7-7) [40. ... 

This is followed by proton transfer to give the intermediate (IV). 

Strong acids catalyse nitration by protonating nitric acid, as shown below H2NO3+ + HSO4-,... 

The argtiments of Norman and his co-workers seem to give affirmative answers to the first and second of these questions, but it is doubtful if the available data further require such an answer for the third question. It can be argued that the crucial comparison made between the behaviour of benzyltrimethylammonium ion and protonated benzyl methyl ether is invalid, and that it is possible to interpret the results in terms of nitration by the nitronium ion, modified by protonation of the oxygen atom of the ether a case for the possible involvement of the nitro-nium ion in specific interaction leading to o-substitution has been made. ... 

Thompson points out that there is no evidence that adducts give other than acetates on thermolysis. The exocyclic methylene intermediate (iv) postulated by Robinson could arise by proton abstraction from a Wheland intermediate analogous to (vll) above, rather than from the adduct (in). Similarly its decomposition does not necessarily require the intermediacy of the adduct (v). The fact that i -methyl-4-nitromethylnaphthalene is the product even when the nitrating medium is nitric acid and nitromethane would then require no separate explanation. 

It is also possible to use NMR spectroscopy in acidic solvent for analytical purposes. The difference in chemical shift induced by protonation will allow in some cases the identification of the compound [e.g., phenyl or arylthiazoles (109)]. 

Furthermore a substance such as HCl that dissociates completely when dissolved m water also dissociates completely when dissolved m an alcohol Many important reactions of alco hols involve strong acids either as reactants or as catalysts In all these reachons the first step IS formation of an alkyloxonium ion by proton transfer from the acid to the alcohol... 

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... 

Addition begins m the usual way by protonation of the double bond to give m this case a secondary carbocation This carbocation can be captured by chloride to give 2 chloro 3 methylbutane (40%) or it can rearrange by way of a hydride shift to give a tertiary carbocation The tertiary carbocation reacts with chloride ion to give 2 chloro 2 methylbutane (60%)... 

Because acetylene is a far weaker acid than water and alcohols these substances are not suitable solvents for reactions involving acetylide ions Acetylide is instantly converted to acetylene by proton transfer from compounds that contain —OH groups... 

Of the two resonance forms A and B A has only six electrons around its positively charged carbon B satisfies the octet rule for both carbon and oxygen It is more stable than A and more stable than a carbocation formed by protonation of a typical alkene... 

Because electrophilic attack on benzene is simply another reaction available to a carbocation other carbocation precursors can be used m place of alkyl halides For exam pie alkenes which are converted to carbocations by protonation can be used to alkyl ate benzene... 

These reactions are usually performed in water or alcohols as solvents and the alkox ide ion intermediate is rapidly transformed to an alcohol by proton transfer The other involves acid catalysis Here the nucleophile is often... 

The mechanism of this reaction is outlined m Figure 17 8 It is analogous to the mech anism of base catalyzed hydration m that the nucleophile (cyanide ion) attacks the car bonyl carbon m the first step of the reaction followed by proton transfer to the carbonyl oxygen in the second step... 

Only the a hydrogens are replaced by deuterium m this reaction The key intermediate IS the enolate ion formed by proton abstraction from the a carbon atom of cyclopen tanone Transfer of deuterium from the solvent D2O to the enolate gives cyclopentanone containing a deuterium atom m place of one of the hydrogens at the a carbon... 

Notice too that the carbonyl oxygen of the carboxylic acid is protonated m the first step and not the hydroxyl oxygen The species formed by protonation of the car bonyl oxygen is more stable because it is stabilized by electron delocalization The pos itive charge is shared equally by both oxygens... 

Step 1 The carboxylic acid is protonated on its carbonyl oxygen The proton donor shown in the equation for this step is an aUtyloxonium ion formed by proton transfer from the acid catalyst to the alcohol... 

Activation of the carbonyl group by protonation of the carbonyl oxygen... 

Acetophenone is the isolated product it is formed from its enol by proton transfers ... 

The amide is activated toward nucleophilic attack by protonation of its carbonyl oxygen The cation produced m this step is stabilized by resonance involving the nitro gen lone pair and is more stable than the intermediate m which the amide nitrogen is protonated... 

This reaction is an example of a Dieckmann cyclization The anion formed by proton abstraction at the carbon a to one carbonyl group attacks the other carbonyl to form a five membered ring... 

Ester enolates generated by proton abstraction with dialkylamide bases add to aldehydes and ketones to give (3 hydroxy esters... 

The O acylation of phenols with carboxylic acid anhydrides can be conveniently catalyzed m either of two ways One method involves converting the acid anhydride to a more powerful acylatmg agent by protonation of one of its carbonyl oxygens Addi tion of a few drops of sulfuric acid is usually sufficient... 

Aldol Addition and Related Reactions. Procedures that involve the formation and subsequent reaction of anions derived from active methylene compounds constitute a very important and synthetically useful class of organic reactions. Perhaps the most common are those reactions in which the anion, usually called an enolate, is formed by removal of a proton from the carbon atom alpha to the carbonyl group. Addition of this enolate to another carbonyl of an aldehyde or ketone, followed by protonation, constitutes aldol addition, for example... 

Intermediate formation of formyl chloride is not necessary since the actual alkylating agent, HCO", can be produced by protonation of carbon monoxide or its complexes. However, it is difficult to obtain an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide. Suitable laboratory preparations involve the reaction of chlorosulfonic acid with formic acid or the reaction of ben2oyl chloride with formic acid ... 

Experiments ( P nmr) using 0.8 and 2 equivalents of octyhnagnesium chloride with ethyl ben2enephosphinate indicate that the nucleophilic displacement occurs first, foHowed by proton abstraction (80). Interestingly, the order of the two steps is reversed when methyhnagnesium chloride is used (81). This reaction demonstrates the difference ia reactivity between the octyl and the methyl Grignard reagents. 

Ca.ta.lysis by Protons. The discovery of hydrogen peroxide hydroxylation of phenol in the presence of strong acids such as perchloric, trifluoromethane-sulfonic, or sulfuric acids allows suppression of all previous drawbacks of the process (18,19). This mode of hydroxylation gives high yields (85% based on H2O2 at phenol conversion of 5—6%). It can be mn without solvents and does not generate resorcinol. Its main advantage rehes on... 

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