1014 General Organic Chemistry

Chapter

23
General Organic Chemistry

Carbon is an essential element of organic compounds, it has four Type of hybridisation sp 3

sp
2
sp
electrons in its outer most shell.
According to the ground state electronic configuration of carbon, it Examples :
is divalent. Tetravalency of carbon can be explained by promoting one of
O
the 2s 2 - electrons to the unocupied 2 p z1 atomic orbital. ||
(i) CH 3  CH  CH  C  CH 3
The four valencies of carbon atom are similar and they are  
  
symmetrically arranged around the carbon atom. According to Le Bell and sp 2 sp 2 sp 2 sp 3
Van’t Hoff the four valencies of carbon do not lie in one plane. They are sp 3
directed towards the corners of a regular tetrahedron with carbon atom at
(ii) CH 2  C  CH 2
the centre and the angle between any two valencies is 109 28.
o


 
sp sp 2
Hybridisation in Organic Compounds sp 2
(1) The process of mixing atomic orbitals to form a set of new (iii) CH 3  CH  CH  CH 2  C  N
equivalent orbitals is termed as hybridisation. There are three types of      
hybridisation, sp 3 sp 2 sp 2 sp 3 sp sp
(i) sp 3 hybridisation (involved in saturated organic compounds
containing only single covalent bonds), (iv) HC  C  CH  CH 2
   
2
(ii) sp hybridisation (involved in organic compounds having sp sp sp 2 sp 2
carbon atoms linked by double bonds) and
(iii) sp hybridisation (involved in organic compounds having  In diamond carbon is sp hybridised and in graphite carbon is
3

carbon atoms linked by a triple bonds). sp 2

hybridised.
Table : 23.1
Type of hybridisation sp3 sp2 sp (ii) Second method : (Electron pair method)
Number of orbitals used 1s and 3p 1s and 2p 1s and 1p
Number of unused Nil One Two
ep = bp + lp; where ep = electron pair present in hybrid orbitals , bp =
p-orbitals bond pair present in hybrid orbitals
Bond Four - Three - Two - Number of bp = Number of atoms attached to the central atom
One - Two -
Bond angle
of the species
109.5 120 180
Geometry Tetrahedral Trigonal planar Linear Central atom
% s-character 25 or 1/4 33.33 or 1/3 50 or 1/2 First atom H
H
(2) Determination of hybridisation at different carbon atoms : It can
C=C
be done by two methods,
Second atom H H
(i) First method : In this method hybridisation can be know by the
number of   bonds present on that particular atom. bp = 3
Third atom
Number of – bond/s 0 1 2 Central atom
1 2
1
H  C  C H 2 H

bp  2
3
bp = 3
 General Organic Chemistry 1015

s  sp  sp 2  sp 3  p

% s - character and electronegativityin decreasing order.
(iii) Bond length variation in hydrocarbons
Number of lp’s can be determined as follows,
(a) If carbon has  - bonds or positive charge or odd electron, than % of s orbital character
lp on carbon will be zero. 1 1
(b) If carbon has negative charge, then lp will be equal to one.  
C  C bond length C  H bond length
Number of electron pairs (ep) tells us the type of hybridisation as
follows, Table : 23.2

ep 2 3 4 5 6 Bond type (C – Bond length Bond type (C – Bond length

Type of hybridisation sp sp 2 sp 3 sp 3 d sp 3 d 2 H) C)

sp 3  s 1.112Å sp 3  sp 3 (alk 1.54 Å

Example :
  (alkanes) anes)
(i) CH 2  CH (ii) CH 2  CH
  sp 2  s 1.103Å sp 2  sp 2 (alk 1.34Å
bp  2 bp  2 (alkenes) enes)
lp  0 lp  1
ep  2, sp sp  s 1.08Å sp  sp (alkyn 1.20Å
ep  3, sp 2

(alkynes) es)

(iii) CH 2  C  CH 3 (iv) CH  C
 (iv) Bond strength in hydrocarbons : The shorter is the bond length,
|
bp 1 the greater is the compression between atomic nuclei and hence greater is
CH 3 lp  1 the strength of that bond.
bp  3 ep  2, sp Table : 23.3
lp  0
ep  3, sp 2 Bond type (C Bond energy Bond type (C Bond energy

– H) (kcal/mole) – C) (kcal/mole)
(v) CH 3  CH  CH 3 104 80 – 90
 sp 3  s sp 3  sp 3
bp  3 (in alkanes) (in alkanes)
lp  1
ep  4 , sp 3 sp  s
2 106 sp 2  sp 2 122 – 164
(3) Applications of hybridisation (in alkenes) (in alkenes)
(i) Size of the hybrid orbitals : Since s - orbitals are closer to the sp  s 121 sp  sp 123 – 199
nucleus than p - orbitals, it is reasonable to expect that greater the s
character of an orbital the smaller it is. Thus the decreasing order of the (in alkynes) (in alkynes)
size of the three hybrid orbitals is opposite to that of the decreasing order
of s orbital character in the three hybrid orbitals. (v) Acidity of hydrocarbons
sp  sp  sp
3 2
(a) Hydrogen present on electronegative carbon is acidic in nature.
(ii) Electronegativity of different orbitals (b) Acidity of hydrogen is directly proportional to the
(a) Electronegativity of s-orbital is maximum. electronegativity of the atom on which hydrogen is present.
(b) Electronegativity of hybrid orbital  % s-character in hybrid
orbitals Thus
H O  H  NH3  CH CH
Orbital sp sp 2 sp 3
   
% s - character
Electronegativityof the atoms
 50 33 . 33 25 Acidityof compounds in decreasing order
s-character in decreasing order and electronegativityin decreasing order
Thus sp-hybrid carbon is always electronegative in character and (c) Acidity of hydrocarbon  % of s-character
3
sp - hybrid carbon is electropositive in character. sp -hybrid carbon can2 CH  CH CH 2  CH 2 CH 3  CH 3
behave as electropositive (in carbocation) as well as electronegative (in % s-character 50 33.33 25
carbanion) in character.
pKa 25 44 50
 
CH 3  CH 2 CH 2  CH s- character and acidity in decreasing order
1
Acidity  Ka and Acidity  ( pKa   log Ka)
sp 2 sp pKa
Order of acidic nature of alkynes is,
Electronegative carbon
Electropositive carbon having positive charge HC  CH  HC  C  CH 3
(c) Electronegativities of different hybrid and unhybrid orbitals in
decreasing order is as follows The relative acidic character follows the order;
 1016 General Organic Chemistry

H 2O  ROH  HC  CH  NH 3  CH 2  CH 2  CH 3  CH 3 Inductive effect or Transmission effect

Obviously, the basic character of their conjugate bases follows the (1) When an electron withdrawing (X) or electron-releasing (Y)
reverse order, i.e., group is attached to a carbon chain, polarity is induced on the carbon atom
and on the substituent attached to it. This permanent polarity is due to
CH 3 CH 2  CH 2  CH   NH 2  HC  C   RO   HO  displacement of shared electron of a covalent bond towards a more
electronegative atom. This is called inductive effect or simply as I – effect.
Steric effect
C  C  C  C Non polar
On account of the presence of bulkier groups at the reaction centre,     
they cause mechanical interference and with the result the attacking reagent C  C  C  C X
finds it difficult to reach the reaction site and thus slows down the reaction.
    
This phenomenon is called steric hinderance or steric effect. C C C C Y
(1) Tertiary alkyl halides having bulky groups form tertiary (2) Carbon-hydrogen bond is taken as a standard of inductive effect.
carbocation readily when hydrolysed because of the presence of the three Zero effect is assumed for this bond. Atoms or groups which have a greater
bulky groups on the carbon having halogen. electron withdrawing capacity than hydrogen are said to have–I effect
Steric strain around this carbon Steric strain is released whereas atoms or groups which have a greater electron releasing power are
CH
3 (More strained species) (less strained species) said to have +I effect.
| 
H 3 C  C  Cl  H 3 C  C  CH 
| 3 N H 3  NO 2  CN  SO 3 H  CHO  CO  COOH  COCl  COOR
CH
|
3 CH > CONH 2  F  Cl  Br  I  OH  OR  NH 2  C6 H 5  H
3
–I power of groups in decreasing order with respect to the reference H
(2) Primary alkyl halide having quaternary  -carbon does not form
ter. alkyl > sec. alkyl > pri. alkyl > CH 3  H
transition state because of the steric strain around  -carbon by the  -
carbon. To release the strain it converts into carbocation. + I power in decreasing order with respect to the reference H
Bulky group
CH + I power  number of carbon in the same type of alkyl groups
3
| CH 3  CH 2  CH 2  CH 2   CH 3  CH 2  CH 2  
CH 3  C CH 2  Cl
|
CH 3  CH 2 
CH Strained carbon due to
3
bulky group present + I power in decreasing order in same type of alkyl groups
around this carbon.
(3) Applications of Inductive effect
(3) Steric strain inhibits the resonance. This phenomenon is known
(i) Magnitude of positive and negative charges : Magnitude of +ve
as steric inhibitions of resonance.
charge on cations and magnitude of –ve charge on anions can be
compared by + I or – I groups present in it.
Electronic displacement in covalent bonds
1
It is observed that most of the attacking reagents always possess  Magnitude of ve charge   I
either a positive or a negative charge, therefore for a reaction to take place  I power of the group
on the covalent bond the latter must possess oppositely charged centres. power of the group.
This is made possible by displacement (partial or complete) of the bonding 1
electrons. The electronic displacement in turn may be due to certain effects,  Magnitude of ve charge   I
 I power of the group
some of which are permanent and others are temporary. The former effects
power of the group.
are permanently operating in the molecule and are known as polarisation
effects, while the latter are brought into play by the attacking reagent and (ii) Reactivity of alkyl halide : + I effect of methyl group enhances –
as soon as the attacking reagent is removed, the electronic displacement I effect of the halogen atom by repelling the electron towards tertiary
disappears; such effects are known as the polarisability effects. carbon atom.
CH 3 CH 3
Electronic displacement
H3C C X  H3C CH X
CH 3
Polarisation effect Polarisability effect  CH 3 CH 2 X  CH 3 X
(permanent) (temporary)
Tertiary > Secondary > Primary > Methyl
(iii) Relative strength of the acids :
Inductive Mesomeric Hyperconjugative Inductomeric Electromeric (a) Any group or atom showing +I effect decreases the acid strength
effect effect effect effect effect as it increases the negative charge on the carboxylate ion which holds the
hydrogen firmly. Alkyl groups have + I effect.
 General Organic Chemistry 1017

Thus, acidic nature is, R2 NH  RNH 2  NH 3  R3 N

C2 H 5
HCOOH  CH 3 COOH  C 2 H 5 COOH  C 3 H 7 COOH  C 4 H 9 COOH
(CH 3 )2 CH RNH 2  NH 3  R2 NH  R3 N
+I effect increases, so acid strength decreases
(CH 3 )3 C NH 3  RNH 2  R2 NH  R3 N
Formic acid, having no alkyl group, is the most acidic among these
acids.
 The relative basic character of amines is not in total accordance
(b) The group or atom having – I effect increases the acid strength with inductive effect (t  s  p) but it is in the following order: Secondary
as it decreases the negative charge on the carboxylate ion. Greater is the
> Primary > Tertiary. The reason is the steric hindrance existing in the t-
number of such atoms or groups (having – I effect), greater is the acid
strength. amines.

Thus, acidic nature is,  In gas phase or in aqueous solvents such as chlorobenzene etc,
the solvation effect, i.e., the stabilization of the conjugate acid due to H -
CCl 3 COOH  CHCl 2 COOH  CH 2 ClCOOH  CH 3 COOH bonding are absent and hence in these media the basicity of amines
Trichloro Dichloro Monochloro Aceticacid
acetic acid acetic acid acetic acid depends only on the +I effect of the alkyl group thus the basicity of amines

(– Inductive effect increases, so acid strength increases)

follows the order : 3 o  2 o  1 o  NH 3 .

