PART-I

TYPICAL COMPLEX ORGANIC REACTIONS

Carbocations (Carbonium Ions)

The carbonium ions are positively charged highly reactive intermediates and have six electrons in the outer shell of central carbon. They may be represented as
H R R C
+

R C
+

H 1 20

C H

H H

So they are very reactive toward any nucleophilic reagent i.e., one that will donate a pair of electrons to carbon to form a fourth covalent bond. Being positively charged they are stabilized inductively by electron-donating substances and rendered less stable by electron-withdrawing substituents. Since carbon of a carbonium ion is in an sp2 hybrid, the ion pair is planar with a vacant p orbital (as in ethylene) which is perpendicular to the plane of three covalent bonds to the carbon.

NOMENCLATURE
As early as 1902 Gomberg suggested that the word carbonium was inappropriate for such species because onium signifies a covalency greater than that of the neutral atom. But the nomenclature went on till about 1964 when George Olah and his coworkers found evidence by mass spectroscopy + the existence of a positively charged intermediate, the CH 5 ion. It was supposed to have been + + formed by the attack of H on CH bond to give the species CH 5 also called the methanonium ion.
C H 3 H + H H 3C H H
+ C H3 + H 2

It has a three centre, two electron bond. In this the formal covalency of carbon is five rather than three. On this basis Olah proposed that the word carbonium ion should be reserved for such penta3

CHAPTER

MECHANISMS IN ADVANCED ORGANIC CHEMISTRY

coordinated species, while other positively charged species originally called carbonium ions be given the name carbenium ions. Olah also suggested the nomenclature carbocations to encompass both the type of species and the IUPAC has accepted this proposal. Although pentacovalent ions are much rarer than other positively charged ions, the general word carbocation is used for all such species. It is interesting to note that another species, the ethanonium ion C2 H5 has also been reported in the gas phase by IR spectroscopy. So now the word carbocation is used to cover all such electron deficient and positively charged species, although some authors still prefer to use the word carbonium ions. The difference between carbenium and carbonium ions is summarized as follows: Carbocation property Carbenium ions
CH3 CH3 C CH3

Carbonium ions
CH 5

Example Number of covalent bonds to carbon No. of electrons in outer shell Electron deficiency

3 6 electron deficient

5 8 not electron deficient

The simplest example of carbenium ion is CH which is so unstable that it is rarely formed even 3 in gaseous phase. The more stable ones have been prepared in solution and in some cases even in the solid state. When in solutions they are formed in polar solvents where they get solvated. They may also be associated with a negative ion called gegenion. The ion pairs are formed in non polar solvents.

STRUCTURE AND STABILITY

The carbocations being reactive intermediates have short life and so they are unstable. But they have been rendered stable after being trapped in strongest super acids which are mixtures of fluorosulphuric and antimony pentafluoride dissolved in SO2 or chlorofluorosulphuric acid SO2CIF. Under these conditions their structure and stability have been correlated. In general, the greater the resonance and hyper-conjugation the greater is the stability of carbocation. The stability also depends on the field strengths. The following examples illustrate this point.

1. Stability depending on the number of canonical forms

We know that among the simple carbocations the order of stability is
te rtiary carb oca tio n secon da ry carb oca tio n p rim ary carb oca tio n

CARBOCATIONS (CARBONIUM IONS)

This is because the greater the number of canonical forms, the greater is the stability. Let us see the canonical forms from a tertiary and a primary carbocation.

Thus a tertiary carbocation like the above will give nine resonating structures while a primary will give only two hyperconjugative forms. This explains why tertiary carbocations are more stable than secondary which in turn is more stable than primary. This also explains why ethyl carbocation ( CH 3CH ) is more stable than methyl carbocation ( CH ). 2 3 In general the more the number of alkyl groups attached to the C, the greater is the stability. During hyperconjugation some charge delocalization occurs between the p-orbital of the positively charged carbon and the bond of the C-H. On the basis of hyperconjugation, among alkyl carbocations, tertiary butyl carbocation has been shown to be most stable, because in the following reaction,
(C D 3 ) 3 C + (C H 3 ) 3 C H (C H 3 ) 3 C + (C D 3 ) 3 C H

since the equilibrium constant = 1.97 which shows that the reaction proceeds more towards right confirming that tertiary butyl carbocation is more stable than (CD 3) 3 C . There appears to be less hyperconjugation in deuterium containing carbocation than (CD 3) 3 C . It has been shown that of all the alkyl carbocations the ter-butyl carbocation is most stable. Even the relatively stable t-pentyl and t-hexyl cations break up at higher temperatures to produce the t-butyl cation. Even methane, ethane and propane in presence of superacids produce t-butyl cation as the main product. Even paraffin wax and polyethylene give t-butyl cation. So the order of stability among alkyl carbocations is:
(CH 3 ) 3 C t-butyl carbocation

