Relative stabilities of cycloakanes. Why all cycloakanes do not show similar stabilities?

Why cyclopropane is most

reactive cycloalkane? Why cycloakane has 5 or more carbons are as stable as their open chain counterparts? Such
questions can be answered on the basis of a very important generalization made by Aldof von Baeyer in 1885. His
arguments for relative stability of different cycloalkanes lead to a theory commonly known as Baeyers strain theory.
The main postulates of this theory are as under
1.
2.
3.

4.
5.
6.
7.
8.

If a carbon is fully saturated its hybridization is sp3, its geometry is tetrahedral and it will make make bond
with other atom that show a bond angle of 10928.
All cycloalkanes are planar or two dimensional. They resemble regular polygon (having same sides, same
internal and external angles)
Internal bond angles of polygons can be calculated using formul i.e. sum of internal angles of a polygon =
(n2)pi radians or (n2)180.The following table shows values of internal angles of different polygons or
cycloalkanes.
Cycloalkanes
Internal angles/bond angle
N = 3 cyclopropane
60
N = 4 cyclobutane
90
N=5 cyclopentane
108
N=6 cyclohexane
120
Thus no cycloalkane shows bond angle equal to normal tetrahedral bond angle i.e. 10928.
A deviation of bond angle from normal tetrahedral brings strain in the molecule or cycloalkane. This strain
is commonly referred as angle strain. This angle strain directly affects the stability of cycloalkane. Baeyer
proposed a formula for calculating angle strain as given below
Angle strain = [10928 bond angle in the ring]
This formula is valid if the angle in ring is acute. If the angle in the ring is obtuse the formula is
Angle strain = [bond angle in the ring 10928 ]
This is because angle strain is always positive. Magnitude of angle strain in different cycloalkane is
tabulated below
4. The stability of the ring depends upon angle strain. If angle strain is more the ring will be high in energy,
less stable and more reactive. The order of stability is
Cyclopropane < cyclobutane < cyclopentane > cyclohexane.
5. The greater the stability more should be ease of formation of ring. The order of stability as predicted by
Baeyer does not match experimental observations. Experimental observations show that cyclopropane is
most reactive followed by cyclobutane and cyclopentane. Cyclohexane and higher cycloalkanes are not
only have equal stability to each other but are as stable as their open chain counter parts. The theory was
accepted because higher cycloalkanes were not prepared or found in nature.
Evidences in support of theory. Experimental information available till that time was in agreement with the
theory. Other points that supported the theory were,
Reactivity of the double bond. A double bond can be regarded as a two membered ring with a carbon
carbon bond angle of 0. So, the angle strain for compounds having double bond (alkene, cyclalkenes and
their derivatives) is +5444 which is maximum for any cycloalkane. Thus these should be highly reactive
which they actually are. Thus this fact supported the theory.
Reactivity of lower cycloalkanes. The order of stability and reactivity for cyclopropane, cyclobutane and
cyclopentane was truly predicted by the theory was in agreement with experimental data. For example
when heat of combustion of cycloalkanes were studied we found that cyclopropane and cyclobutane were
possessing 38.5 kJ and 27.6 kJ of energy more than corresponding straight chain alkane (for each CH2)
group. So, they should be less stable and more reactive. Further, the value was much lower in case of
cyclopropane than in case of cyclobutane. So, cyclopropane should be more reactiove than cyclobutane
which actually is true. Cyclopropane inspite of absence of double bond show many addition reactions as
shown by alkenes.
Limitations of Baeyers strain theory. Some of the points as proposed by Baeyer were not in agreement
with the experimental observations. They are given below

According to Baeyers theory stability and ease of formation are directly linked. More stable rings should
be more easily formed where as less stable rings should be formed with difficulty. On this basis alkene
having double bond must not be formed easily which actually is not the case. We have many methods with
the help of which we can form them. Example dehydrohalogenation, dehalogenation, dehydration, etc.
