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: CH2N = N:

<>

CH2 = N = N:

II

<-->

: CH2N = N:

HI

But these structures are not complete since the. formal charges on some of the atoms are missing. Let us
now calculate the formal charge on each of the atoms in all the three Lewis structures.
Lewis structure I
Formal charge on carbon = 4 - y x 6 - 2 = -1
Formal charge on central nitrogen = 5 - y * 8 - 0 = + l
Formal charge on terminal nitrogen = 5- ^ x 6 - 2 = 0
_
+
Thus, the complete Lewis structure (I) is : CH 2 N = N:
Lewis structure II
Formal charge on carbon = 4 - y * 8 - 0 = 0
Formal charge on central nitrogen = 5- y * 8 - 0 = + l
Formal charge on terminal nitrogen = 5 - y *4 - 4 = -1

+ .. _

Thus, the complete Lewis structure (II) is CH2 = N = N :


Lewis structure HI
Formal charge on carbon = 4 - y x 6 - 2 = - l
1
Formal charge on central nitrogen = 5- y * 6 - 2 = 0
' 1
'
1
Formal charge on terminal nitrogen = 5 - y x 4 - 2 = +1
-

Thus, the complete Lewis structure (III) is : CH2N = N:


Thus, diazomethane is a resonance hybrid of the following three Lewis structures:
CH2-N = N: <> CH2 = N = N f <>
CH2N = N:
1
11
HI
In each of the three Lewis structures written above, the sum of the formal charges is zero, therefore,
diazomethane as a whole is an electrically neutral molecule.
g g | METHODS OF DETERMINING REACTION MECHANISM
The mechanism of a reaction implies the path which the reactants follow on their way to products. Since
many chemical reactions proceed very rapidly (~ 1 0 ~ 1 4 5), it is not possible to follow the reaction path directly
and hence our knowledge about reaction mechanisms is mostly based upon indirect evidence. After
characterising the products, a number of mechanisms consistent with all the experimental observations are
proposed. In most of the cases, new experiments are carried out to eliminate some of these mechanisms If sac :
eliminations lead to only one mechanism then it is said to be the established mechanism of the reacti - Lr
general, the proposed mechanism for a reaction (i)'should be energetically favourable (it) should accouxx
all the experimental observations and (Hi) must be consistent with the mechanisms of the analogous -eiczc
A number of methods are used to determine the mechanism of a reaction. These include
ORGANIC CHEMISTRY VOL. 1.

(/') Product analysis {i.e. identification of products) (/;') Detection and isolation of the intermediates
(Hi) Isotopic labelling (;v) Isotope effects (v) Kinetic studies and (vi) Stereochemical studies.
All these methods are briefly discussed below. It may, however, be noted that it is not necessary to apply
all the methods to determine the mechanism of a particular reaction.
1. Product analysis. The first step in investigating the mechanism of a reaction is the identification of
products and determining their relative amounts. To illustrate this point, let us consider the following
reactions.
(/) The hydrolysis of two isomeric allyl chlorides (I and II) yields a mixture of 85% of a tertiary alcohol ^11)
and 15% of a primary alcohol (IV). Since the composition of the products remains to be the same in either case,
therefore, the hydrolysis of these two compounds occurs through a common intermediate (V)
ch,

CH

CH3CCH = CH2

C CI

CH3

I
C H 3 C t - C H j CH2

OH"

CH, -CCH = CH,


I
OH

(V)

3-Chloro-3 -methylbut-1 -ene (I)

Ionization

2-Methylbut-3-en-2-ol (III)
(5 Alcohol. 85%)

(-CP)

ch 3
i 1
c h 3 c = chch 2 -jl-c1

CH3C = CHCH2

4-Ch!oro-2-methylbut-2-ene (II)

'

OH"

>

ch3c = ci^-ch2oh
3 -Methylbut-2-en-1 -ol (IV)
(1 Alcohol, 15%)

(V)

ch 3

CH,

(//) Ketoximes* on treatment with an acid (H 2 S0 4 , H 3 P0 4 , PC15, SOCl2, etc.) undergo Backmann
rearrangement to give the corresponding substituted amides. Product analysis has revealed that during this
rearrangement, it is always the group anti (or trans) to the OH group which migrates and has thus helped to
determine the mechanism of the Beckmann rearrangement. Thus,
Ar-,.