(c) Strength of aliphatic carboxylic acids and benzoic acid (vii) Basicity of alcohols : The decreasing order of base strength in
alcohols is due to +I effect of alkyl groups.
R COOH C6 H 5 COOH
  (CH 3 )3 COH  (CH 3 )2 CHOH  CH 3 CH 2 OH  CH 3 OH
 I group  I group (3 o ) (2 o ) (1 o )

(viii) Stability of carbonium ion :+I effect tends to decrease the (+ve)
charge and –I effect tends to increases the +ve charge on carbocation.
Hence benzoic acid is stronger acid than aliphatic carboxylic acids
but exception is formic acid. Thus, (CH 3 )3 C   (CH 3 )2 CH   CH 3 CH 2  CH 3
HCOOH > C 6 H 5 COOH > RCOOH
(ix) Stability of carbanion : Stability of carbanion increases with
Acid strength in decreasing order increasing – I effect.
 Decreasing order of acids :
CH 3  CH 3 CH 2  (CH 3 )2 CH   (CH 3 )3 C 
NO 2CH 2COOH  FCH2COOH  ClCH 2COOH  BrCH2COOH .
Resonance effect or mesomeric effect
F3C  COOH  Cl3C  COOH  Br3C  COOH  I3C  COOH .
(1) The effect in which  electrons are transferred from a multiple
CH 3 OH  CH 3 CH 2 OH  (CH 3 ) 2 CHOH  (CH 3 )3 COH bond to an atom, or from a multiple bond to a single covalent bond or lone
Methyl Ethyl Iso  propyl Tert butyl pair (s) of electrons from an atom to the adjacent single covalent bond is
alcohol Alcohol alcohol alcohol called mesomeric effect or simply as M-effect. In case of the compound with
As compared to water, phenol is more acidic (–I effect) but methyl conjugated system of double bonds, the mesomeric effect is transmitted
through whole of the conjugated system and thus the effect may better be
alcohol is less acidic (+I effect).
known as conjugative effect.
OH  H  OH > CH 3 OH (2) Groups which have the capacity to increase the electron density
Phenol Water Methyl alcohol
of the rest of the molecule are said to have  M effect. Such groups
(vi) Relative strength of the bases (Basic nature of  NH 2 ) possess lone pairs of electrons. Groups which decrease the electron density
of the rest of the molecule by withdrawing electron pairs are said to have
The difference in base strength in various amines can be explained
 M effect, e.g.,
on the basis of inductive effect. The +I effect increases the electron density
(a) The groups which donate electrons to the double bond or to a
while –I effect decreases it. The amines are stronger bases than NH 3 as
conjugated system are said to have  M effect or  R effect.
the alkyl groups increase electron density on nitrogen due to + I effect while
ClNH 2 is less basic due to –I effect. “So more is the tendency to donate  M effect groups :
electron pair for coordination with proton, the more is basic nature, i.e., .. ..
more is the negative charge on nitrogen atom (due to +I effect of alkyl  Cl,  Br,  I,  N H 2 ,  NR 2 ,OH ,OR,SH ,OCH 3 , S R
group), the more is basic nature”. ..

Thus, the basic nature decreases in the order; (b) The groups which withdraw electrons from the double bond or
from a conjugated system towards itself due to resonance are said to have
(C 2 H 5 )2 NH  CH 3 CH 2 NH 2  CH 3 NH 2  NH 3  ClNH 2
Diethyl Ethyl Methyl Ammonia Chloro  M effect or  R effect.
amine amine amine amine
 M effect groups :
The order of basicity is as given below;
O
Alkyl groups (R– ) Relative base strength ||
R2 NH  RNH 2  R3 N  NH 3  NO 2 ,C  N ,  C ,CHO ,COOH ,SO 3 H
CH 3
 1018 General Organic Chemistry
(3) The inductive and mesomeric effects, when present together, (iv) Resonating structures due to hyperconjugation may be written
may act in the same direction or oppose each other. The mesomeric effect is involving “no bond” between the alpha carbon and hydrogen atoms.
more powerful than the former. For example, in vinyl chloride due to – I
effect the chlorine atom should develop a negative charge but on account of 
H H
mesomeric effect it has positive charge. | 
H  C  CH  CH 2  H  C  CH  C H 2 
..  .. | |
: Cl  CH  CH 2  : Cl  CH  CH 2 H H
.. ..
H H
Application of mesomeric effect : It explains,  |  | 
(1) Low reactivity of aryl and vinyl halides, H C  CH  C H 2  H  C  CH  C H 2
|
(2) The acidic nature of carboxylic acids, H H

(3) Basic character comparison of ethylamine and aniline,
(4) The stability of some free radicals, carbocations and carbanions. (v) Number of resonating structures due to the hyperconjugation =
Number of  -hydrogens + 1.
Difference between Resonance and Mesomerism : Although both
resonance and mesomerism represent the same phenomenon, they differ in Applications of hyperconjugation
the following respect : Resonance involves all types of electron (1) Stability of alkenes : Hyperconjugation explains the stability of
displacements while mesomerism is noticeable only in those cases where a certain alkenes over other alkenes.
multiple bond is in conjugation with a multiple bond or lone pair of
Stability of alkenes  Number of alpha hydrogens  Number of
electron.
resonating structures
Example :
CH 3  CH  CH 2  CH 3  CH 2  CH  CH 2  CH 3  CH  CH  CH 2
 |
..  CH 3
(i) H 2 C  CH  CH  CH 2  H 2 C  CH  CH  C H 2 Stability in decreasing order

.. (2) Carbon-carbon double bond length in alkenes : As we know that

..
:O :O: the more is the number of resonating structures, the more will be single
|| .. ||  bond character in carbon-carbon double bond.
(ii) R  C  O  H  R  C  O  H
..
.. (3) Stability of alkyl carbocations : Stability of alkyl carbocations 
Both (i) and (ii) are the examples of mesomerism and resonance number of resonating structures  number of alpha hydrogens.
..   (4) Stability of alkyl free radicals : Stability of alkyl free radicals can
effect. Let us consider the following example H Cl :  H Cl . be explained by hyperconjugation. Stability depends on the number of
.. resonating structures.
Such an electron displacement is the example of resonance only (not the
(5) Electron releasing (or donating) power of R in alkyl benzene :
mesomerism).
CH 3  (or alkyl group) is  R group, ortho-para directing group and
Hyperconjugative effect activating group for electrophilic aromatic substitution reaction because of
(1) When a H  C bond is attached to an unsaturated system such the hyperconjugation.
as double bond or a benzene ring, the sigma () electrons of the H  C The electron donating power of alkyl group will depends on the
bond interact or enter into conjugation with the unsaturated system. The number of resonating structures, this depends on the number of hydrogens
interactions between the electrons of  systems (multiple bonds) and the present on -carbon. The electron releasing power of some groups are as
adjacent  bonds (single H  C bonds) of the substituent groups in follows,
organic compounds is called hyperconjugation. The concept of
hyperconjugation was developed by Baker and Nathan and is also known as CH 3
Baker and Nathan effect. CH 3 |
CH 3   CH 3  CH 2   CH   CH 3  C 
In fact hyperconjugation effect is similar to resonance effect. Since |
there is no bond between the  -carbon atom and one of the hydrogen CH 3
CH
atoms, the hyperconjugation is also called no-bond resonance. 3

(2) Structural requirements for hyperconjugation Increasing inductive effect

(i) Compound should have at least one sp 2 -hybrid carbon of
either alkene alkyl carbocation or alkyl free radical.
(ii)  -carbon with respect to sp 2 hybrid carbon should have at
least one hydrogen.
If both these conditions are fulfilled then hyperconjugation will take
place in the molecule.
(iii) Hyperconjugation is of three types
Electron donating power in decreasing order due to the
hyperconjugation.
(6) Heat of hydrogenation : Hyperconjugation decreases the heat of
hydrogenation.
(7) Dipole moment : Since hyperconjugation causes the
development of charges, it also affects the dipole moment in the molecule.
 General Organic Chemistry 1019

The increase in dipole moment, when hydrogen of formaldehyde Electromeric effect

(  2.27 D) is replaced by methyl group, i.e., acetaldehyde (  2.72 D)
can be referred to hyperconjugation, which leads to development of charges. (1) The phenomenon of movement of electrons from one atom to
another in multibonded atoms at the demand of attacking reagent is called
H H electromeric effect. It is denoted as E-effect and represented by a curved
H
| |  arrow ( ) showing the shifting of electron pair.
H  C  O , H  C  CH  O  H  C  CH  O 
(  2 . 27 D) | |
H H A B

E
A B :
(  2 . 72 D) Reagent

(8) Orienting influence of alkyl group in o, p -positions and of

(2) (i)When the transfer of electrons take place towards the
CCl 3 group in m -position : Ortho-para directing property of methyl
attacking reagent, the effect is called  E effect. The addition of acids to
group in toluene is partly due to  I effect and partly due to alkenes.
hyperconjugation.
Reverse Hyperconjugation : The phenomenon of hyperconjugation is CC  H   C  C
also observed in the system given below, |
H
X 
| CH 3 CH  CH 2  H   CH 3  C H  CH 3
 C  C  C ; where X  halogen Propene
|
Since, CH 3 group is electron donating, the electrons are
In such system the effect operates in the reverse direction. Hence transferred in the direction shown.
the hyperconjugation in such system is known as reverse hyperconjugation.
The attacking reagent is attached to that atom on which electrons
 have been transferred.
Cl Cl
|  (ii) When the transfer of electrons takes place away from the
Cl  C  CH  CH 2  Cl  C  CH  CH 2  attacking reagent, the effect is called  E effect. Example, The addition of
| |
Cl Cl cyanide ion to carbonyl compounds.

Cl Cl
 |  |  C  O  CN   C  O
Cl C  CH  CH 2  Cl  C  CH  C H
2
|
| CN
Cl Cl
 The attacking reagent is not attached to that atom on which
electrons have been transferred.
The meta directing influence and the deactivating effect of CX 3
(3) Direction of the shift of electron pair : The direction of the shift
group in electrophilic aromatic substitution reaction can be explained by of electron pair can be decided on the basis of following points.
this effect.
(i) When the groups linked to a multiple bond are similar, the shift
X X X X can occur in either direction.
| |  |  | 
X  C X X C X X C X X C X (ii) When the dissimilar groups are linked on the two ends of the
| || || || double bond, the shift is decided by the direction of inductive effect.
 +
In the case of carbonyl group, the shift is always towards oxygen,
i.e., more electronegative atom.

 
Inductomeric effect C  O  C O :
Inductomeric effect is the temporary effect which enhances the In cases where inductive effect and electromeric effect
inductive effect and it accounts only in the presence of an attacking reagent. simultaneously operate, usually electrometric effect predominates.
Example,
H Cleavage (fission or breaking) of covalent bonds
H Breaking of covalent bond of the compound is known as bond
HO  H  C  Cl  HO....... ..... C..... ....... Cl fission. A bond can be broken by two ways,
H (1) Homolytic bond fission or Homolysis
H H (i) In homolysis, the covalent bond is broken in such a way that
H each resulting species gets its own electron. This leads to the formation of
Cl  odd electron species known as free radical.
 HO  C  H
H . .
A : B  A  B
In methyl chloride the –I effect of Cl group is further increased Free radical
temporarily by the approach of hydroxyl ion.
 1020 General Organic Chemistry
(ii) The factor which favours homolysis is that the difference in
electronegativity between A and B is less or zero.
(iii) Homolysis takes place in gaseous phase or in the presence of
non polar solvents (CCl 4 , CS 2 ) , peroxide, UV light, heat ( 500 o C) ,
electricity and free radical.
(iv) Mechanism of the reaction in which homolysis takes place is
known as homolytic mechanism or free radical mechanism.
(2) Heterolytic bond fission or heterolysis
is termed as carbocation. If negative charge is present on the carbon then
anion is termed as carbanion.
(ii) The factor which favours heterolysis is greater difference of
electronegativities between A and B .
(iii) Mechanism of the reaction in which heterolysis takes place is
known as heterolytic mechanism or ionic mechanism.
(iv) The energy required for heterolysis is always greater than that
for homolysis due to electrostatic forces of attraction between ions.

(i) In heterolysis, the covalent bond is broken in such a way that Reaction Intermediates
one species (i.e., less electronegative) is deprived of its own electron, while
the other species gains both the electrons. Short lived fragments called reaction intermediates result from
homolytic and heterolytic bond fission. The important reaction
  intermediates are free radicals, carbocations, carbanions, carbenes, benzyne
A : B  A:  B and nitrenes.
carbanion carbocation

Thus formation of opposite charged species takes place. In case of

organic compounds, if positive charge is present on the carbon then cation
Table : 23.4
Characteristic Free radical Carbocation Carbanion Carbene
Nature Neutral having odd electron Positive charge on C Negative charge on C Neutral, divalent with 2
unshared electrons
Hybridisation sp2 sp2 sp3 (non-conjugated) (i) sp2 (singlet)
sp2 (Conjugated) (ii) sp (triplet)
Structure Planar Planar Pyramidal/Planar (i) Planar (singlet)
(ii) Linear (triplet)
Magnetism Paramagnetic Diamagnetic Diamagnetic (i) Diamagnetic
(ii) Paramagnetic
Stability order . . .      Triplet > singlet
Ph3 C  Ph2 CH  Ph CH 2  Ph3 C  Ph2 CH  PhCH 2  Ph3 C  Ph2 CH 
 
.
CH 2  CH  CH 2  PhCH 2  Allyl
CH 2  CH  CH 2  3 o  2 o 
 
. . 3 o  2 o  1o  CH 3 CH 2  1o  2 o  3 o
1o  CH 2  CH 2  CH


Benzyne (ii) It reacts with strong nucleophile like NH 2
(1) 1, 2-Didehydrobenzene, C6 H 4 and its derivatives are called NH
 NH
H
2
2

benzyne or arynes and the simplest member is benzyne.  N H 2  

(2) It is neutral reaction intermediate derived from benzene ring by 
removing two substituents, of ortho positions, one in the form of
electrophile and other in the from of nucleophile leaving behind two ..
electrons to be distributed between two orbitals. Nitrenes (R – N : )
(1) The nitrogen analogous of carbenes are called nitrenes.
Abnormal  bond (2) There is possibility of two spin states for nitrenes depending on
whether the two non-bonding electrons (the normal nitrogen lone pair
remains paired) have their spins paired or parallel.
Two sp -orbitals ouside
2

the ring ..
R – .N. These two are lone pair of electrons
(3) Benzyne intermediate is aromatic in character. 
(4) When halobenzene is heated with sodamide formation of These two may be paired or unpaired
benzyne takes place. (3) In general nitrenes obey Hunds rule and the ground state triplet
Cl with two degenerate sp -orbitals containing a single electron each.