On the basis of Baeyers strain theory rings having six, seven and more carbons should be less stable and
order of stability should be cyclopentane > cyclohexane>cycloheptane>cyclooctane. But heat of
combustion data shows that they are equally stable.
Due to these demerits it was proposed that they should be rejected. But with amendments made in the later
years this theory is still in use.
Heats of combustion and relative stabilities of cycloalkanes. We have studied in lower classes about heat of
combustion. It is defined as the amount of heat evolved when one mole of a compound is completely burnt
in air or free supply of oxygen to form oxides of constituting elements. For hydrocarbons the products are
carbondioxide and water.
This property furnishes valuable information regarding the stability of nthe compound and helps us to
compare stabilities of different compounds. Let us study the heats of combustions of cycloalkanes and
correlate these with their stability to check the validity of Baeyers strain theory.
From the table it is clear that heat of combustion per CH2 group are 696.4 and 685.5 kJ/mol respectively
and for cyclopentane and cyclohexane these are 663.4 and 657.9 kJ/mol respectively. For n-alkane its value
is 657.9 kJ/mol. By comparison we can access relative stabilities of different alkanes as compared to
stability of straight chain alkanes.
CH2 group on combustion will form 1 mole each of CO2 and H2O. CH2 + 3/2 O2 = CO2 + H2o + heat
It is considered that heat of combustion must be same irrespective of the molecule that contains it. It is
found true in case of all alkanes. However, in case of cyclopropane, cyclobutane and cyclopentane we find
deviation in value of heat of combustion for CH2 group. This shows that CH2 groups possess more energy.
Heat of combustion of each CH2 group when added will give value of total energy possessed by the
molecule of cycloalkane as cycloalkanes are polymethylenes.
So, total energy of cyclopropane will be much more than theoretical expected total energy of the molecule.
Additional energy possessed by the molecule indicates its lesser stability or higher reactivity.
The difference in total heat of combustion calculated theoretically and experimentally become a factor for
finding stability and reactivity. Higher difference means higher reactivity or lesser stability. Thus, the
relative reactivities on the basis of heats of combustion are cyclopropaane > cyclobutane > cyclopentane
>cyclohexane = all other higher cycloalkanes. On the basis of Baeyers strain theory the order of reactivity
is cyclopropane > cyclobutane > cyclopentane <cyclohexane <cycloheptane < cyclooctane and so on. Thus
the two orders do not match with each other. Experimental data is always correct. So there is problem with
theory. The first three members reactivity or stability found according to theory match with experimental
data. So, the theory is valid for them. Higher memberss data is against the theory so it is not valid for them.
In nutshell we can say Baeyers theory is not valid for stability or reactivity of higher cycloalkanes.
Sachse-Mohr theory of strainless rings. Untill now we donot have any new theory which can give the
reactivity order and heat of combustion value matching the experimental orders and values. So rather than
rejecting the angle strain theory we have accepted it as such for rings up to six carbons and modified form
of it has been applied to explain the reactivity or stability of higher rings or cycloalkane. The modifications
were suggested by Sachse and Mohr. They proposed theory of strainless rings. According to them all rings
occupy a stereochemistry most suitable to them in terms of stability. Rings will have or try to have three
dimensional structure if possible. No three dimensional structure is possible for three member as well as
four membered rings. They always have planar rings and live with angle strain.
On the other hand sp3 hybridised carbons form bonds in such a manner that out of all possible attachments
only those are picked which brings minimum strain .Thus, they acquire three dimensional structure.
cyclopentane rather than existing as regular pentagon exist as half chair or half boat. Similarly cyclohexane
in place of existing as regular hexagon exists in the form of chair or boat. These forms (3-D)which a ring
can occupy to get rid of angle strain are called conformation or conformers. Different conformation are free

from angle strain but may possess strain of other types like torsional strain, dihedral strain , etc. Higher
rings or cycloalkanes will always have puckered ring structure and show many conformations. Important
points or strain free ring are.