/R

HCk

/V^

(V

C
II

PC15

Tautomenses

^Ar

-Ar

HCK
C
II

PCI5

^ H

N-Aryl acid amide

Syw-Alkyl aryl
ketoxime

R.
/V

Ar^

Ar-

'<*>H

/ R
V

Tautomenses

V -

A r

r-

.4nfi-Alkyl aryl
ketoxime

N-Alkyl acid amide

(/'//) Cross-over experiments. Cross-over experiments are quite useful in determining whether a particular
reaction is a one-step or a two-step process. In these experiments, the same reaction is carried out with a
mixture of two similar but non-identical reactants and the products thus obtained are analysed. To illustrate the
role of cross-over experiments in determining the mechanism of organic reactions, let us discuss Friesrearrangement of esters, VI and VII, which involve migration of the acyl or the aroyl group from the oxygen
' T h e prefixes syn and anti indicate the relationship o f f i r s t named group w.r.t. the hydroxyl grotlp.

MECHANISM OF ORGANIC REACTIONS

atom to the benzene ring. These two esters on treatment with anhyd. A1C13 under similar conditions undergo
rearrangement at approximately the same rate to give the products VIII and IX respectively.
OCOC 6 H 5
OH
OCOCH3
OH
Anhyd.

COC H

AICI3

COCH3

CH

CH 3
4-Tolylbenzoate

2-Hydroxy5-methylbenzophenone
(VIII)

(VI)

VI + VII

Anhyd.

AICI3

CH 3

2-Chloro-4methylphenyl
actate (VII)

:oi

VIII + IX +

CH

XOCH 3

2-Hydroxy-5methylacetophenone(X)

2-Hydroxy-3-chloro5-methylacetophenone
(IX)

OH
Cl\^k/COC6H5

kT
CH

2-Hydroxy-3chloro-5-methylbenzophenone(XI)

If the same reaction is now carried out with the mixture of these two esters (VI and VII) under similar
conditions, two possibilities arise :
(/) If the reaction occurs concertedly or in one step, the ester (VI) will always give the ketone (VIII) while
the ester (VII) will always give the ketone (IX).
(//) If, however, the reaction occurs in two steps, then the migrating group, /'.?.-6H5CO in ester (VI) and
CH3CO group in ester (VII) must become free during the course of the rearrangement, and hence cross-over
products, (X and XI) must also be formed in addition to the expected products (VIII and IX).
In actual practice, when the same reaction was carried out with the mixture of these two esters (VI and
VII), the cross-over products (X and XI) were also isolated in addition to the expected products thereby
confirming that Fries-rearrangement is a two-step process.
2. Detection and isolation of intermediates. Many organic reactions occur through formation of
intermediates which may either be stable or unstable. The stable intermediates are isolated and then characterised.
The unstable intermediates, on the other hand, are either detected by spectroscopic methods or are isolated by
trapping them with reactive substrates as discussed below :
(a) Isolation. If the intermediates are stable, they are usually isolated by stopping the reaction before it is
completed or by using relatively milder conditions. For example, three intermediates, i.e., N-bromoamide,
)

(RCONHBr), its anion, (RCO NBr) K+ and the isocyanate (RN = C = O) have been isolated in the Hofmann
bromamide rearrangement of 1 amides to 1 amines on treatment with Br2/KOH
O
O
O
II
.
.
K+ -KBr
KOH
B15/KOH
>
RCN
RCNHBr -h O'
RCNH2
2
-KBr,-H20
N-Bromoamide

1 Amide

-> RN = C = 0
Isocyanate

2 KOH

RNH2 + K 2 C0 3
1 Amine

Acylnitrene

Thus, any proposed mechanism for this rearrangement must account for the formation of all these
intermediates.