 
NaNH 2
R–N

(5) (i) It behaves as dienophile and gives Diels-Alder reaction with sp-Triplet nitrene
diene. (4) Nitrenes can be generated, in situ, by the following methods,
 General Organic Chemistry 1021

(i) By action of Br2 in presence of a base on a 1 o amide (2) Nucleophiles : Electron rich species or electron donors are called
nucleophiles. Nucleophiles can be classified into three categories :
(Hofmann-bromamide reaction),
(i) Charged nucleophiles : Negatively charged species are called
O  O O charged nucleophiles.
||  || 
|| . .
R  C  NH 2 2 R  C  NHBr   R  C  N  Br
Br / NaOH OH      
1 o Amide  H 2O .. H , O H , R  O, C H 3 , X , S H , R  S

 (ii) Neutral nucleophiles : It can be classified into two categories :
(a) Neutral covalent compound, in which central atom has complete
O octet, has at least one lone pair of electrons and all atoms present on
|| . . central atom should not be electronegative, is neutral nucleophile.
   R  C  N  O  C  N  R 
Rearrangem ent
 Br . . Isocyanate  .. .. .. .. .. ..
N H 3, R  N H 2 , R2 N H , R3 N , N H 2  N H 2 (Nitrogen nucleophile)
KOH

 R  NH 2  K 2 CO 3
(Hydrolysis) 1 o Amine .. .. ..
H  O  H , R  O  H , R  O  R (Oxygen nucleophiles)
(ii) By decomposition of azides in presence of heat or light. .. .. ..
..  .. .. .. .. ..
 or h ν
R  N  N  N :  R  N :  N  N H  S  H , R  S  H , R  S  R (Sulphur nucleophiles)
Alkylazide Alkylnitrene .. .. ..
.. .. .. .. ..
(iii) Unsubstituted nitrene (H  N :) can be obtained by photolysis P H 3 , R P H 2 , R 2 P H , R3 P (Phosphorus nucleophiles)
of (or by passing electric discharge through) NH 3 , N 2 H 4 or N 3 H . (b) Organic compound containing carbon, carbon multiple bond/
bonds behaves as nucleophile.
Attacking reagents
Alkenes, Alkynes, Benzene,
The fission of the substrate molecule to create centres of high or
low electron density is influenced by attacking reagents. Most of the CH 2  CH  CH  CH 2 , CH 2  CH  C  CH
attacking reagents can be classified into two main groups. (iii) Ambident nucleophiles : Species having two nucleophilic
Electrophiles or electrophilic reagents and Nucleophiles or centres out of which, one is neutral (complete octet and has at least one
nucleophilic reagents. lone pair of electrons) and the other is charged (negative charge) behaves as
(1) Electrophiles : Electron deficient species or electron acceptor is ambident nucleophile
an electrophile.
O
It can be classified into two categories :  ..  ..  
(i) Charged electrophiles : Positively charged species in which C  N , O  N  O, O  S  OH

central atom has incomplete octet is called charged electrophile.
O
O  
H , X , R, N , N  O, S O3 H  Organometallic compounds are nucleophiles.
O ..  Nucleophiles are Lewis bases.
All cations are charged electrophiles except cations of IA, IIA group Organic compounds which behave as an electrophile as well as a
 nucleophile : Organic compound in which carbon is bonded with
elements, Al    and NH 4 electronegative atom (O, N, S) by multiple bond/bonds behaves as
(ii) Neutral electrophiles : It can be classified into three categories, electrophile as well as nucleophile :
(a) Neutral covalent compound in which central atom has O O O O
|| || || ||
incomplete octet is neutral electrophile,
R  C  H , R  C  R, R  C  OH , R  C  Cl ,
. .. ..
BeCl 2 , BH 3 , ZnCl 2 , AlX3, FeX 3 , CH 3 , CH 2 , CX 2 O O
|| ||  
(b) Neutral covalent compound in which central atom has complete R  C  OR, R  C  NH 2 , R  C  N , R  N  C
or expended octet and central atom has unfilled –d-sub-shell is neutral  During the course of chemical reaction electrophile reacts with
electrophile,
nucleophile.
SnCl 4 , SiCl4 , PCl5 , SF6 , IF7  Strong Lewis acid is stronger electrophile
(c) Neutral covalent compound in which central atom is bonded  
only with two or more than two electronegative atoms is called neutral CO 2  N O 2  S O 3 H . Stronger is an acid, weaker is its conjugated
electrophile. base or weaker is the nucleophile.
BeCl 2 , BX 3 , AlX3 , FeX 3 , SnCl 4 , PCl3 ; Examples : HF  H 2 O  NH 3  CH 4
..
PCl5 , NF3 , C X 2 , CO 2 , SO 3 , CS 2 , F   OH   NH 2  CH 3
Increasing order of nucleophilicity.
Cl 2 , Br2 and I2 also behave as neutral electrophiles.
Electrophiles are Lewis acids. Types of organic reactions
 1022 General Organic Chemistry
It is convenient to classify the numerous reactions of the various (iii) The leaving power of some nucleophilic groups are given below
classes of organic compound into four types, in decreasing order,
 Substitution reactions,  Addition reaction, O
O O
 Elimination reactions,  Rearrangement reactions, ||  ||  || 
CF3  S  O  Br S  O  CH 3 SO 
Substitution reactions || || ||
Replacement of an atom or group of the substrate by any other O O O
atom or group is known as substitution reactions. O O
Substituting or ||  || 
Examples : attacking group C 6 H 5  S  O  CH 3  S  O
Leaving group
|| ||
O O
CH 3  CH 2  Br NaOH  CH 3  CH 2 OH  NaBr O O
Ethyl bromide Ethyl alcohol
  ||     || 
(Bromine atom is replaced by hydroxyl group)  I  Br  CF3  C  O  H O  Cl  F  CH 3  C  O
(iv) In these reactions leaving group of the substrate is replaced by
Types of substitution reactions : On the basis of the nature of another nucleophile. If reagent is neutral then leaving group is replaced by
attacking species substitution reactions are classified into following three negative part of the reagent. Negative part of the reagent is always
categories, nucleophilic in character.
    
(1) Nucleophilic substitution reactions E  Nu
R  L    R  Nu  L ; R  L  Nu  R  Nu  L
(2) Electrophilic substitution reactions (v) In S N reactions basicity of leaving group should be less than
(3) Free radical substitution reactions the basicity of incoming nucleophilic group. Thus strongly basic nucleophilic
(1) Nucleophilic substitution reactions group replaces weakly basic nucleophilic group of the substrate.
 
(i) Many substitution reactions, especially at the saturated carbon Example : R  Cl 
OH
 R  OH  Cl .....(A)
( NaOH )
atom in aliphatic compounds such as alkyl halides, are brought about by
  
nucleophilic reagents or nucleophiles. Basicity of OH is more than Cl hence OH replaces Cl as Cl .
 
R  X  OH   R  OH  X R  OH  R  Cl  OH ......(B)
Cl
Substrate Nucleophile Leaving group
( HCl )

Such substitution reactions are called nucleophilic substitution   

Basicity of Cl is less than OH , hence Cl will not replace OH as
reactions, i.e., S N reactions (S stands for substitution and N for 
nucleophile). OH hence reaction (B) will not occur.
(vi) Unlike aliphatic compounds having nucleophilic group as
(ii) The weaker the basicity of a group of the substrate, the better leaving group, aromatic compounds having same group bonded directly
is its leaving ability. with aromatic ring do not undergo nucleophilic substitution reaction under
ordinary conditions.
1
Leaving power of the group  The reason for this unusual reactivity is the presence of lone pair of
Basicityof the group
electron or  bond on the key atom of the functional group. Another factor
for the low reactivity is nucleophilic character of aromatic ring.
HI  HBr  HCl  HF
Example :  (vii) The S N reactions are divided into two classes, S N 2 and S N 1
Decreasing acidity
reactions.
   
I Br Cl F

Increasing basicity

Decreasing leaving ability

Table : 23.5 Distinction between S 2 and S 1 reactions

N N

Factors S 2 Reactions
N
S 1 Reactions
N

Number of steps  
R : L  R   : L
Slow
One: R : L  : Nu  R : Nu  : L Two: (i)
(ii) R   : Nu   R : Nu
Fast

Reaction rate and order Second order: First order:

Rate  [Substrate] [Nucleophile] or Rate Rate  [Substrate] or Rate = K1 [RL]

= K 2 [RL][: Nu ]
Molecularity Bimolecular Unimolecular
TS of slow step  
 
 
: Nu    C   : L : Nu    C    L    Nu :
Reacting nucleophile The nucleophile attacks the carbon of the substrate The nucleophile can attack the carbon of the substrate both
exclusively from the back side. from the back and front sides although the back side attack
 General Organic Chemistry 1023

predominates.
Stereochemistry Complete inversion of configuration takes place. Inversion and retention takes place.
Reactivity order of alkyl halides Methyl>1°>2°>3°halides. (I  Br  Cl  F) 3°>2°>1° > methyl halides. (I  Br  Cl  F)
Rearrangement No rearranged product is formed (except for Rearranged products can be formed.
allylic).
Nature of nucleophiles Favoured by strong and high concentration of Favoured by mild and low concentration of nucleophiles.
nucleophiles.
Polarity Favoured by solvents of low polarity. Favoured by solvents of high polarity.
Reaction rate determining factor By steric hindrance. 
By electronic factor (stability of R ).
Catalysis Not catalysed by any catalyst (phase transfer). Catalysed by Lewis and Bronsted acids, e.g.,

Ag, AlCl3 , ZnCl 2 and strong HA.

(2) Electrophilic substitutions reactions : Electrophilic substitution written as S E1 (unimolecular)and if the order is 2, it is S E 2
involves the attack by an electrophile. It is represented as S (S stands for
E
(Bimolecular).
substitution and E stands for elctrophile). If the order of reaction is 1, it is
S 1 Reaction mechanism : Electrophilic substitution in aliphatic compounds are very S 2 Reaction mechanism : Electrophilic substitution is very
E E

rare; some of the important examples are: common in benzene nucleus (aromatic compounds) in which -
(i) Replacement of the metal atom in an organometallic compound by hydrogen : electrons are highly delocalized and an electrophile can attack this
  region of high electron density.
RM H RH M In all electrophilic aromatic substitution reactions, it involves:
 

 MgBr H Step 1. The formation of an electrophile, E, i.e.,
e.g., CH 3  CH 2  MgBr  CH 3  CH 2  CH 3  CH 3
 
  In halogenation; Cl  Cl  FeCl3  Cl  Fe Cl 4
CH 3  CH 2  MgBr  H  Br  CH 3  CH 2 
H
CH 3  CH 3  MgBr2   
CH 3  CH 2 Na  C6 H6  CH 3  CH 3  C6 H5 Na In nitration; HNO 3  2 H 2 SO 4  NO 2  2 HSO 4  H 3 O
 
(ii) Decarboxylation of silver salt of carboxylic acid by means of bromine: In sulphonation; 2 H 2 SO 4  SO 3  HSO 4  H 3 O
     
R3 C  C  OAg  Br  Br  R3 C  C  O  Br Br  Ag In Friedel-crafts reaction; R  Cl  AlCl3  R  AlCl4
|| ||
 
O O RCOCl  AlCl3  RCO  AlCl4
 R3C  Br  CO 2  AgBr
Step 2. The electrophile attacks the aromatic ring to form
(iii) Isotopic exchange of hydrogen for deuterium or tritium: carbonium ion (or arenium ion) which is stabilized by resonance.
H E H E H E
 
RH D⇋ RDH   
E
 
R H T ⇋ R T H Benzene +

Step 3. Carbonium ion loses the proton to form substitution

product.
H E
E
+
+ H+

The bromination of benzene in the presence of FeBr3 is

a example of electrophilic substitution reaction.
Similarly, Nitration, sulphonation and Friedel-Crafts
reaction…..etc., in benzene nucleus are the other examples of
electrophilic substitution reactions.