1 Except cyclopropane all rings will try to have puckered ring like structure. Cyclopbutane ring need not to
be planer. However, puckering in this case will increase angle strain. Similarly cyclopentane need not to be
planar but a planar arrangement here would permit bond angles to be nearly tetrahedral. If, energy is
provided or at high temperature, X-ray structures of cyclobutane and cyclopentane show their existence in
the form of puckered rings.
Higher rings can occupy many three dimensional structures which differ from eadch other in relative
positions of bonds in space though they always form a bond angle that is typical of sp3 hybridised atom
i.e10928. These different arrangements are called conformations.
Larger rings must be difficult to form as terminal carbons hardly come close enough to get overlapped, a
certain condition necessary for formation of sigma covalent bond. But once formed this bond will be very
stable sand so will be cycloalkane molecule. These modifications, when incorporated to Baeyers strain
theory, give a platform for discussing various aspects of chemistry of ringed compounds.
Now the question arises, if larger rings are stable why are they difficult to synthesis. Baeyers assumption
that a compound difficult to synthesise is necessarily unstable is incorrect. Actually for ring closure to
occur it is essential that the two ends of carbon chain possessing the functional groups must, come
sufficiently close together, to react with each other. This has lesser probability in case of long chain
compounds which act as precursors for larger cycloalkanes.
Under these conditions there would be greater probability for the two different chains coupling together
(intermolecular condensation) rather than the two ends of the same chain undergoing ring closure
(intramolecular condensation) as shown.
Thus the difficulty encountered in the synthesis of large membered ring is the competition between inter
and intra molecular condensation. Inter molecular condensation is preferred over intra molecular
condensation. However, recently this difficulty has been overcome by carrying out the reaction in highly
dilute solutions. Under these conditions the collisions between two different chains are minimized
considerably and intramolecular condensation or ring closure reaction, although slow is the principal
reaction. This is called Zeigler technique of eliminating intermolecular reaction competing with intra
molecular to form one product.
The Case of cyclopropane. (Banana bond). Since cyclopropane is known to be cyclic molecule all of the
CCC inter nuclear angles must be 60. An atom having valency of four cannot have angle less than 90
but cyclopropane molecule has no choice. They combine together somehow and form a geometry
corresponding to equilateral triangle. The angle strain is very high which comes into play due to large
distortion. Energy of activation is expected and actually found to be very high. If we draw Newmann
projections all the CH2 groups eclipse each other. All types of strain are present in the cyclopropane but the
difference in the heat of combustions is not that high. It is 115 kJ/mol. Quantum mechanical calculations
show that all hybridized orbitals of a carbon of cyclopropane do not have same share of s and p orbitals.
Orbitals which will participate in carbon-carbon bond formation will have more p-character. On the other
hand orbitals involved for forming CH bond have less p-character. Since p-orbitals are oriented at 90 to
one another, unlike 10928 orientation of sp3 hybridised orbitals. This helps to relieve the strain present in
the ring system. The nature of bonding in the carbon-carbon bonds of cyclopropane has been depicted in
the diagram given below.
Such bonds are sometimes known as banana bonds from the spectral data (IR spectra) it can be seen that
the carbon-hydrogen bond of cyclopropane resemble those of ethane (sp2-hybridised carbon. Thus some
share of p-orbital will pass on to carbon. Another proof comes from the behavior of cyclopropane during its
chemical reactions. It undergoes addition reactions much easily as compared to other cycloalkanes just like
alkenes. Some 9 kcal/mol of torsional strain has been observed in case of cyclopropane. We can see that
carbon-carbon bonds of cyclopropane are bent and pure sigma bond. The overlap in cyclopropane is neither

end on nor lateral, so it is a bond which is intermediate between the two. Thus the cyclopropane molecule
indicates new aspects of bonding which we not so often come across in normal molecules.