(b) Detection. Unstable intermediates are often detected by spectroscopic methods. For example,
intermedial of carbocation intermediates in ^ 1 (unimolecular nucleophilic substitution) and E j (unimolecular
elimination) reactions has been established by nuclear magnetic resonance (NMR) spectroscopy. S i m i l a r l y ,
carbocation intermediates such as XII in electrophilic substitution reactions have been characterized by their
NMR and electronic spectra.

+ H F + BF

O T

:H

CH

Mesitylene

(XII)

Free radical intermediates can be detected by electron spin resonance (ESR) spectroscopy.
(c) Trapping. Unstable intermediate can also be characterized by trapping. For this purpose, the reaction
is carried out in presence of a compound with which it is known to react rapidly.
(0 Carbene formed during photochemical decomposition of diazomethane can be trapped as cyclopropane
derivative when the decomposition is carried out in presence of cyclohexene.
T
/V

:CH2-LN s n :
Diazomethane

:CH 2

o ><Q

Cyclohexene

Carbene

Bicyclo[4.1.0]heptane
(A cyclopropane derivative)

(ii) Benzyne formed during decomposition of benzcnediazonium-2-carboxylate can be trapped by


anthracene to form triptycene.
O

cQN

0'

hv

-co2, - N 2
2

Benzenediazonium
-2-carboxylate

0 0 0 .

Benzyne
Triptycene

(iii) Carbocations are trapped by reacting them with nucleophiles. For example, the carbocation formed
during the addition of Br 2 to ethylene can be trapped by a number of nucleophiles such as I", N0~, H 2 0, etc.
^C
OHV2 ^ B r - f t r
CH2
Ethylene

BrCH2CH2Br

CH2CH2Br + BrCarbocation

NO;

Br"

-> 0 2 N0CH 2 CH 2 -Br

CH 2 CH 2 Br
ICH2CH2Br

Carbocation

H2O
-H

> HOCH2CH2Br

(iv) Free radicals can be trapped by carrying out the reaction in presence of nitric oxide with which it is
known to react rapidly. For example, free radical formed during thermal decomposition of azidoisobutyronitrile
(AIBN) is trapped by nitric oxide to form hydroxylamine derivative.
MECHANISM OF ORGANIC REACTIONS

CH \
CH:
3

-CH3

cN = NC<
CN

CN

-CH,

CH3-

3X

CH,"

+N a N
>C
I
CN

Free radical

Azidoisobutyronitrile

CN

CH \
3

c h /

C
I
CN

+ N0

(CH3)2Cx
(CH3)2C>1^(CH
I
CN
CN

'

3 ) 2

A hydroxylamine derivative

3. Isotopic labelling. The mechanism of many reactions can be studied by using molecules in which an
atom is substituted by its isotope. For example,
(i) Hydrolysis of esters. The mechanism of hydrolysis of an ester whether it involves acyl-oxygen or
alkyl-oxygen fission can be solved by hydrolysing -amyl acetate in H 2 18 0.
O

O
CH 3 COC 5 H n +H 2 1 8 0

OH"

CHC 18 0~ + (^H, ,OH

n-Amyl acetate

Since the hydrolysis yields an unlabelled alcohol and a labelled acid, hydrolysis of esters involves acyloxygen rather than alkyl-oxygen fission.
(ii) Cannizzaro reaction. Cannizzaro reaction involves transfer of a hydrogen from one molecule to the
other. The question whether the hydrogen which gets transferred comes from water or the aldehyde can be
solved by carrying out the reaction with deuterated benzaldehyde (C6H5CDO) instead of benzaldehyde.
O

+ OH"

2C 6 H r

H2O

C6H5CO" + C6H5CD2OH

Deuterated benzaldehyde

Deuterated benzyl alcohol

Since the deuterium is exclusively located on the carbon atom of the benzyl alcohol carrying the hydroxyl
group, the possibility of exchange of hydrogen with the hydrogen atom of water is ruled out. Thus, there is
transfer of deuterium (or hydrogen) from the carbonyl group of one molecule to the other and during this
transfer, deuterium (or hydrogen) never gets detached.
A plausible mechanism consistent with the above observations can be visualized as follows :
<>0
-D +/

i
C6H5C^-D

OH

O
II

C H CO"+C H CD OH

C6H5COH + C6H5-

Benzyl alcohol-a-d2

Further, support to the above mechanism comes from the observation that when the reaction of
benzaldehyde was carried out in D 2 0, the recovered alcohol contained no a-deuterium indicating thereby that
the hydrogen comes from another molecule of aldehyde and not from the solvent.
If!
" O R G A N I C :v'CHEMISTRY V
"""O
L.1.