(3) Free radical substitution reactions : Free radical substitution CH 4  Cl 2  CH 3 Cl  HCl
UV
reactions involves the attack by a free radical. These reactions occurs by free Methane light Methyl chloride
radical mechanism which involves Initiation, Propagation and Termination
steps. Examples, (ii) Arylation of aromatic compounds (Gomberg reaction) : The
(i) Chlorination of methane : The chlorination of methane in the reaction of benzene diazonium halide with benzene gives diphenyl by a free
presence of ultraviolet light is an examples of free radical substitution. radical substitution reaction.
 1024 General Organic Chemistry

C6 H 5  H  C6 H 5 N 2 X   C6 H 5  C6 H 5 
Alkali
N 2  HX CH 3
Benzene diazonium halide Diphenyl
CH 3  CH  CH 2 , C  CH 2 ,
(iii) Wurtz reaction : Ethyl bromide on treatment with metallic CH 3
sodium forms butane, ethane and ethylene by involving free radical
C6 H 5
mechanism.
C  CH  C 6 H 5 , C6 H 5  CH  CH 2
(iv) Allylic bromination by NBS (N-Bromosuccinimide) : NBS is a
C6 H 5
selective brominating agent and it normally brominates the ethylenic
compounds in the allylic (CH 2  CH  CH 2 ) position. This type of Following alkenes will not give addition reaction according to
Markownikoff’s rule.
reaction involving substitution at the alpha carbon atom with respect to the
double bond is termed Allylic substitution. It is also used for benzylic R R
bromination. Some examples are: CH 2  CH 2 , R  CH  CH  R, C C ,
CH 2  CO R R
CH 3  CH  CH 2  N  Br 
CCl 4
C6 H 5 C6 H 5
Propene
CH 2  CO CC
NBS
C6 H 5 C6 H 5
CH 2  CO (vi) Unsymmetrical alkenes having the following general structure
Br  CH 2  CH  CH 2  NH give addition according to anti Markownikoff’s rule.
Allylbromide
CH 2  CO CH 2  CH  G , where G is a strong –I group such as
Succinimide

Addition reactions O
||
These reactions are given by those compounds which have at least  CX 3 , NO 2,  CN ,CHO ,COR ,COOH , C  Z
one  bond,
(Z  Cl, OH, OR, NH 2 )
O
|| Example:
i.e., ( C  C ,C  C , C , C  N ). In such reaction there
Cl
is loss of one  bond and gain of two  bonds. Thus product of the |
reaction is generally more stable than the reactant. The reaction is a CH 2  CH  CHO  HCl 
 CH 2  CH 2  CHO
Anti- Markowniko ff's addition

spontaneous reaction.
(vii) Mechanism of electrophilic addition reactions is as follows,
Types of addition reactions : Addition reactions can be classified
  |
into three categories on the basis of the nature of initiating species. CC  E  
Slow
C C E
Olefin Electrophile |
(1) Electrophilic additions Carbonium ion
(2) Nucleophilic additions  |  |

(3) Free radical additions C C E  X 

Fast
C  C E
| Nucleophile | |

(1) Electrophilic addition reactions X

Addition product
(i) Such reactions are mainly given by alkenes and alkynes. (2) Nucleophilic addition reactions : When the addition reaction
(ii) Electrophilic addition reactions of alkenes and alkynes are occurs on account of the initial attack of nucleophile, the reaction is said to
generally two step reactions. be a nucleophilic addition reaction. Due to presence of strongly
(iii) Alkenes and alkynes give electrophilic addition with those electronegative oxygen atom, the  -electrons of the carbon-oxygen double
reagents which on dissociation gives electrophile as well as nucleophile. bond in carbonyl group ( C  O ) get shifted towards the oxygen atom
(iv) If the reagent is a weak acid then electrophilic addition is and thereby such bond is highly polarised. This makes carbon atom of the
carbonyl group electron deficient.
catalysed by strong acids (Generally H 2 SO 4 ).
   
(v) Unsymmetrical alkenes and alkynes give addition reactions with CO  C O  C O
unsymmetrical reagents according to Markownikoff’s rule.
The negative part of the addendum adds on that doubly bonded Example : The addition of HCN to acetone is an example of
carbon of the alkene which has least number of hydrogen atom. nucleophilic addition.
This rule can be used only in those alkenes which fulfil the CH 3 CH 3 OH
following conditions: C  O  HCN  C
(a) Alkene should be unsymmetrical. CH 3 CH 3 CN
Acetone Acetone cyanohydri n
(b) Substituent/substituents present on doubly bonded carbon/(s)
should only be +I group. The mechanism of the reaction involves the following steps:

(c) If phenyl group is present on doubly bonded carbon, then both Step 1. HCN gives a proton (H ) and a nucleophile, cyanide ion
doubly bonded carbons should be substituted by phenyl groups. 
For example, the following alkenes will give addition according to (CN ) .
the Markownikoff’s rule.
 General Organic Chemistry 1025

HCN  H   CN  Elimination reactions are generally endothermic and take place on

heating.
Step 2. The nucleophile (CN ) attacks the positively charged Elimination reactions are classified into two general types,
carbon so as to form an anion [ H  does not initiate the negatively (I) - elimination reactions or 1, 1-elimination reactions.
charged oxygen as anion is more stable than cation].
 (II) - elimination reaction or 1, 2-elimination reactions.
CH 3 CH 3 O
 CH 3  (I) -elimination reactions or 1,1-elimination reactions: A reaction in
CN C  O  CN C  O or C which both the groups or atoms are removed from the same carbon of the
CH
3 CH 3 CH 3 CN molecule is called - elimination reaction. This reaction is mainly given by
Step 3. The proton (H  ) combines with anion to form the gem dihalides and gem trihalides having at least one - hydrogen.
addition product. .. 
Alc. KOH /
CH 3 CHX 3   CX 2  X  H
CH 3 | CH 3 OH
 Product of the reaction is halocarbenes or dihalocarbenes. which are
CN C  O  H  NC  C  OH or C key intermediates in a wide variety of chemical and photochemical reactions.
CH 3 | CH 3 CN
(II) -elimination reactions or 1, 2-elimination reactions: Consider the
CH 3 following reactions,

In C  O compounds, the addition of liquid HCN gives  

CH 3  CH 2  CH 2  L  CH 3  CH  CH 2  H  L
 
cyanohydrin and the addendum is CN  ion and not HCN directly
(addition is catalysed by bases or salts of weak acids and retarded by acids A reaction in which functional group (i.e., leaving group) is
or unaffected by neutral compounds). removed from - carbon and other group (Generally hydrogen atom) from
 the - carbon is called - elimination reaction. In this reaction there is loss
   O  OH
H CN   CN H of two  bonds and gain of one  bond. Product of the reaction is generally
C  O    C  O  C 
 C
( A.R.) less stable than the reactant.
CN CN

Nucleophilic addition (A ) reactions on carbonyl compounds will be (1) Types of - elimination reactions : In analogy with substitution
reactions, - elimination reactions are divided into three types:
N

in order:
H H3C H 3C (i) E (Elimination unimolecular) reaction, (ii) E (Elimination
1 2

bimolecular) reaction and (iii) E (Elimination unimolecular conjugate base)

C O  C O  C O 1cb

reaction
H H H 3C
(i) E (Elimination unimolecular) reaction : Consider the following
Decreasing order of nucleophilic addition in some species. 1

reaction,
O O
|| || CH 3
C 6 H 5 CH 2 COCH 3  CH 3 COCH 3  C 6 H 5  C  CH 3  C 6 H 5  C  C 6 H 5  CHO   CH 3
| C H O/  
CH 3  C  Cl 25 CH C  C 2 H 5 OH  Cl
COCH 3  COCl  COOCH 3  CONH 2  COOH |
2

CH 3 CH 3
(3) Free radical addition reactions : Those reactions which involve
the initial attack by a free radical are known as free radical reactions. (a) Reaction velocity depends only on the concentration of the
Addition of hydrogen bromide to alkenes (say, propylene) in the presence of substrate; thus reaction is unimolecular reaction.
peroxide (radical initiator) follows free radical mechanism. Free radical
Rate  [Substrate]
reactions generally take place in non-polar solvents such as CCl 4 , high
temperature, in presence of light or a free radical producing substance like (b) Product formation takes place by the formation of carbocation
as reaction intermediate (RI).
O 2 and peroxides.
(c) Since reaction intermediate is carbocation, rearrangement is
Elimination reactions possible in E reaction.
1

Elimination reactions are formally the reverse of addition reactions (d) Reaction is carried out in the presence of polar protic solvent.
and involve the removal of the two groups (Generally, one being a proton)
from one or two carbon atoms of a molecule to form an unsaturated (e) The E reaction occurs in two steps,
1

linkage or centre. Step 1.

Elimination reaction is given by those compounds which have a
nucleophilic group as leaving group, CH 3 CH 3
| | 
  
   R

R CH 3  C  Cl  CH 3  C - - - - - Cl   CH 3  C  CH 3  Cl
Slow step
| | |
i.e., X, OH, OR, N 2 , N 3 , H 3 O, N R, S CH 3 CH 3 CH 3
(TS 1 )
R R ( RI)

Step 2.
 1026 General Organic Chemistry

   In E reactions, product formation always takes place by Saytzeff

1

  rule.
..   
B  H  CH 2  C  CH 3   B - - - - H - - - -CH 2 - - - - C  CH 3 
| |  In E reactions, product formation always takes place by
CH 3  CH 3  1cb

  Hofmann rule.
 TS 2 
 In E reactions, product formation takes place by Saytzeff as well
2

CH 3
 as Hofmann rule. In almost all E reactions product formation take place by
2

 B H  CH 2  C
fast
Saytzeff rule.
CH 3
(ii) E (Elimination bimolecular) reaction : Consider the following
2
(3) Examples of  - elimination reactions
reaction, (i) Dehydrohalogenation is removal of HX from alkyl halides with
  alcoholic KOH or KNH 2 or ter- BuOK (Potassium tertiary butoxide) and
CH 3  CH 2  CH 2  Br   CH 3  CH  CH 2  H  Br
Base ( B )
 an example of - elimination,
(a) Reaction velocity depends only on the concentration of the e.g., CH 3  CH 2 X   H 2 C  CH 2 ;
Alc.KOH
substrate and the base used; thus reaction is bimolecular reaction. Rate ( HX ) Ethene
[Substrate] [Base]
CH 3  CH  CH 3  CH 3 CH  CH 2 Alc.KOH
| ( HX )
(b) Since the reaction is a bimolecular reaction, the product Propene

formation will take place by formation of transition state (TS). X

(c) Rearrangement does not take place in E reaction but in case of CH 3  CH 2  CH  CH 3   CH 3  CH  CH  CH 3 
Alc.KOH
2
| ( HX ) 2 - Butene (Major)
allylic compound rearrangement is possible. X
(d) Reaction is carried out in the presence of polar aprotic solvent. CH 3  CH 2  CH  CH 2
1- Butene (Minor)
(e) The E 2
reaction occurs in one step,
.. (ii) Dehydration of alcohol is another example of elimination
B H H  B  - - - - H   H 
| |  |  reaction. When acids like conc. H 2 SO 4 or H 3 PO4 are used as

CH 3  C  C  H   CH 3  C
Slow step
C  H dehydrating agents, the mechanism is E . The proton given by acid is taken
| |  |   1

H Br  H Br  up by alcohol.
 TS 
Dehydration is removal of H 2 O from alcohols,


 CH 3  CH  CH 2  BH  Br
fast
e.g.,
Conc. H 2 SO 4 , 170 C
(2) Orientation in  - elimination reactions : If substrate is CH 3  CH 2  OH    H 2 C  CH 2
( H 2 O )
unsymmetrical, then this will give more than one product. Major product of
the reaction can be known by two emperical rules. Conc. H 2 SO 4 , 170 C
CH 3  CH 2  CH 2  OH    CH 3  CH  CH 2
Propan -1 - ol ( H 2 O ) Propene
(i) Saytzeff rule : According to this rule, major product is the most
  Dehydration of alcohols is in the order:
substituted alkene i.e., major product is obtained by elimination of H from
Tertiary  Secondary  Primary
that - carbon which has the least number of hydrogen. Product of the (3) (2) (1)
reaction in this case is known as Saytzeff product.
 2° and 3° alcohol by E process and 1° alcohol by E process.
1 2