>

(CH 3 ) 2 CH isopropyl carbocation

>

CH 3CH 2 ethyl carbocation

>

CH3 methyl carbocation

Canonical forms can also be drawn for benzylic cations and allylic cations.
CH2 CH2 CH2 CH2 CH2

B e nzylic ca tio ns

MECHANISMS IN ADVANCED ORGANIC CHEMISTRY

CH2 CH2

CH2

CH

CH

CH2

a llyl ca tion s (Tw o ca no nica l structu res)

So the order of reactivity is:

C H 6 H 5 C H 2 > C H 2 = C H C H 2

> C H 3 C H 2C H 2

and the above is also their stability. Now lest us study the stability of triphenyl and phenylalkyl cations. The triphenylmethyl carbocation shows its stability because the positive charge on the carbon is distributed uniformly over a number of structures.
C C C

C C

e tc.

Thus a number of canonical structures is possible. Like triphenylmethyl cation, diphenylmethyl cation is also very stable. In some cases the carbocations are so stable that their salts have been A isolated in the solid state. The solid salt of triphenylmethyl cation with boron fluoride as (C6 H5 )3C BF4 is available commercially. Arylmethyl cations are further stabilized if they have electron-donating groups in ortho and para positions.

2. The stability increases when the positive charge is in conjugation with a double bond
This is due to increased delocalization of the positive charge over two atoms instead of being concentrated at one.
R C R C R C R R R C R C R R C R R R C R C R C R

3. The presence of a heteroatom adjacent to the cationic centre and bearing an unshared pair of electrons, like nitrogen, oxygen or halogen increases stability
Such ions are stabilized by resonance
R R C

.. O ..

R CH3 R C

..

CH3

CARBOCATIONS (CARBONIUM IONS)

Simple acyl cations have been prepared in solution and even in the solid state. It has been found that acetyl cation CH 3CO is as stable as ter-butyl cation. Their canonical forms are represented as:
R C O ..

..

O ..

It has been shown that although the positive charge is located on cation, this structure contributes more than that containing a triple bond. Therefore in general the carbocation stability is increased due to resonance.

4. Conjugation between the bent orbitals and p-orbitals of the cation

In this connection the case of cyclopropylalkyl cation and substituted cyclopropyl cations is interesting. Cyclopropylmethyl cation has been found to be more stable than benzyl cation and the stability increases with each addition of cyclopropyl groups. Thus
C CH

CH3 C CH3 D im e th ylcyclo pro pyl cation

D icyclop ro pyl cation

Th ricyclop ro pyl cation

This increased stability has been explained between the bent orbitals of cyclopropyl rings and the vacant p orbital of the cation carbon. The vacant p orbital lies parallel to C2C3 bond of the cyclopropane ring and not perpendicular to it. Thus the geometry becomes similar to that of a cyclopropane ring conjugated with an oblefinic bond.

Vacan t p o rb ital

C2

C3

The structure of carbocation has been measured by 13C nmr shift of the carbon atom carrying the positive charge. The shift agrees with the electron density on this carbon. The following table given by Olah and J. Denovan (J. Amer. Chem. Soc. 1977.90.5026) shows that substitution of an ethyl for a methyl group or a methyl for hydrogen causes a downfield shift showing that the central carbon becomes somewhat more positive. Table 1.1
Ions (C2H5)2C CH3 (CH3)2C C2H5 (CH3)3C HC(OH)2 C(OH)3 Chemical shift 139.4 139.2 135.4 +17.0 +28.0 Temperature C 20 60 20 30 50

The presence of hydroxy group decreases the positive character of the central carbon.

MECHANISMS IN ADVANCED ORGANIC CHEMISTRY

GENERATION OF CARBOCATIONS
Following are some of the methods used to generate carbocations. 1. By direct ionisation: The direct ionisation of alkyl halides gives carbocations.
S o lven t R+X R X (x = C l, Br, I)

The process is accelerated due to the presence of metal ions like Ag. 2. Form alkenes: A proton or other positive species adds to one atom of an unsaturated system leaving a positive charge on the adjacent carbon.
C Z+ H C Z H

3. Decomposition of an alkyl diazonium ions:

R N N R + N2

4. By protonation of alcohols: The protonated alcohols give carbocations on decomposition.

.. R OH + H .. R H OH .. R + H2O

5. By reaction of acyl halides in presence of anhydrous aluminium chloride: The FrielelCrafts acylation reactions came under this heading.
a nh yd ro us R COCl A lC l 3 RCO

A lC l 4

R C O + A lC l4

REACTIONS OF CARBOCATIONS
The carbocations being highly reactive intermediates of very short life react further without being isolated and give stable products. In general they give the following reactions: 1. 2. 3. 4. Reaction with nucleophiles Elimination of a proton Rearrangements Addition to unsaturated systems.

1. Reaction with nucleophiles

The carbocations react with species, the nucleophiles
R + Y

R Y

Y = O H , halide ion or may be even a neutral species.