i^rct c f c e p ' s

(Hi) Nucleophilic substitution-Benzvne mechanism. When chlorobenzene is treated with NaNH2 in


liquid NH3, aniline is formed. The mechanism of this nucleophilic substitution reaction involves a benzyne
intermediate as shown in Sec. 2.13.2 on page 89. This mechanism is supported by the observation that when
chlorobenzene in which chlorine is attached to labelled carbon (C14), two types of anilines are produced;
one in which the NH2 group is attached to C14 while the other in which NH2 group is attached to a C12
carbon next to the C14 carbon as shown below :

NH2+

'QT

l- 1 4 C-Chlorobenzene

l- 1 4 C-Aniline (47%)

2- u C-Aniline (53%)

4. Isotope effects. While discussing isotopic labelling as a tool to investigate reaction mechanism, we
have made an important assumption that there is no difference in the chemical behaviour of different isotopes
and hence the chemical properties of the compounds are not quantitatively changed when a particular atom in
a compound is replaced by its isotope. However, in actual practice, isotopes because of their different masses,
do affect the rates of the chemical reactions.
The variation in the rate of a reaction when an atom in a compound is replaced by its isotope is called
isotope effect Usually, it is very small. However, if the replacement ofan atom by its isotope is involved in the
rate-determining step of the reaction, the magnitude of the isotopic effect may be quite large and is called
primary isotope effect*. Since the mass of a deuterium atom is double and that of a tritium atom is triple than
that of a hydrogen atom, therefore, the magnitude of the primary isotope effect is the greatest when a hydrogen
atom is replaced by a deuterium (D) or tritium (T). It is usually expressed in terms of the rate ratio, i. e. K H /K D or
Kh/Kt respectively. The value of this rate ratio is always greater than one which means that the compound
containing hydrogen reacts faster than that containing deuterium or tritium. Typical values for K H /K D and
Kh/Kt are 7 and 16 respectively.
The reason for the primary isotope effect is that bond-dissociation energy of the CD bond is more than
that of CH bond and even greater for the CT bond. Therefore, the energy of activation for cleaving the
CD bond would be much greater than that of a CH bond and hence the rate of the reaction involving
CD bond cleavage will be slow. It may, however, be noted here that if the CD and CH bond cleavages
are not involved in the rate-determining step of the reaction, then the rate of the reaction will be hardly affected
when hydrogen is replaced by its isotope, D or T. Most of the studies of isotope effect have been carried out
using deuterium and not tritium because it is more easily available and also because tritium is radioactive.
Primary isotope effect and reaction mechanism. Primary isotope effect is a powerful tool in determining
the mechanism of many reactions. For example,
(a) Dehydrohalogenation of isopropyl bromide. The rate of dehydrohalogenation of isopropyl bromide
with sodium ethoxide is considerably reduced when the hydrogen atoms of the methyl group are replaced by
deuterium.
S e c o n d a r y isotope effect. Deuterium isotope effects have been found even where it is certain that the C H bond
does not break at all in the reaction. Such effects are called secondary isotope effects and their magnitude is quite small as
compared to the primary isotope effects. These are further classified as a, (3 and y according as the deuterium atom is
present at a, p or y-position w.r.t. the carbon at which the reaction is taking place. An example of P-secondary isotope
effect is the solvolysis (i.e., hydrolysis by the solvent) of isopropyl bromide, i.e.
(CH 3 ) 2 CHBr + H 2 0
(CD 3 ) 2 CHBr + H 2 0

Kh

> (CH 3 ) 2 CHOH + HBr

Kd

> (CD 3 ) 2 CHOH + HBr

The Kh/Kd rate ratio for this reaction is found to be 1-34. The most probable reason for the secondary isotope effect
is hyperconjugation.