Arenes II
Introduction. After studying about the structure of benzene and similar aromatic compounds we now wish
to study their reactions. Due to presence of unsaturation it is expected that they will show addition
reactions like other unsaturated compounds. Contrary to expectations, they show electrophilic substitution
reactions. This contrast can be explained by considering delocalization of pi-electrons above and below the
carbon skeleton of benzene ring. Thus, aromatic compound can give electrons to incoming electrophile.
Attack of electrophile may complete with attack of nucleophile but this will lead to loss of aromaticity. In
order to maintain aromaticity they lose a proton to give substitution product. This class of reaction has been
extensively studied from the stand point of reaction mechanism, structure-reactivity relationship,
regioselectivity, stereoselectivity and applications in organic synthesis. This procedure offers facile
introduction of several functional groups on the aromatic ring. The groups can subsequently be treated for
conversion into other functional groups.
Aromatic electrophilic substitution (AES) General pattern of mechanism. All carbons in benzene are sp2
hybridised and thus are expected to show addition reactions. In place of this it shows electrophilic
substitution reactions. High degree of conjugation or delocalization results in presence of two pi electron
clouds- one lying above and other below the plane of the ring. When benzene reacts it does so by using its
sigma electrons of CH bond which cleaves and some group similar to outgoing H (leaves as H+) forms a
sigma bond with carbon. We know that pi-electrons are more prone for participation as compared to sigma
electrons as they are loosely held by sp2 hybridised carbon. On looking at products it appears as if they
remain intact during the reaction. Mechanistically the reaction is considered to proceed by one of the
following sequences. 1. Electrophilic substitution involves loss and gain of electrophile. Leaving
electrophile is H+ and new electrophile can be any commonly available electrophile (here represents as E+
in general). It is suggested that breaking of CH bond and making of CE bond occurs simultaneously. In
simple words it is considered to be a concerted reaction. A transition state is supposed to be involved (cf.
SN2 reaction).
Here we consider the reaction to occur in two steps. In the first step attack of electrophile on a carbon of the
ring. The sigma bond between the carbon and incoming electrophile is formed at the cost of one pi-bond.
This forms a resonance stabilized carbocation intermediate which is commonly called Wheland
intermediate or arenium ion intermediate or sigma complex.
In the second step this resonance stabilised carbocation intermediate loses a proton to restore aromaticity
and gives substitution products. It is difficult to predict rate determining steps without further studies. The
diagrammatic representation of these two steps is shown below:
Which out of the two mechanisms is actually followed by the reactants to change into products? Additional
experimental studies helped us to reach the conclusion that the second mechanism is mostly followed.
Evidences in support of this two step reaction mechanism. Wheland intermediate or arenium ion
intermediate or sigma complex has not only been detected but has also been isolated in several cases. When
nitration is carried out for trifluoromethylbenzene or benzotrifluoride using nitrilefluoride in the presence
of Lewis acid like BF3 as catalyst at 193 K, we obtain a yellow crystalline compound. This is ionic
compound having Wheland intermediate and BF4 anion. This complex upon heating to 223 K
decomposes to form metanitrobenzotrifluoride, BF3 and HF. This reaction is written below:
The intermediate involves actual sigma bond formation between NO2+ (electrophile) and meta positioned
carbon of benzene ring. This type of intermediate is commonly known as sigma complex.
Another example where similar sigma complex intermediate formed is detected and isolated in reaction of
mesitylene with fluoroethane (giving ethyl carbocation which act as electrophile) in presence of catalyst
like BF3 at 193 K.This upon heating undergoes dissociation resulting in formation of 2-ethylmesitylene,
BF3 and HF.
All arenium cations can be detected with the help of most widely used spectroscopic techniques i.e. NMR
at low temperature (134C).