CARBOCATIONS (CARBONIUM IONS)

Br C H3 C C H3 C H3 C H3 C C H3 + O H

Br

C H3

C C H3 C H3

..

C H3

C C H3

O H

..

C H3 C H3 C C H3 OH + H

2. Elimination of a proton
In this process the elimination of a proton results in the formation of an alkene. Thus the dehydration of alcohols gives rise to alkene in presence of conc. H2SO4.
R C H2 C H2 OH ..

..

H .. H 2 O RCH 2 CH2 OH .. H C H2

C H2

C H2 or

C H

RCH = CH2

1 catio n

It m ay re arra ng e RCH CH3 2 catio n

So carbocations can adopt two pathways to give the stable product.

3. Rearrangements
As shown in the example due to rearrangement 1 carbocation rearranges to 2 cation. This rearrangement may involve the migration of a hydrogen with its pair of electron when it is called the hydride shift or it may involve the migration of an alkyl group with its bonding electrons in which case it is called the alkyl shift. They hydride shift is given in the above example. The alkyl shift may be represented as
H C R C H C H C R H

4. Addition to unsaturated systems

A carbocation may add to an alkene producing a new positive charge at a new position as shown in the following example.

10

MECHANISMS IN ADVANCED ORGANIC CHEMISTRY

C H3 R C H C H 2 + C C H3 C H3 R CH C H2 C H3 C C H3 C H3

Formed by any of the two methods, the new carbocation reacts further to stabilize itself. This generally happens either by reacting with a nucleophile or by the loss of a proton. If the new cation formed by union with an alkene further combines with an alkene, this will result in the formation of a polymer. A number of reactions have been explained on the basis of generation of carbocations. The examples include the Friedel-Crafts alkylation and arylation reactions. Besides pinacol-pinacolne rearrangement, Beckmann rearrangement and Wagner-Merwein rearrangement are other examples.

NON-CLASSICAL CARBOCATIONS OR BRIDGED CARBOCATIONS

The carbocations so far studied are called classical carbocations in which the positive charge is localized on one carbon atom or delocalized by resonance involving an unshared pair of electrons or a double or triple bond in the allylic positions (resonance in phenols or aniline). In a non-classical carbocation the positive charged is delocalized by double or triple bond that is not in the allylic position or by a single bond. These carbocations are cyclic, bridged ions and possess a three centre bond in which three atoms share two electrons. The examples are 7-norbornenyl cation, norbornyl cation and cyclopropylmethyl cation.
H 7 4 5 3 6 (1 ) 7 5 1 6 n orb orn yl cation 2 CH2 CH CH2 cyclo p rop ylm eth yl cation 3 CH2 2 2 (a) 2 (b) 4 3 1 2 1 (a) 7 -no rbo rn en yl catio n 1 (b) 1 (c) H H

CH2

CH

CH2 CH2 CH2 3 (b) CH CH2

CH2 3 (a)

CARBOCATIONS (CARBONIUM IONS)

11

It we accept the existence of bridged ions, the question to be answered is why should such ions be formed in preference to classical carbocations in any particular reaction. One reasonable answer is that when several intermediates are possible, the most stable one is the one likely to be formed. Since charge is most diffuse in the bridged ion than in the classical ion, the bridged structure would be expected to be more stable than the classical structure.

GENERATION OF NON-CLASSICAL CARBOCATIONS

The non-classical carbocations can be generated if proper substrate is chosen. For example the norbornyl carbocation can be generated by the departure of a leaving group from an exosubstitued substrate

ro ute X Y e xo su b stitu ted n orb orn yl com p un d 4

ro ute X

4 (a)

4 (b)

This is called the route to a non-classical carbocation because of the participation of a bond. If a bond is involved then it is called a route. Many chemists aruge that the structure written from 7-norbornenyl cation are not non-classical carbocations because they are not canonical forms but real structures and there is rapid EQUILIBRIUM between them.

Distinction between neighbouring group participation and non-classical carbocation

It is important to distinguish between neighbouring group participation and non-classical carbo-cation. A non-classical carbocation can be formed due to participation of several species as a neigh-bouring group. Some of these neighbouring groups are

1. C = C as a neighbouring group

Here we have a c = c group attached to a carbon atom which is adjacent to be carbon atom where nucleophilic substitution can occur and during the course of the reaction 5 (a) 5 becomes bonded of partially bonded to the reaction centre to form a non-classical or bridged ion (Fig. 1 to 1(c)). Thus the rate and/or the stereochemistry may be affected. This explains why the acetolysis of 5 is 1011 times faster than that of 5(a), because it involves the formation of a non-classical carbocation

2. The carbon-carbon single bond as a neighbouring group

This has been explained in Fig. (2 2(b)) and also in Fig. (3 to 3(b)).

3. The 2-nor-bornyl system

This is given in Fig. (2 to 2(b)).