MECHANISM OF ORGANIC REACTIONS ^

Relative rate
(CH3)2CHBr+CjHjO(CD3)2CHBr+ C,H5Cr

CH3CH=CH2 + qHsOH+Br"
CD3CH= C D 2 + C ^ O D + B r

1-0

0-15

1-0

K h /K d = Q ^ g = 6 66 (nearly 7)
This large isotope effect definitely suggests that the rate-determining step of the reaction involves the
cleavage of the CH bond. As such the following mechanism for the above reaction is ruled out because in
this mechanism CH bond cleavage is a fast step.
(CH3)2CHBr

Ionization
Slow

-> v(CH3),CH
'

C2H50-

'in

Fast

CH 3 CH=CH 2 +C2H 5 OH

The correct mechanism for this reaction may be as follows:


H
Slow

C2H5O

C2H5<

H.

H CH 3
I I
.Br 5+
.CC
I I
H H

Transition state

I Fast
C2H5OH + CH2 = CHCH3 + Br
Thus, we conclude that it is CH bond cleavage and not CBr bond cleavage which is involved in the
rate-determining step of the reaction.
(b) Nitration of benzene. Nitration ofbenzene is an electrophilic substitution reaction. Here nitronium ion
(N0 2 ) attacks the benzene ring forming a carbocation intermediate which then loses a proton to give
nitrobenzene. In case hexadeuterated benzene or hexatritiated benzene is used is place ofbenzene, the rate of
nitration has been found to be the same. This means that nitration of benzene does not show any isotope
effect. In other words, the rate-determining step of the reaction does not involve breaking of the CH
(or CD or CT) bond. Conversely, attack of N 0 2 on the benzene ring is the rate-determining step while the
cleavage of the CH bond is a fast step. Thus the correct mechanism for nitration of benzene may be
formulated as follows:
+

NO 2

Slow

f ^ X l

Fast

r r V

H+

5. Kinetic evidence. The kinetic evidence alone is not sufficient to determine the mechanism of a particular
reaction. However, these studies give useful information about the rate-determining step of the reaction. It is
often possible to rule out many mechanisms simply on the basis of rate law. The most important example where
kinetic studies have been useful in determining the mechanism of the reaction is the hydrolysis of alkyl
halides. For example, the hydrolysis of methyl bromide shows second order kinetics, i.e.
-c/[CH 3 Br]
= &[CH 3 Br][OH~]
dt
This rate law suggests that both CH3Br and OH~ ion are participating in the rate-determining step of the
reaction. Such reactions are called SN2 reactions and occur in one-step through the participation of a
transition state.
In contrast, the hydrolysis off-butyl bromide shows first order kinetics, i.e.,
i~*t~CM d e e p ' s

- m a w * )
at
Since the rate law depends only on the concentration of (CH3)3CBr and is independent of the concentration
of OH" ion, therefore, rate-determining step involves only (CH3)3CBr. Such reactions are calledSN1 reactions
and occur in two steps. The first step involves ionization ofthe alkyl halide to give a carbocation intermediate.
This is the rate-determining step of the reaction. In the second step, the carbocation intermediate is rapidly
attacked by the nucleophile giving the substitution product.
6. Stereochemical evidence. Sometimes the mechanism of a reaction can be determined by following the
stereochemistry of the reactants and the products. For example, the mechanism of nucleophilic substitution
reactions (SN1 and S N 2) have been investigated by carrying out reactions with optically active compounds
and then checking the optical purity of the products.
(a) Mechanism of S N I reactions. Hydrolysis of optically active 1-chloro-l-phenylethane with aqueous
KOH gives racemic 1-phenylethanol.