Isotope effect. Aromatic hydrocarbons do not show isotope effect during Electrophilic substitution
reactions. It means rate of second step which involves cleavage of CH bond to get back aromaticity
remains unchanged even when H is replaced with its isotopes (D, deuterium or T, tritium). From this we
can conclude that second step is not the rate determining step. Hence, first step i.e. formation of Wheland
intermediate or arenium ion intermediate or sigma complex is slow and rate determining step. The lower
reactivity towards formation of carbocation can be assigned to extra stable nature of aromatic compounds
due to aromaticity and resonance energy.
Now, from these two evidences we can say that reaction do not follow one step or concerted mechanism as
we do not have any experimental proof or evidence in its favour.
Substitution Vs addition reaction. After studying general mechanism of Electrophilic substitution reactions
of benzene and similar compounds a question arises, why the intermediate cation formed in the first step of
the mechanism does not add nucleophile to form the product. In simple words, why substitution is preferred
over addition reaction in case of benzene and other aromatic hydrocarbons. In other unsaturated
hydrocarbons addition is preferred over substitution. Answer to this question is very simple. In aliphatic
unsaturated compounds addition is preferred because it releases more energy than that for substitution
reaction. Same does not happen in case of aromatic hydrocarbons because of following reasons:
Aromatic compounds are extra stable due to resonance. Attack of electrophile leading to formation of
Wheland intermediate or arenium ion intermediate or sigma complex involves loss of aromaticity and
cleavage of pi-bond. Both these actions need energy.
If nucleophile attaches to positively charged carbon atom, the product will not be aromatic. Energy
corresponding to bond formation is released which is much less than the energy of activation for the first
step. This makes overall reaction highly endothermic.
If proton is given away the electrons of CH bond are transferred to ring and aromaticity is restored. Here,
larger amount of energy is released which compensates for high energy of activation for first step.
It is obvious nature favours the process which either releases the energy or absorbs lesser energy. From this
fact and data of energies for addition and substitution reactions, the later is favoured due to its requirement
of lower energy.
Thus, benzene and other aromatic compounds do not undergo Electrophilic addition reaction since the
second step is endothermic at least by 150.48 kJ/mol (= resonance of energy of benzene). One more fact
has become clear from the discussion. It is slow reactivity of benzene and other aromatic hydrocarbons as
compared to alkenes. Alkenes and aromatic hydrocarbons form carbocations in similar fashion but changes
brought by attacking electrophile in them are different. Alkenes do not have resonance stabilization and
thus are converted directly into carbocations. Aromatic hydrocarbons absorbs energy equal to resonance
energy and then allow the attack of electrophile. Thus total activation energy is much higher for aromatic
hydrocarbons. On comparing rates of reactions of alkenes and aromatic hydrocarbons it has been observed
that rate of reaction is directly proportional to the stability of the compound. More is the stability, lesser is
the reactivity. Any group or factor that reduces the resonance in aromatic hydrocarbons must increase the
rate of Electrophilic substitution reactions.
Role of sigma and pi-complex. From the pattern of Electrophilic substitution mechanism formation of
sigma complex is proved. Formation of sigma complex is not easy due to resonance or delocalized nature
of pi-bonds in the aromatic hydrocarbons. This is because the electrophile must stay close to carbon till the
energy required for dearomatisation (loss of aromaticity) is absorbed and three pi-bonds start behaving like
isolated double bonds. This on one side provide justification of high energy requirement for the reaction,
slow rate of reaction, etc. and on the other hand indicates that some action does occur before formation of
sigma complex or Wheland intermediate.
Detailed experimental studied and quantum mechanical considerations suggest that formation of sigma
complex precedes formation of another complex called pi-complex. Thus complete reaction has following
steps:
Mixing of aromatic hydrocarbons with electrophile or electrophile generating species in a proper solvent.
Formation of pi complex between the two due to physical forces of attraction.

Absorption of energy to destroy aromaticity and formation of sigma complex (actual bond formation) or
Wheland intermediate or arenium ion intermediate.