Cl Alcohols leading to conjugated alkenes are more easily dehydrated than the
2 |
Alc.KOH /  alcohols leading to non-conjugated alkenes. CH 2  CH  CH  CH 3 is
CH 3  CH  CH  CH 3 
 CH 3  C  CH  CH 3 |
|  1  HCl |
OH
CH 3 CH
3 easily dehydrated than
Saytzeff p roduct
CH 3  CH 2  CH  CH 3 and so
(ii) Hofmann rule : According to this rule, major product is always |

least substituted alkene i.e., major product is formed from - carbon which OH
has maximum number of hydrogen. Product of the reaction in this case is OH OH OH
known as Hofmann product. > >
CH 3 Br CH 3
| | |
Alc.KOH / 
CH 3  C  CH 2  CH  CH 3   CH 3  C  CH 2  CH  CH 2
| 2  1 | (iii) Dehalogenation : It is removal of halogens, e.g.,
CH 3 CH 3
Hofmann product CH 2  CH 2  Zn dust  H 2 C  CH 2 in CH 3 OH , heat

| | (-ZnBr2 ) Ethylene
Br Br
Ethylene bromide
 General Organic Chemistry 1027

(iv) Dehydrogenation : It is removal of hydrogen, e.g., (3) Rearrangement or migration to free radical species (Free radical
Cu , 300 C rearrangement) : Those rearrangement reactions in which the migrating
CH 3  CH  CH 3 
 CH 3  C  CH 3
| ( H 2 ) || group moves to a free radical centre. Free radical rearrangements are
OH O comparatively rare.
Isopropyl alcohol Acetone
(4) Aromatic rearrangement : Those rearrangement reactions in
Rearrangement reactions which the migrating group moves to aromatic nucleus. Aromatic
The reactions, which involve the migration of an atom or group compounds of the type (I) undergo rearrangements in the manner
mentioned below,
from one site to another within the molecule (nothing is added from
outside and nothing is eliminated) resulting in a new molecular structure, X–Y X–H X–H
are known as rearrangement reactions. The new compound is actually the Y
structural isomer of the original one.
+ +
It is convenient to divide rearrangement reactions into following
types: (I) Y
The element X from which group Y migrates may be nitrogen or
(1) Rearrangement or migration to electron deficient atoms oxygen.
(Nucleophilic rearrangement) : Those rearrangement reactions in which
migrating group is nucleophilic and thus migrates to electron deficient Isomerism
centre which may be carbon, nitrogen and oxygen.
Organic compounds having same molecular formula but differing
Y B B: from each other at least in some physical or chemical properties or both are

|
Y | | | | | known as isomers (Berzelius) and the phenomenon is known as isomerism.
 C  C    C  C    C  C 
| |  | | The difference in properties of isomers is due to the difference in
X: X X the relative arrangements of various atoms or groups present in their
Bridged or molecules. Isomerism can be classified as follows:
non-classical carbocation
X= Nucleophilic species, Y = Electronegative group, B = Another
nucleophile.
(2) Rearrangement or migration to electron rich atoms (Electrophilic
rearrangement) : Those rearrangement reactions in which migrating group
is electrophile and thus migrates to electron rich centre.
Isomerism

Constitutional or structural isomerism Configurational or stereo isomerism

Without referring to space, the isomers differ in the The isomerism arises due to different arrangement of atoms or groups
arrangement of atoms within the molecule is called in space. It deals with the structure of molecules in three dimensions.
structural isomerism. Thus structural isomers have:
Thus stereoisomers have:

Chain Position Ring chain Functional Meta Tauto - Geometrical Optical Conformational
isomerism isomerism isomerism isomerism merism merism isomerism isomerism isomerism

Constitutional or structural isomerism CH 3

|
(1) Chain, nuclear or skeleton isomerism : This type of isomerism CH 3  C H  CH 2  CH 3 , CH 3  C  CH 3
| |
arises due to the difference in the nature of the carbon chain (i.e., straight CH 3 CH 3
or branched) which forms the nucleus of the molecule. Isopentane Neopentane

 Except alkynes chain isomerism is observed when the number of

Examples :
carbon atoms is four or more than four.
(i) C H : CH 3  CH 2  CH 2  CH 3 , CH 3  CH  CH 3
4 10
 Chain isomers differ in the nature of carbon chain, i.e., in the
n Butane |
CH 3 length of carbon chain.
Isobutane  The isomers showing chain isomerism belong to the same
homologous series, i.e., functional group, class of the compound (Cyclic or
(ii) C H : (Three) CH 3  CH 2  CH 2  CH 2  CH 3 ,
5 12
open) remains unchanged.
n  Pentane
 Chain and position isomerism cannot be possible together
between two isomeric compounds. If two compounds are chain isomers
then these two will not be positional isomers.
 1028 General Organic Chemistry
(2) Position isomerism : It is due to the difference in the position of O
the substiuent atom or group or an unsaturated linkage in the same carbon
chain. C H NO : C 2 H 5  N
2 5 2
; C2 H 5  O  N  O
Ethyl nitrite
(ii) C H Cl : CH 3  CCl 2  CH 3 , CH 3  CH 2  CH  Cl 2 , O
3 6 2
Nitro ethane
2, 2 Dichloro propane, 1,1Dichloro propane
(gemdihalide) (gemdihalide) (vi) Amines (Primary, secondary and tertiary)
CH 3  C H  C H 2 , C H 2  CH 2  C H 2 C H N : CH 3  CH 2  CH 2  NH 2 ;
3 9

| | | | Propan -1 - amine
Cl Cl Cl Cl
1, 2  Dichloro propane 1, 3  Dichloro propane H
( , - dihalide)
(Vicdihalide) CH 3  CH 2  N
 Aldehydes, carboxylic acids (and their derivatives) and cyanides CH 3
do not show position isomerism. N  Methyl ethanamine

 Monosubstituted alicylic compounds and aromatic compounds CH 3

do not show position isomerism. CH 3  C H  CH 3 ; CH 3  CH 2  N
|
 Structural isomers which differ in the position of the functional NH 2 CH 3
Propan - 2- amine N , N  Dimethyl methanamine
group are called regiomers. For example, (i) CH 3  CH 2  CH 2  OH
(vii) Alcohols and phenols
(ii) CH 3  CH  CH 3
| CH OH
2
OH
OH CH 3

(3) Functional isomerism : This type of isomerism is due to CHO ;

7 8

difference in the nature of functional group present in the isomers. The

following pairs of compounds always form functional isomers with each Benzyl alcohol o-Cresol
(viii) Oximes and amides
other.
O
Examples : ||

(i) Alcohols and ethers (C H O)

C H NO : CH 3  CH  NOH ; CH 3  C  NH 2
2 5

n 2n+2
Acetaldoxime Acetamide
C H O : CH 3  CH 2  OH ; H 3 C  O  CH 3
2 6

Ethyl alcohol Dimethyl ether (4) Ring-chain isomerism : This type of isomerism is due to different
modes of linking of carbon atoms, i.e., the isomers possess either open chain
C H O : CH 3  CH 2  CH 2  OH ; C 2 H 5  O  CH 3
3 8 or closed chain sturctures.
n  propyl alcohol Ethyl methyl ether
H2
CH O
4 10
: CH 3  CH 2  CH 2  CH 2  OH ; C
n Butyl alcohol

C2 H 5  O  C2 H 5 H 2C CH 2
Diethyl ether CH : 6 12
| | ;
(ii) Aldehydes, ketones and unsaturated alcohols …etc. (C H O) H 2C CH 2
n 2n

O C
|| H2
C H O : CH 3  CH 2  CHO ; CH 3  C  CH 3 ;
3 6
Cyclohexan e
Propionald ehyde
CH 2  CH 2
Acetone

CH 2  CH  CH 3 ; CH 2  CH  CH 2 OH | CHCH 3
Allylalcohol C H 2  CH 2 ; CH 3 CH 2CH 2CH 2CH  CH 2
O Methyl cyclopentane 1  Hexene
1, 2 Epoxy propane
 Ring – chain isomers are always functional isomers.
(iii) Acids, esters and hydroxy carbonyl compounds …etc. (C H O ) n 2n 2

(5) Metamerism : This type of isomerism is due to the difference in

C H O : CH 3 COOH ; HCOOCH 3
2 4 2
the nature of alkyl groups attached to the polyvalent atoms or functional
Aceticacid Methyl formate
group. Metamers always belong to the same homologous series. Compounds
C H O : CH 3  CH 2  COOH ; CH 3 COOCH 3 ;
3 6 2
like ethers, thio-ethers ketones, secondary amines, etc. show metamerism.
Propionic acid Methyl acetate
CH 3 C2 H 5
O (i) C H N : C3 H 7  N
5 13
; C2 H 5  N
|| CH 3 CH 3
CH 3 C HCHO ; CH 3  C  CH 2  OH Dimethyl propyl amine Diethyl methyl amine
| 1  Hydroxy propan - 2 - one
OH (ii) C H N : C 3 H 7  NH  C 3 H 7 ; C 2 H 5  NH  C4 H 9
6 15

2  Hydroxy propanal Dipropyl amine Butyl ethyl amine

(iv) Alkynes and alkadienes (C H ) n 2n-2

C H : CH 3  CH 2  C  CH ; H 2C  CH  CH  CH 2 ;  If same polyvalent functional group is there in two or more

4 6

1  Butyne 1, 3  Butadiene organic compounds, then chain or position isomerism is not possible, there
CH 3  C  C  CH 3 ; H 2C  C  CH  CH 3 will be metamerism e.g.,
2  Butyne 1, 2  Butadiene (a) CH 3  C  CH 2  CH 2  CH 3 ;
||
(v) Nitro alkanes and alkyl nitrites (  NO 2 and O  N  O ) O
(Pentan  2  one)
 General Organic Chemistry 1029

CH 3 CH 2  C  CH 2 CH 3 are metamers and not position isomers. O O

|| || ||
OH
O CH 3  C  CH 2  R CH 3  C  C H  R
(Pentan  3  one) Keto form – HO
2


(b) CH 3  C  CH 2 CH 2 CH 3 ; 
|| O OH
| |
O
(Pentan  2  one)  CH 3  C  CH  R  CH 3  C  CH  R
H 2O

OH (Enol)
CH 3  C  C H  CH 3 are metamers and not chain isomers. (c) Triad system containing nitrogen : Examples
|| | Nitrous acid exists in 2 forms
O CH 3
(3 - Methylbutan - 2 - one) O
H O N O HN
 Alkenes does not show metamerism. nitrite form O
Nitro form
(6) Tautomerism
(i) The type of isomerism in which a substance exist in two readily Nitro acinitro system
interconvertible different structures leading to dynamic equilibrium is
known as tautomerism and the different forms are called tautomers (or O O
CH 3  CH 2  N CH 3  CH  N
tautomerides). O OH
nitro form (i) Aci form (ii)
The term tautomerism (Greek: tauto = same; meros = parts) was
used by Laar in 1885 to describe the phenomenon of a substance reacting (iii) Characteristics of tautomerism
chemically according to two possible structures. (a) Tautomerism (cationotropy) is caused by the oscillation of
(ii) It is caused by the wandering of hydrogen atom between two hydrogen atom between two polyvalent atoms present in the molecule. The
polyvalent atoms. It is also known as Desmotropism (Desmos = bond and change is accompanied by the necessary rearrangement of single and double
tropos = turn). If the hydrogen atom oscillates between two polyvalent bonds.
atoms linked together, the system is a dyad and if the hydrogen atom (b) It is a reversible intramolecular change.
travels from first to third atom in a chain, the system is a triad. (c) The tautomeric forms remain in dynamic equilibrium. Hence,
their separation is a bit difficult. Although their separation can be done by
(a) Dyad system : Hydrocyanic acid is an example of dyad system in special methods, yet they form a separate series of stable derivatives.
which hydrogen atom oscillates between carbon and nitrogen (d) The two tautomeric forms differ in their stability. The less

atoms. H  C  N ⇌ C  N  H stable form is called the labile form. The relative proportion of two forms
varies from compound to compound and also with temperature, solvent etc.
(b) Triad system The change of one form into another is also catalysed by acids and bases.
Keto-enol system : Polyvalent atoms are oxygen and two carbon (e) Tautomers are in dynamic equilibrium with each other and
atoms.
interconvertible (⇌).
Examples : (f) Two tautomers have different functional groups.
O H OH (g) Tautomerism has no effect on bond length.
|| | | (h) Tautomerism has no contribution in stabilising the molecule
 C C ⇌  C  C  and does not lower its energy.
| | (i) Tautomerism may occur in planar or nonplanar molecules.
(Keto) (Enol)
 Keto=enol tautomerism is exhibited only by such aldehydes and
Acetoacetic ester (Ethyl acetoacetate) : ketones which contain at least one  -hydrogen.
O OH For example
|| |
CH 3  C  CH 2 COOC 2 H 5 ⇌ CH 3  C  CHCOOC 2 H 5 CH 3 CHO, CH 3 CH 2 CHO, CH 3 COCH 2 COCH 3 etc,.
Keto form (92.1%) Enol form (7.9%)
 Tautomerism is not possible in benzaldehyde (C 6 H 5 CHO) ,
Acetoacetic ester gives certain reactions showing the presence of
keto group (Reactions with HCN , H 2 NOH , H 2 NNHC 6 H 5 , etc.) and benzophenone (C 6 H 5 COC 6 H 5 ) , tri methyl acetaldehyde,
certain reactions showing the presence of enolic group (Reactions with (CH 3 )3 C  CHO and chloral CCl 3  CHO as they do not have
Na, CH 3 COCl , NH 3 , PCl5 , Br2 water and colour with neutral FeCl3 , H.
etc.). Number of structural isomers
Enolisation is in order
Molecular formula Number of isomers
CH 3 COCH 3  CH 3 COCH 2 COOC 2 H 5  C 6 H 5 COCH 2 COOC 2 H 5
Alkanes
 CH 3 COCH 2 COCH 3  CH 3 COCH 2 CHO C4 H10 Two
O Three
||
H
C5 H12
Acid catalysed conversion CH 3  C  CH 2  R
Keto C6 H14 Five
OH OH C7 H16 Nine
| |
H 
CH 3  C  C H  R  CH 3  C  CH  R C8 H18 Eighteen
 | (Enol form)
H C9 H 20 Thirty five
(Intermediate)
Base catalysed conversion
 1030 General Organic Chemistry