CH

H5C6

\ ACI

"~C J-C.
CH

HA T H
6

KOH (aq)^
Slow *

cr
3

Carbocation
(planar)

(S)-l-Ch!oro-lphenylethane
(Optically active)

CH

C6H5

(Frontal attack)

CH

H^C-OH

CH

(R>1 -Phenylethanol (50%)


(One enantiomar)

(S>l-Phenylethanol (50%)
(Other enantiomer)
Racemic mixture

Racemisation of the product suggests that the reaction occurs through a planar carbocation intermediate
since the attack of the nucleophile, i.e. OH" ion on this carbocation can occur from both the faces (front and
rear) with almost equal ease giving a 50:50 mixture of the two enantiomers.
From the above discussion, we conclude that SN1 reactions occur through carbocation intermediates.
(b) Mcchanism of S N 2 reactions. Hydrolysis of optically active 2-bromooctane gives optically active 2octanol. This can be explained if we assume that attack of the OH" occurs from the side opposite to the bromine
atom giving first a transition state which then expels the Br" ion to give the product
H

13C6v

s\

i ^ A
CH

(S )-2-Bromooctane
(Optically active)

8-

CH
6

/C6Hi 3

I
8HO- C r - B r
H^ X C H 3
Transition state

HO-C^

CH

(R>2- Octanol
(Optically active)

During this reaction inversion of configuration occurs. This is called Walden inversion.

MECHANISM OF ORGANIC REACTIONS ^

From the above discussion, we conclude that SN2 reactions are one-step reactions in which optically
active reactants give optically active products with inverted configuration.
(c) Elimination reactions. The dehydrohalogenation ofcis-l, 2-dichloroethene gives chloroacetylene
twenty times faster than the corresponding /raws-isomer. This suggests that E2 reactions occur more rapidly
when the departing groups are in /raws-orientation than when they are cis.
H
I CIC = CH
bast
Chloroacetylene

Slow

P
CI

trans- 1,2-Dichloroethene
(Hand CI are cis)

cis- 1,2-Dichloroethene
{Hand CI are trans)

wmmmmmmmmmmmmmm

Fish arrows are used to indicate one-electron movements, curved arrows are used to denote twoelectron movements while double headed arrows are used to separate various canonical structures.
2. If a covalent bond breaks in such a way that each atom of the covalent bond takes away one electron of
the shared pair, it is called homolytic fission. Homolytic fission produces free radicals. It usually occurs
in non-polar solvents and is favoured by high temperature or ultraviolet radiations.
3. If a covalent bond breaks in such a way that both the electrons of the covalent bond are taken away by
one of the bonded atoms, the mode of bond fission is called heterolytic fission. It usually occurs in
polar solvents.
4. Electrophiles. Electron-loving species are called electrophiles. These may be neutral or positively charged
species.
Neutral nucleophiles : R ,: CX2, RN:, BF3, A1C13, FeCl3, SnCl4 etc.
Positively charged electrophiles : H+, H 3 0 + , Cl+, Br+, R+, NO+, C 6 H 5 N+ etc.
5. Nucleophiles. Nucleus loving species are called nucleophiles. These may be neutral or negatively
charged.
Neutral nucleophiles : H 2 6 : , NH 3 , RNH 2 , ROH, R-

-R, RMgX, LiAlH4 etc.

Negatively charged nucleophiles : CI", Br, I", OH", CN", RO", NH",: R", H", RC s C" etc.
6.

Organic reactions are of seven types :


(0 Reactions in which one atom or a group in an organic molecule is substituted by another atom or a
group are called substitution reactions. These can be nucleophilic, electrophilic or free radical
substitution reactions. Nucleophilic substitution reactions (SNl and SN2) are characteristic of alkyl
halides, electrophilic substitution reactions (halogenation, nitration, sulphonation and FriedelCrafts reactions) are characteristic of aromatic compounds while free radical substitution reactions
(halogenation, vapour phase nitration and sulphonation) are characteristic of alkanes.
(if) Reactions in which two molecules combine to give a single product are called addition reactions.
These can be nucleophilic (characteristic of aldehydes and ketones) electrophilic (characteristic of alkenes
and alkynes) free radical (characteristic of alkenes and alkynes in presence of peroxides) addition reactions.
(ii() Reactions which involve the loss of two atoms or groups from the same or adjacent atoms of a
substance leading to the formation of a multiple bond are called elimination reactions. They are
classified as a - , f5- and y- elimination reactions according as the two atoms or groups are lost from the
a, [3 or y-positions.
/ ^ r o d e e p ' s ' ORGANIC CHEMISTRY VOL. -I.