Loss of proton from the carbon which has formed bond with the electrophile to form the product.
Loss of energy due to resonance on restoration of aromaticity.
It has been proved that pi-complexes are formed before formation of sigma complex. Let us see details of
this with the help of following examples,
Benzene was treated HCl in the presence of anhydrous AlCl3. On mixing we obtain a coloured complex
which was capable of conducting electricity proving it to be ionic in nature. Then, HCl was replaced with
DCl in the above reaction. Benzene protons were exchanged with deuterium. The proton deuterium
exchange can be explained if we consider attacking deuterium as attacking electrophile. This got attached
to carbon and sigma complex was formed. Proton and deuterium became equivalent and proton was
released to restore stability, aromaticity and complete the reaction (exchange).
The same experiment was performed but in the absence of AlCl3. 1:1 complex was again formed. But the
solution of the complex did not show the properties of sigma complex formed previously. The solution of
complex was colourless and did not conduct electricity. On replacing HCl with DCl no proton-deuterium
exchange was observed. The benzene recovered did not contain any deuterium. Thus, the complex formed
between benzene and HCl was a pi-complex where no bond was actually formed. On replacing HCl with
DCl we obtained a new complex between benzene and DCl but due to non-bond formation protons of
benzene were not exchanged. They remain associated only by electrostatic forces of attraction. So, picomplex is a result of attraction of positive charge on the electrophile with pi-electron cloud of benzene or
other aromatic hydrocarbons.
Hence we can conclude that role of sigma and pi-comleses is to facilitate the process which otherwise is
slow, high energy requiring and difficult to occur. More over sigma complex can not be formed without
formation of pi-complex. Thus, the complete picture of mechanism of Electrophilic substitution would be
as follows:
After proving the formation of pi-complex and sigma complex during Electrophilic substitution reactions of
benzene and other aromatic hydrocarbons a new problem is faced by us. Which complex is formed first? To
answer this we have to study energy profile diagrams for aromatic Electrophilic substitution reactions. If
the rate determining step of the reaction involves the formation of pi-complex, the energy profile diagram
for aromatic Electrophilic substitution reaction is shown below:
However, if the rate determining step of the reaction involves the formation of sigma complex, then the
energy profile diagram for the AES reaction is shown below:
Many reactions were experimentally studied and it was concluded that pi-complex is formed first and then
it changes into sigma complex or Wheland intermediate. The energy profile diagram also supports this
conclusion. From first figure, the formation of sigma complex requires less energy than for formation of picomplex. Second step involving conversion of pi-complex to sigma complex is exothermic and for
conversion of sigma complex to pi-complex is endothermic. This means reaction needs lesser energy in the
beginning followed by a kick (in the form of energy), if the pi complex is preceded by sigma complex. The
reaction starts with difficulty and then sails smooth if sigma complex is preceded by pi-complex. The latter
case is observed in almost all the examples. Thus, the conclusion is that pi-complex formation is fast and
reversible and its conversion into sigma bond is slow and thus rate determining. For example,
Electrophilic substitution reactions of benzene. We have studied pattern for AES reactions in general. Now
we will study some examples of electrophilic substitution reactions of benzene. Most commonly occurring
electrophilic substitution reactions of benzene are
Nitration
Halogenations
Sulphonation
Mercuration
Friedal-Craft alkylation
Friedel-Craft acylation

Nitration. Benzene and other aromatic hydrocarbons undergo nitration (replacement of H with NO2), when
treated with nitrating mixture at high temperature. Mixture of concentrated nitric acid and H2SO4 is
commonly known as nitrating mixture. The product obtained is nitrobenzene or nitroarene depending upon
the starting material chosen.
Mechanism. Various steps involved in the reaction are as follows:
Generation of electrophile. Electrophile for this reaction is nitronium ion (NO2+). It can be generated by
the reaction of conc. HNO3 with Conc. H2SO4). Conc. HNO3 accepts a proton and results in formation of
protonated nitric acid, which, with the loss of water generates the NO2+ electrophile.