C10 H 22 Seventy five The compounds which have same molecular formula but differ in
the relative spatial arrangement of atoms or groups in space are known as
Alkenes and cycloalkanes
geometrical isomers and the phenomenon is known as geometrical
C3 H 6 Two (One alkene + one cycloalkane)
isomerism. The isomer in which same groups or atoms are on the same side
C4 H 8 Six (Four alkene + 2 - cycloalkane) of the double bond is known as cis form and the isomer in which same
groups or atoms are on the opposite side is called trans-isomer.
C5 H10 Nine (Five alkenes + 4 – cycloalkanes)
Examples :
Alkynes
C3 H 4 Two H  C  COOH H  C  COOH
|| ||
C4 H 6 Six H  C  COOH HOOC  C  H
Maleic acid (cis) Fumaric acid (trans)
Monohalides
C3 H 7 X Two H 3 C  C  COOH H 3 C  C  COOH
|| ||
C4 H 9 X Four H  C  COOH HOOC  C  H
Citraconic acid (cis- isomer) Mesaconic acid (trans  isomer)
C5 H11 X Eight
(1) Conditions for geometrical isomerism : Compound will show
Dihalides geometrical isomerism if it fulfils the following two conditions
C2 H 4 X 2 Two (i) There should be frozen rotation about two adjacent atoms in the
molecule.
C3 H 6 X 2 Four
(a) CC frozen rotation about carbon, carbon double
C4 H 8 X 2 Nine bond in alkenes.
C5 H10 X 2 Twenty one
Alcohols and ethers
Two (One alcohol and one ether) (b) frozen rotation about carbon, carbon single bond in
C2 H 6 O cycloalkanes.
C3 H 8 O Three (Two alcohols and one ether) (c) C  N  frozen rotation about carbon, nitrogen double
bond in oxime and imine.
C4 H10 O Seven (Four alcohols and three ethers)
(ii) Both substituents on each carbon should be different about
C5 H12 O Fourteen (Eight alcohols and six ethers) which rotation is frozen.
If these two conditions are fulfilled, then compound will show
Aldehydes and ketones geometrical isomerism.
C3 H 6 O Two (One aldehyde and one ketone)  The compounds of the following type will not show geometrical
isomerism.
C4 H 8 O Three (Two aldehydes and one ketone)
a  C a x  C a a  C a
C5 H10 O Seven (Four aldehydes and three ketone) || || ||
x C y aC a x C  x
Monocarboxylic acids
and esters (2) Distinction between cis- and trans- isomers
Two (One acid and one ester) (i) By cyclization method : Generally, the cis-isomer (e.g. maleic
C 2 H 4 O2 acid) cyclises on heating to form the corresponding anhydride while the
C3 H 6 O2 Three (One acid and two esters) trans-isomer does not form its anhydride.
C4 H 8 O2 Six (Two acids and four esters) H  C  COOH H  C  CO
||  
Heat
|| O
C5 H10 O2 Thirteen (Four acids and nine esters)
H  C  COOH H  C  CO
Maleicacid(cis) Maleic anhydride
Aliphatic amines
C2 H7 N Two (One 1°-amine and one 2°-amine)  Note that the two reacting groups (–COOH) are near to each
other.
C3 H 9 N Four (Two 1°-amines, one 2°-amine and one
3°-amine) H  C  COOH Heat
Eight (Four 1°-amines, three 2°-amines and ||  No anhydride
C4 H11 N
one 3°-amines) HOOC  C  H
Fumaric acid (trans)
Aromatic compounds
Four  Note that the two reacting groups (–COOH) are quite apart
C8 H 10 from each other, hence cyclisation is not possible.
C9 H 12 Nine (ii) By hydroxylation (Oxidation by means of KMnO4 ,OsO4 or
C7 H 8 O Five H 2 O2 in presence of OsO4 ) : Oxidation (Hydroxylation) of alkenes by
means of these reagents proceeds in the cis-manner. Thus the two
geometrical isomers of an alkene leads to different products by these
Geometrical or cis-trans isomerism reagents. For example,
 General Organic Chemistry 1031

H  C  COOH OH
H COOH
||  
KMnO 4
H COOH
H  C  COOH OH
Maleicacid(cis) meso  Tartaricacid

OH
H  C  COOH H COOH
|| 
KMnO 4

HOOC  C  H HOOC H
Fumaric acid (trans )
OH
() Tartaric acid

OH
HOOC H

H COOH
OH
() Tartaric acid

(iii) By studying their dipole moments : The cis-isomer of a

symmetrical alkene (Alkenes in which both the carbon atoms have similar
groups) has a definite dipole moment, while the trans-isomer has either
zero dipole moment or less dipole moment than the cis-isomer. For
example, 1,2-dichloroethylene and butene-2.
H  C  Cl H  C  Cl H  C  CH 3 H  C  CH 3
|| || || ||
H C Cl Cl C  H H C CH 3 CH 3 C  H
cis Dichloroethylene trans  Dichloroethylene cis Butene  2 trans  Butene  2
(  1 .9 D) (   0 . 0 D) (   0 . 0 D)

In trans-isomer of the symmetrical alkenes, the effect produced in

one half of the molecule is cancelled by that in the other half of the
molecule.
In case of unsymmetrical alkenes, the cis-isomer has higher dipole
moment than the corresponding trans-isomer.
 General Organic Chemistry 1033
For Example, The following rules are followed for deciding the precedence order
of the atoms or groups;
H 3 C  C  Cl CH 3  C  Cl
|| || (i) Higher priority is assigned to the atoms of higher atomic
CH 3  CH 2  C  Cl Cl  C  CH 2 CH 3 number. For example, the order of preference in the following atoms,
cis  2, 3  Dichloropentene  2 trans 2, 3  Dichloropentene  2 H , Cl, I, Br is : I (at. no. 53)> Br (at. no. 35)>Cl (at. no. 17)>H (at. no. 1).
(High dipole moment) (Less dipolemoment )
(ii) If isotopes of the same element are attached, the isotope with
Similar is the case with hexene-2. higher mass number is given higher order of preference. For example,
H 3C
C C
CH 2 CH 2  CH 3 deuterium  D
2
1 is assigned higher priority in comparison to hydrogen
H H
cis Hexene  2(more polar)
 .
1
1H
(iii) In the groups, the order of preference is also decided on the
H CH 2 CH 2  CH 3 basis of atomic number of first atom of the group. For example, in the
C C
CH 3 H following set,
trans  Hexene  2(Less polar)
Cl,OH,COOH , NH  CH 3 ,SO 3 H .
(iv) By studying other physical properties: (a) The cis-isomer of a The order of the precedence is :
compound has higher boiling point due to higher polarity, higher density  Cl   S O3 H   O H   N HCH 3   C OOH
and higher refractive index than the corresponding trans-isomer (Auwers-     
( at.no17) (at.no.16) (at.no.8) (at.no.7) (at.no. 6)
skita rule).
When the order of preference of the groups cannot be settled on
CH 3  C  H CH 3  C  H the first atom, the second atom or the subsequent atoms in the groups are
|| ||
CH 3  C  H H  C  CH 3 considered. For example, in the set CH 2  CH 3 ,CH 3 ,COOH , the
cis 2  Butene trans  2 Butene
b.p 4 C 1 C order cannot be decided on the basis of first atom as it is same in all the
m.p. 139  C 106  C
groups. However, in CH 2  CH 3 , the second atom is carbon, in
H  C  Cl H  C  Cl CH 3 , the second atom is hydrogen while in COOH , the second atom
|| ||
H  C  Cl Cl  C  H is oxygen. Hence, the order of preference is :
cis1, 2  Dichloroethene trans 1, 2  Dichloroethene
60 C
 80 C
48 C
 50 C
C O OH  CH 2  C H 3  C H 3
  
(at.no.8) (at.no.6)
(b) The trans-isomer has higher melting point than the cis-isomer (at.no.1)
due to symmetrical nature and more close packing of the trans-isomer. (iv) A doubly or triply bonded atom is considered equivalent to two
(v) Stability : Trans-isomer is more stable than cis-isomer due to or three such atoms. For example,
symmetrical structure.
The group C  O is equal to C O and the group C  N
 Terminal alkenes such as propene, 1-butene and 2-methyl |

propene do not show geometrical isomerism. O

 Cis-trans isomers are configurational isomers but not mirror N
|
images, hence cis and trans isomers are always diastereomers.
is equal to  C N .
 Non-terminal alkenes with the same atoms or groups either on |
one or both the carbon atoms of the double bond such as 2-methyl-2- N
butene, 2,3-dimethyl –2 – butene etc. do not show geometrical isomerism. (4) Number of geometrical isomers in polyenes
(3) E and Z system of nomenclature : ‘Cis’ and ‘Trans’ designations (i) When a compound has n double bonds and ends of a polyene
cannot be used if four different atoms or groups are attached to the carbon
are different, the number of geometrical isomers  2n
atoms of a double bond.
C6 H5  CH  CH  CH  CH  CH  CH  CH  CH  Cl
a d
CC The given compound has four double bonds and the two ends are
b e
different (One is C6 H 5 and other is Cl). Therefore, number of geometrical
In such cases, E and Z system of nomenclature is used. This system
is based on a priority system developed by Cahn, Ingold and Prelog. isomers  2n  24  16 .
In this system, the two atoms or groups attached to each of the (ii) When the ends of polyene are same.
doubly bonded carbon are put in order of preference on the basis of Case I : When number of double bonds (=n) is even then the
sequence rules.
number of geometrical isomers  2n 1  2[(n / 2)1]
The symbol ‘E’ is assigned to an isomer in which the atoms or
groups of higher preference are on the opposite side (E from German word Cl  CH  CH  CH  CH  CH  CH  CH  CH  Cl
n  4 , even
Entgegen = across or opposite).
The symbol ‘Z’ is assigned to an isomer in which the atoms or Number of geometrical isomers  2n 1  2(n / 2)1  2 3  21
groups of higher preference are on the same side (Z from German word,  8  2  10 .
Zusammen = together). Case II : When number of double bonds (=n) is odd.
 n 1 
1 2 1 1   1
CC CC Number of geometrical isomers  2 n 1  2  2 
2 1 2 2
E  isomer Z isomer C6 H 6  CH  CH  CH  CH  CH  CH  C6 H 5
(n  3, odd )
 1 signifies higher preference and 2 signifies lower preference.
Preference in most of the cases ‘Z’ corresponds to cis-form and ‘E’ to trans- Number of geometrical isomers  2 2  2 2 1  2 2  21
form. However, there are many exceptions. 42 6.
(5) Geometrical Isomerism in nitrogen compounds
 1034 General Organic Chemistry

(i) Geometrical isomerism due to C  N  bond. The optical activity was first observed in organic substances like
The important class of compounds exhibiting geometrical isomerism quartz, rock-crystals and crystals of potassium chlorate (KClO3 ) ,
due to C  N  bond are oximes, nitrones, hydrazones and potassium bromate (KBrO3 ) and sodium periodate (NaIO4 ) .
semicarbazones. But the most common compound is oxime.
Oximes : In aldoxime, when hydrogen and hydroxyl groups are on (2) Measurement of optical activity : The measurement of optical
the same side, the isomer is known as syn. (analogous to cis) and when activity is done in terms of specific rotation which is defined as the rotation
these groups are on the opposite side, the isomer is known as anti produced by a solution of length of 10 centimetres (One decimetre) and
unit concentration (1 g/mL) for the given wavelength of the light at the
C6 H 5  C  H C6 H 5  C  H
given temperature.
(analogous to trans) || ||
N  OH HO  N  obs
Syn - benzaldoxime Anti benzaldoxime Specific rotation,  twavelength
C

lC
In ketoximes the prefixes syn and anti indicate which group of
ketoxime is syn or anti to hydroxyl group. For example: Where  obs is the rotation observed, l is the length of the solution
CH 3  C  C2 H 5 in decimeters and C is the number of grams in 1mL of solution. The specific
|| this compound will be named as; rotation of the sucrose at 20°C using sodium light (D-line, =5893Å) is
N OH
+66.5°C and is denoted as:  20 C
 66.5C(C  0.02 g / mL water)
(a) Syn-ethyl methyl ketoxime  HO and C2 H 5 are syn or D