(;'v) Reactions in which two or more molecules of the same or different reactants combine to form a S
product with or without the loss of simple molecules such as H20, HCl, NH3, ROH etc. are condensation U
M
reactions. For example, aldol condensation, Claisen condensation, Claisen-Schmidt condensation etc. M
(v) Reactions involving the migration of an atom or a group from one atom to another within the same A
molecule are called rearrangement reactions. For example, 1, 2-hydride or 1, 2-methyl shift in R
Y
carbocations, Beckmann rearrangement, Hofmann bromamide reaction etc.
iaaa
(vi) Reactions which involve interconversion of one isomer into another keeping the molecular formula tffi
E
as well as carbon skeletons of the reactants and the products intact are called isomerisation reactions. V
For example, photochemical isomerization of Zram-but-2-ene to cw-but-2-ene and that of 1-bromobutane I
E
to 2-bromobutane in presence of anhyd. A1C13 at 575 K.
W
(vii) Concerted reactions which occur through cyclic transition states are called pericyclic reactions.
For example, electrocyclic (interconversion of buta-1, 3-diene to cyclobutene) and cycloaddition (i.e.
Diels-Alder) reactions.
7. The ultimate criterion of feasibility of an organic reaction is AG = AH - TAS.
8. According to collision theory, the rate of the reaction = PZ e~Eact/RT where P is the probability factor, Z
is the collision frequency, E act is the energy of activation and e - E a c t / R T is the fraction of collisions
having energy greater than Eact.
9. According to transition state theory, reactants on their way to products pass through an activated
complex or the transition state (T.S.). The energy difference between the T.S. and the reactants is called
the free energy of activation. Higher the free energy of activation, slower is the reaction and viceversa.
10. Many organic reactions occur through the formation of an intermediate which may or may not be
isolable. Such reactions occur through two transition states. If the free energy of activation of the first
transition state is higher than that of second, the reactive intermediate cannot be isolated. If, however,
the free energy of activation of the second transition state is higher than that of the first, the intermediate
can be isolated.
11. The number of transition states formed during a stepwise reaction is equal to the number of steps by
which the reaction occurs. Thus, a two-step reaction has two transition states of which the one having
the higher free energy of activation constitutes the rate-determining step of the reaction.
12. The geometry of a T.S. can be studied in terms of Hammond's postulate which states that for any single
reaction step, the geometry of the T.S. for that reaction resembles the side to which it is closer in free
energy of activation. Thus, the T.S. may be reactant-like, product-like or intermediate-like according as
its energy lies closer to the reactant, product or the intermediate respectively.
13. A catalyst increases the rate of a reaction by providing an alternate path from reactants to products with
a lower energy transition state.
14. Most of organic reactions occur through the participation of certain chemical species which are generally
short-lived and highly reactive. These are called reactive intermediates. These are of seven types : (/)
carbocations, (ii) carbonions, (iii) free-radicals, (iv) carbenes, (v) nitrenes, (vi) arynes and (vii) enamines.
15. Chemical species carrying a positive charge on carbon are called carbocations. These are planar
species (i.e. C is s/>2-hybridized) and are produced by heterolytic fission of covalent bonds. Their
stability follows the order : 3 > 2 > 1 > CHJ. This order of stability can be explained on the basis of
inductive effect and hyperconjugation effect. In contrast, unsaturated carbocations are stabilized by
resonance.
16. Chemical species carrying a negative charge on carbon are called carbanions. These may be pyramidal
or planar and are produced by heterolytic cleavage of covalent bonds. Simple alkyl carbanions are
pyramidal in which the carbon is sp3-hybridized. Carbanions in which the charged carbon is next to a
double bond or a benzene ring are stabilized by resonance. Such carbanions are planar in which the
carbon atom bearing negative charge is j/?2-hybridized. The order of stability of simple alkyl carbanions
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is : CH~ > 1 > 2 > 3. This order of stability can be explained on the basis of inductive effect.
MECHANISM OF ORGANIC REACTIONS