Formation of sigma complex or arenium ion or carbocation intermediate. Nitronium ion formed in the first
step attack one of the pi-bond of the benzene ring resulting in formation of sigma complex carbocation or
Wheland intermediate or Arenium ion. This ion is resonance stabalised through various resonating
structure. Formation of this intermediate is rate determining step because it is slow as compared to other
steps.
Loss of proton by intermediate. The resonance stabilised intermediate loses a proton to form nitrobenzene
as product. Proton is taken up by the base to generate H2SO4. This step is fast and thus does not effect rate
of reaction.
Evidences in support of mechanism. Following observations during the reaction can be put as evidences in
favour of above described mechanism.
Nitronium ion is the attacking electrophile. Any substance which is capable of producing nitronium ion can
be used for bringing about the nitration of benzene. Most commonly used nitronium salt for nitration of
benzene are nitronium perchlorate (NO2+ClO4), nitronium nitrate (NO2+NO3), and nitronium
tetrafluoroborate (NO2+BF4). The ease with which NO2+ ion is released by the salt influences the rate of
reaction. The rate of reaction is same as that of reaction with standard reagent (nitrating mixture).
Isotope effect. The above described mechanism is also supported by isotope effect. If we carry out nitration
of benzene and hexdeuterated benzene the rate of both the reactions are same. This means loss of proton or
deuterium cation has no role in determining the rate of the reaction. If this step would have been rate
determining step, then rate of two reactions must have been different. This is diagrammatically represented
as:
Halogenation. Replacement of one H of benzene or other aromatic hydrocarbons (arenes) is known as
halogenations. This is another example of AES reaction of aromatic hydrocarbons (benzene and arenes).
Reaction occurs at low temperature (310 320 K) as compared to other electrophilic substitution reactions
which occurs at high temperature when carried out in the presence of lewis acids such as anhydrous FeCl3
or AlCl3. The mechanism of the reaction involves following steps.
Generation of electrophile. Halogens combine with Lewis acids like AlCl3 to form chloronium ion (Cl+)
and aluminium tetrachloride (AlCl4) anion.
Formation of sigma complex or carbocation intermediate. The chloronium ion formed as a result of
dissociation of AlCl3.Cl2 complex attacks one of the carbons of benzene and results in formation of sigma
complex or Wheland intermediate or arenium ion which is resonance stabilised by resonating structures
shown below:
This step is slow and hence is rate determining step of reaction.
Loss of proton by intermediate. The resonance stabilised intermediate loses a proton to form halobenzene
as product. Proton lost here reacts with AlCl4 to form HCl and AlCl3. This step is fast and does not effect
rate of reaction. This reaction is called direct halogenations of benzene or arenes.
Other methods are also available for halogenations of benzene or arenes. One method is use of hypohalous
acid (hypochlorous acid or hypobromous acid in the presence of strong acids. Proton from strong acid adds
on oxygen of hypohalous acid to produce corresponding oxonium ion (unstable) which gives positive
charge on halogen upon dissociation during the attack on benzene or arene carbon. Thus areneium
carbocation is formed (sigma complex). This being slow is rate determining step. Other steps are same.
Another method uses interhalogen compounds inplace of halogens in the presence of Lewis acids such as
anhydorous AlCl3. A very interesting thing is observed in this case. The more electropositive halogen of the
interhalogen compound act as electrophile and corresponding halobenzene is formed. This is shown below:

Use of ICl will give iodobenzene (not chlorobenzene). The mechanism follows the same pattern as
discussed in case of halogenations.
Use of BrCl will give bromobenzene (not chlorobenzene).
Use of IBr will give iodobenzene (not bromobenzene)
Use of ClF will give chlorobenzene (not fluorobenzene)
Sulphonation
Mercuration
Friedal-Craft alkylation
Friedel-Craft acylation