(b) Anti-methyl ethyl ketoxime  HO and C 2 H 5 are anti. + sign indicates the rotation in clockwise direction.
Similarly consider the following structure (3) On the basis of the study of optical activity, the various organic
C 2 H 5 C CH 3 compounds were divided into four types :
|| (i) The optical isomer which rotates the plane of the polarised light
N OH to the right (Clockwise) is known as dextrorotatory isomer (Latin: dextro =
Syn  methyl ethyl ketoxime
or Anti ethyl methyl ketoxime right) or d-form or indicated by +ve sign.
(ii) Geometrical isomerism due to N = N bond. (ii) The optical isomer which rotates the plane of the polarised light
C6 H 5  N C6 H 5  N to the left (Anticlockwise) is known as laevorotatory isomer (Latin; laevo =
|| ||
left) or l-form or indicated by –ve sign.
C H N N C6 H 5
6 5 Anti azobenzene
Syn - azobenzene (iii) The optical powers of the above two isomers are equal in
(6) Geometrical isomerism show by cumulatrienes : Cumulatrienes magnitude but opposite in sign. An equimolar mixture of the two forms,
(Trienes with three adjacent double bonds) show only geometric isomerism. therefore, will be optically inactive due to external compensation. This
This is because their molecule is planar, as such the terminal CH 3 mixture is termed as racemic mixture or dl-form or () mixture.
groups and H- atoms lie in the same plane. Therefore, in this case their (iv) Optical isomer with a plane of symmetry is called meso form. It
planar structure can exist in two diastereoisomeric forms, cis- and trans- is optically inactive due to internal compensation, i.e., the rotation caused by
but no enantiomeric forms are possible. upper half part of molecule is neutralised by lower half part of molecule.
H 3C CH 3 (4) Chirality, (i) Definition : A molecule (or an object) is said to be
CCCC chiral or dissymmetric, if it is does not possess any element of symmetry
H H
cis Hexa  2, 3 , 4  triene and not superimposable on its mirror image and this property of the
molecule to show non-superimposability is called chirality.
H 3C H
CCCC On the other hand, a molecule (or an object) which is
H CH 3 superimposable on its mirror image is called achiral (non-dissymmetric or
trans  Hexa  2, 3 , 4  triene
symmetric).
(7) Geometrical isomerism in cycloalkanes : Disubstituted
cycloalkanes show geometrical isomerism. To understand the term chiral and achiral let us consider the
alphabet letters ‘P’ and ‘A’ whereas ‘P’ is chiral, ‘A’ is achiral as shown in fig.
CH
OH
3

H OH H Mirror Mirror
H CH 3
H OH HO
H
H Cis-1,2-cyclohexanediol
Cis-1,2-dimethylcyc Trans-1,2-cyclopent
lopropane anediol
 Certain compounds show geometrical as well optical isomerism. Non-superimposable Superimposable
Such type of isomerism is known as geometrical enantiomerism. (Chiral or dissymmetric) (Achiral or non-dissymmetric)
(ii) Elements of symmetry : There are three elements of symmetry,
Optical isomerism
(a) Plane of symmetry : It may be defined as a plane which divides a
(1) Compounds having similar physical and chemical properties but molecule in two equal parts that are related to each other as an object and
they have the ability to rotate the plane of polarised light either to the right mirror image. e.g.,
(Clockwise) or to the left (Anticlockwise) are termed as optically active or
optical isomers and the property is called optical activity or optical
isomerism.
 General Organic Chemistry 1035

COOH a CH 3
| | |

H  C  OH d C b *
HO  C *  H
| |
| c COOH
Plane of symmetry
H  C  OH Lacticacid

|  Carbons that can be chirality centres are sp 3 -hybridised

COOH
carbons; sp 2 and sp -hybridised carbons cannot be chiral carbons because
(b) Centre of symmetry : It may be defined as a point in the they cannot have four group attached to them.
molecule through which if a line is drawn in one direction and extended to
 Isotopes of an atom behave as different group in
equal distance in opposite direction, it meets another similar group or atom,
stereoisomerism.
eg.
Centre of symmetry D H1
CH 3 CH 3 CH 3 H
| |
| NH  CO | | NH  CO |
H — C* — T Cl 35 — C * — Cl 37
C C and C  C
| |
| CO  NH | | CO  NH |
Br H2
H H H CH 3 Lactic acid
cis  Dimethyl diketo piperazine Trans  Dimethyl diketo piperazine
 Carbon of the following groups will not be a chiral carbon
Since trans form contains a centre of symmetry, it is optically
O
inactive.
||
(c) Alternating axis of symmetry : A molecule is said to possess an  CH 3 ,  CH 2 OH ,  CHX 2 ,  CHO ,  C  Z
alternating axis of symmetry if an oriention indistinguishable from the
 Maleic acid (HOOC  CH  CH  COOH ) show
original is obtained when molecule is rotated Q degree around an axis
geometrical isomerism while malic acid
passing through the molecule and the rotated molecule is reflected in a
mirror that is perpendicular to the axis of rotation in step (I). (HOOC  CH 2  CHOH  COOH ) show optical isomerism.
Reflection perpendicular to
axis rotation
(5) Calculation of number of optical isomers
Cl H H F H (i) If molecule is not divisible into two identical halves and molecule
Cl
H F 180 rotation
o

Cl H F has n asymmetric carbon atoms then

around axis H
F H H Cl H Number of optically active forms  2 n  a
H Cl F H F
H Cl
Number of enantiomeric pair  a/2

(iii) Symmetric, Asymmetric and Dissymmetric molecules Number of racemic mixture  a/2

(a) Symmetric molecules : If any symmetry is present in the Number of meso form  0
molecule then molecule will be symmetric molecule. (ii) If molecule is divisible into two identical halves, then the
(b) Dissymmetric molecules : Molecule will be a dissymmetric number of configurational isomers depends on the number of asymmetric
molecule if it has no plane of symmetry, no centre of symmetry and no carbon atoms.
alternating axis of symmetry. Case I : When compound has even number of carbon atoms, i.e.,
(c) Asymmetric molecules : Dissymmetric molecule having at least n  2, 4, 8, 10, 12, ..... :
one asymmetric carbon is known as asymmetric molecule. All asymmetric
molecules are also dissymmetric molecules but the reverse is not necessarily (i) Number of optically by active forms  a  2n 1
true. (ii) Number of enantiomeric pairs  a / 2
COOH (iii) Number of racemic mixture  a / 2
| CHO
(iv) Number of meso forms  m  2(n / 2)1
H — C  — OH |
(v) Total number of configurational isomers  a  m
| H — C  — OH
Case II : When compound has odd number of carbon atoms, i.e.,
H — C  — OH | n  3, 5, 7, 9, 11, ...... :
| CH 3
C6 H 5 No plane of symmetry (i) Number of optically active forms  a  2n 1  2(n 1) / 2

No plane of symmetry Dissymmetric molecule (ii) Number of enantiomeric pairs  a / 2
 
Dissymmetric molecule Asymmetric molecule (iii) Number of racemic mixutre  a / 2

Asymmetric molecule (iv) Number of meso forms  m  2(n 1) / 2
(iv) Chiral or asymmetric carbon atom : A carbon bonded to four (v) Total number of configurational isomers  a  m
different groups is called a chiral carbon or a chirality centre. The chirality (6) Optical activity of compounds containing one asymmetric
centre is indicated by asterisk. e.g., carbon
Examples :
 1036 General Organic Chemistry
 
Number of optical isomers  a  2 2 1  2
CH 3  C HOH  COOH ; CH 3  C HOH  CHO
Lacticacid
Number of meso forms  m  2 0  1
 
CH 2 OH  C HOH  CHO ; C6 H 5  C HCl  CH 3 Total number of configurational isomers  3
Glyceraldehyde 1 - chloro-1 - phenyletha ne
(8) Optical activity in compounds containing no assymmetric carbon
Any molecule having one asymmetric carbon atom exists in two : Although the largest number of known optically active compounds are
configurational isomers which are nonsuperimposible mirror images. optically active due to the presence of chiral carbon atom, some compounds
COOH COOH are also known which do not possess any chiral carbon atom, but on the
whole their molecules are chiral (such molecules were earlierly called
| | dissymmetric); hence they are optically active. Various types of compounds
H — C — OH HO — C — H belonging to this group are allenes, alkylidene cycloalkanes, spiro
| | compounds (spirans) and properly substituted biphenyls.
CH 3 CH 3 (i) Allenes : Allenes are the organic compounds of the following
(I) (II) general formulae.
(I) and (II) have the same molecular formula, the same structure C C C
but different configurations, hence (I) and (II) are known as configurational
isomers. (I) and (II) are nonsuperimposable mirror images, hence (I) and Allenes exhibit optical isomerism provided the two groups attached
(II) are optical isomers. Configurational isomers which are to each terminal carbon atom are different, i.e.,
nonsuperimposable mirror images are known as enantiomers. Thus (I) and a a a x
(II) are enantiomers. Pair of (I) and (II) is known as enantiomeric pair.
CCC or C C C
(i) Properties of Enantiomers : All chemical and physical properties
b b b y
of enantiomers are same except two physical properties.
Mode of rotation : One enantiomer rotates light to the right and the (ii) Alkylidene cycloalkanes and spiro compounds : When one or
other by an equal magnitude to the left direction. both of the double bonds in allenes are replaced by one and two rings, the
resulting systems are respectively known as alkylidene cycloalkanes and
(ii) Racemic Mixture : An equimolar mixture of two enantiomers is spirans.
called a racemic mixture (or racemate,  form, (dl) form or racemic
H 3C H
modification). Such a mixture is optically inactive because the two
enantiomers rotate the plane polarised light equally in opposite directions C
and cancel each other’s rotation. This phenomenon is called external H COOH
compensation. 1-Methylcyclohexylidene-4- acetic acid
(Alkylidene cycloalkane)
 Racemic mixture can be separated into (+) and (–) forms. The a CH 2 CH 2 a
separation is known as resolution. C C C
 The conversion of (+) or (–) form of the compound into a b CH 2 CH 2 b
racemic mixture is called racemisation. It can be caused by heat, light or by Spirans
chemical reagents.
(iii) Biphenyls : Suitably substituted diphenyl compounds are also
 Racemic mixture is designated as being (  ) or (dl). devoid of individual chiral carbon atom, but the molecules are chiral due to
(7) Optical activity of compounds containing two asymmetric restricted rotation around the single bond between the two benzene nuclei
carbon and hence they must exist in two non-superimposable mirror images of
each other. Such types of stereoisomerism which is due to restricted
Case I : When molecule is not divisible into two identical halves. rotation about single bond, is known as atropisomerism and the
The number of optical isomers possible in this case is four stereoisomers are known and atropisomers. Examples
(a  2 2  4 ) . Further there will be two pairs of enantiomers and two COOH ON2
F HOOC
racemic modifications. In practice also it is found to be so.
Configurational isomers which are not mirror images are known as
diastereomers. NO HOOC COOH F
Properties of Diastereomers : Diastereomers have different physical The above discussion leads to the conclusion that the essential
2

properties, e.g., melting and boiling points, refractive indices, solubilities in
different solvents, crystalline structures and specific rotations. Because of
differences in solubility they often can be separated from each other by
fractional crystallisation; because of slight differences in molecular shape
and polarity, they often can be separated by chromatography.
Diastereomers have different chemical properties towards both
chiral and achiral reagents. Neither any two diastereomers nor their
transition states are mirror images of each other and so will not necessarily
have the same energies. However, since the diastereomers have the same
functional groups, their chemical properties are not very dissimilar.
Case II : When molecule is divisible into two identical halves.
condition for optical isomerism is the molecular disymmetry or molecular
chirality and not the mere presence of a chiral centre. However, it may be
noted that the molecules having only one chiral centre are always chiral and
exhibit optical isomerism.
(9) Fischer projection formulae : The arrangement of the atoms or
groups in space that characterises a stereoisomer is called its configuration.
Emil Fischer (1891) provided an easy method to represent the three
dimensional formulae of various organic molecules on paper. Fischer
projection is, thus, a planar representation of the three dimensional
structure.
 General Organic Chemistry 1037
By convention, the following points are followed in writing the i.e., out of six substituents on two asymmetric carbons, at least two
Fischer formula. should be same.
(i) The carbon chain of the compound is arranged vertically, with When two like groups in Fischer projection formula are drawn on
the most oxidised carbon at the top. the same side of the vertical line, the isomer is called erythro form; if these
(ii) The asymmetric carbon atom is in the paper plane and is are placed on the opposite sides, the isomer is said to be threo form.
represented at the interaction of crossed lines.
R CH 3 CH 3
Asymmetric
Carbon atom | | |
a—C—b H — C — Cl H — C — Cl
| | |
c—C—b H — C — Br Br — C — H
| | |
C
R  C6 H 5 C6 H 5
Erythro form Erythro form Threo form
(iii) Vertical lines are used to represent bonds going away from the
observer, i.e., groups attached to the vertical lines are understood to be (c) R,S Nomenclature (Absolute configuration)
present behind the plane of the paper. The order of arrangement of four groups around a chiral carbon
(iv) Horizontal lines represent bonds coming towards the observer, (stereocentre) atom is called the absolute configuration around that atom.
i.e., groups attached to the horizontal lines are understood to be present System which indicates the absolute configuration was given by three
above the plane of the paper. chemists R.S. Cahn, C.K. Ingold and V. Prelog. This system is known as (R)
and (S) system or the Cahn-Ingold Prelog system. The letter (R) comes
(10) Name of optical isomers : Following three nomenclatures are from the latin rectus (means right) while (S) comes from the latin sinister
used for optically active compounds, (means left). Any chiral carbon atom has either a (R) configuration or a (S)
(i) D,L. System of nomenclature : This nomenclature is mainly used configuration. Therefore, one enantiomer is (R) and other is (S). A racemic
in sugar chemistry or optically active polyhydroxy carbonyl compounds. This mixture may be designated (R) (S), meaning a mixture of the two. (R) (S)
nomenclature was given by Emil Fischer to designate the configurations of nomenclature is assigned as follows :
various sugars relative to the enantiomeric (+) and (–) glucose as reference.
Step I : By a set of sequence rules given below the atoms or groups
All sugars whose Fischer projection formula shows the OH group connected to the chiral carbon are assigned a priority sequence.
on the chiral carbon atom adjacent to the terminal CH 2 OH group on the Sequence Rules for Order of Priority
right hand side belong to the D -series. Similarly if OH is on the left
Rule 1 : If all four atoms directly attached to the chiral carbon are
hand side, then the sugars belong to the L -series. different, priority depends on their atomic number. The atom having
| | highest atomic number gets the highest priority, i.e., (1). The atom with the
H — C — OH HO — C — H lowest atomic number is given the lowest priority, i.e., (2), the group with
| | next higher atomic number is given the next higher priority (3) and so on.
CH 2 OH CH 2 OH Thus,
D  series L  series
Cl 3
Examples :
| |
CHO CHO
| | F — C — I  4 — C —1
H — C — OH HO — C — H | |
| |
CH 2 OH CH 2 OH Br 2
D(d ) glyceraldehyde L (l) glyceraldehyde
or or
F Cl Br I

D( ) glyceraldehyde L () glyceraldehyde Increasing atomic number
 It must be noted that there is no relation between the sign of 4 3 2 1
rotation (+, – or d, l) and the configuration (D and L) of an enantiomer. Increasing priority
 Any compound that can be prepared from, or converted into COOH 4
D(+) glyceraldehyde will belong to D-series and similarly any compound that | |
can be prepared from, or converted into L(–) glyceraldehyde will belong to H 2 N — C — Br  3 —C —1
the L-series. | |
 This nomenclature is also used in  -amino acids. OH 2
C N O

Br
(ii) Erythro and Threo system of nomenclature : This nomenclature Increasing prioritywith atomic number
is used only in those compounds which have
Rule 2 : If two or more than two isotopes of the same element is
(a) Only two chiral carbons and present, the isotope of higher atomic mass receives the higher
(b) The following structure, R  Cab  Cbc  R priority.
1 2 3
1 H 1H 1H

Increasing priority
3 2 1
 1038 General Organic Chemistry

F 3
| |
Br  C  H  1 C  4
| |
Cl 2
Rule 3 : If two or more of the atoms directly bonded to the chiral In this Fischer projection the least priority number is not at the
carbon are identical, the atomic number of the next atoms are used for bottom of the plane.
priority assignment. If these atoms also have identical atoms attached to In such cases the Fischer projection formula of the compound is
them, priority is determined at the first point of difference along the chain. converted into another equivalent projection formula in such a manner that
The atom that has attached to it an atom of higher priority has the higher atom or group having the lowest priority is placed vertically downward.
priority. This may be done by two interchanges between four priority numbers. The
first interchange involves the two priority numbers, one is the least priority
I 2 H and Br
| 
number and other is the priority number which is present at the bottom of
I  H 2 C  H 2 C  C  C H 2  Br the plane. In the above case first interchange will takes place between 2 and
 | 4.
2 H and C CH 2  CH 2  CH 3
3 3

2 H and C
| First interchange |
1 C  4 1 C  2
| Between 2 and 4 |
2 4
In this example the atoms connected directly to the chiral carbon
(A) (B)
are iodine and three carbons. Iodine has the highest priority. Connected, to
the three carbons are 2H and Br, 2H and C and 2H and C. Bromine has the First interchange of two groups at the chiral centre inverts the
configuration and this gives enantiomer of the original compound. Thus (A)
highest atomic number among C,H and Br and thus CH 2 Br has highest
and (B) are enantiomer. The second interchange involves the remaining two
priority among these three groups (i.e., priority no. 2).The remaining two groups.
carbons are still identical (C and 2H) connected to the second carbons of 3 1
these groups are 2H and I and 2H and C. Iodine has highest priority among | Second interchange |
these atoms, so that CH 2  CH 2  I is next in the priority list and 1 C  2 3 C  2
| between remaining |
CH 2  CH 2  CH 3 has the last priority. 4 groups, i.e., 1 and 3 4
(B) (A)
I 1
|
Example : Arrangement of 1, 2 and 3 are
I  CH 2  CH 2  C  CH 2  Br  3 2 clockwise, hence configuration is R
|
H O
CHO C
CH 2 CH 2 CH 3 4 | O
|
H  C  OH  H  C  OH 
Rule 4 : If a double or a triple bond is linked to chiral centre the | |
involved atoms are duplicated or triplicated respectively. CH 2OH CH 2OH
D-glyceraldehyde
O N O O 2 2
| | || | | First interchange |
 C  O   C  O ;  C  N   C  N ;  C  OH   C  OH 4 C  1 3 C  1
| | | |
| Between 3 and 4 |
N O
3 4
1
By this rule, we obtained the following priority sequence : Second interchange
3 2
CH  CR 2 , CN , CH 2 OH, CHO, CO, COOH Between 1 and 2
4

Increasing priority 
Step 2 : The molecule is then visualised so that the group of lowest Clockwise
CHO 2 R-configuration
priority (4) is directed away from the observes (At this position the lowest | 1
| (i) First interchange between 3 and 4
priority is at the bottom of the plane). The remaining three groups are in a HO  C  H 
| 1 C  4 2 32
plane facing the observer. If the eye travels clockwise as we look from the | (ii) Sec. interchange between 1and 2
CH 2OH
group of highest priority to the groups of second and third priority (i.e., L -Glyceraldehyde
3 4
1  2  3 with respect to 4) the configuration is designated as R. If
Anticlockwise
arrangement of groups is in anticlocwise direction, the configuration is 
designated as S. S-configuration
Glyceraldehyde (For example) has one asymmetric carbon, hence it has
For example:
two configurational isomers (I) and (II).
2 2 CHO CHO
| | | |
1 C  3 3 C  1 H  C  OH HO  C  H
| | | |

4 4 CH 2 OH CH 2 OH
( R ) glyceral dehyde (S ) glyceral dehyde
Clockwise arrangement of Anticlockwise arrangement of (I) (II)
1 , 2 and 3  R 1 , 2 and 3  S One can draw a number other configurations for glyceraldehyde but
Let us apply the whole sequence to bromochlorofluoro methane. each of them will be a repetition of either (I) or (II). In this connection it is
 General Organic Chemistry 1039
important to note that if two projection formulae differ by an odd number Conformational isomerism
of interchanges (1, 3, 5, 7, …..) of positions of groups on the chiral carbon,
they are different. But if the two differ by an even number of interchanges (1) Definition : The different arrangement of atoms in a molecule
(2, 4, 6, …..) they are identical. which can be obtained due to rotation about carbon-carbon single bond are
For example : called conformational isomers (conformers) or rotational isomers
CHO (rotamers). This type of isomerism is found in alkanes and cycloalkanes and
CHO
| | their substituted derivatives.
H  C  OH  CH 2 OH  C  H 
H , CH 2OH

Second interchange
| First interchange | between OH , CHO
It may be noted that rotation around a C  C sigma bond is not
CH 2 OH H
( I) ( II) completely free. It is in fact hindered by an energy barrier of 1 to 20 kJ mol –1

OH in different bonds. There is a possibility of weak repulsive interactions

| between the bonds or electron pairs of the bonds on adjacent carbon atoms.
CH 2 OH  C  CHO   
Third intrerchange
Such type of repulsive interaction is known as torsional strain.
| CH 2OH , OH
H (2) Difference between conformation and configuration : The term
( III) conformation should not be confused with the configuration which relates
CH 2 OH CH 2 OH to those spatial arrangements of the atoms of a molecule that can be
| |
changed only by the breaking and making of bonds whereas the spatial
HO  C  CHO  HO  C  H Fourth interchange
arrangements in conformation are changed simply by rotation about a
| H , CHO |
H CHO single bond.
( IV ) (V )
(3) Representation of conformations : Conformers can be
Thus (I), (III) and (V) are identical. Similarly (II) and (IV) are represented in two simple ways. These are : (i) Saw horse representation
identical. and (ii) Newman projection
(11) Resolution of racemic modifications : The separation of racemic (i) Saw horse representation : In this projection, the molecule is
mixture into its enantiomers is known as resolution. viewed along the axis of the model from an oblique angle. The central
 Group X reacts with group O to give new group W. carbon-carbon bond ( C  C ) is draw as a straight line slightly tilted to
right for the sake of clarity. The front carbon is shown as the lower left
(12) Asymmetric synthesis and Walden inversion hand carbon and the rear carbon is shown as the upper right hand carbon.
(i) Asymmetric synthesis : The synthesis of an optically active The three bonds around each carbon atom (C  H in ethane or C  C in
compound (asymmetric) from a symmetrical molecule (having no higher alkanes) are shown by three lines.
asymmetric carbon) without resolution to form (+) or (–) isomer directly is
termed asymmetric synthesis. For example the reduction of pyruvic acid H
O Back carbon
||
(CH 3  C  COOH ) in presence of nickel catalyst gives () lactic acid C
(racemic mixture). On the other hand, pyruvic acid is reduced to (–) lactic H H H Back carbon
acid only by yeast. H H
H H
CH 3 CH 3 C Front carbon
| |
Front carbon

 H  C  OH  H  C  H
2H H H
' Ni' | |
COOH COOH H H
CH 3 ( ( Saw horse Newman projection : This is a Newman
(ii) representation projection
) Lactic acid ) Lactic acid
|
 simple method to represent the
C O   
Reduction mixture
conformations. In this method, the molecule is viewed from the front along
|
COOH the carbon-carbon bond axis. The two carbon atoms forming the -bond
CH 3
(Pyruvic acid)
(2 - Keto propanoic acid) | are represented by two circles; one behind the other so that only the front

 HO  C  H
2H
carbon is seen. The front carbon atom is shown by a point whereas the
Yeast |
carbon further from the eye is represented by the circle. Therefore, the
COOH
() Lactic acid C  H bonds of the front carbon are depicted from the centre of the
(ii) Walden inversion: The conversion of (+) form into (–) form and circle while C  H bonds of the back carbon are drawn from the
vice-versa is called Walden inversion. When an atom or group directly circumference of the circle at an angle of 120° to each other.
linked to an asymmetric carbon atom is replaced; the configuration of the (4) Conformation in alkanes
new compound may be opposite to (inverse) that of the original, i.e., (i) Conformations of ethane : When one of the carbon atom is kept
CH 3 CH 3 COOH fixed and other is rotated about C  C bond an infinite numbers of
| | | isomers are possible. Out of all the conformations for ethane, only two
H  C  OH  Cl  C  H
PCl5

 HO  C  H
AgOH
| | | extreme conformations are important and these are:
CH 2COOH CH 2 COOH CH 2COOH
() Malic acid () Chloro succinic acid () Malic acid
(a) Staggered conformation
(b) Eclipsed conformation
COOH COOH
| | 60°
 H  C  Cl
PCl5

 H  C  OH
AgOH H H
| |
H 60° H
CH 2COOH CH 2COOH H 60°
( ) Chloro succinic acid ( ) Malic acid H H
H H H H
H
60° Eclipsed conformation
Staggered
conformation
 1040 General Organic Chemistry
Staggered conformation of ethane is more stable than eclipsed.
(ii) Conformations of propane : The next higher member in alkane
series, propane (CH 3  CH 2  CH 3 ) also has two extreme
conformations, the energy barrier in propane is14kJmol , which is slightly
(i) Stability of cycloalkanes : Compounds with three and four
membered rings are not as stable as compounds with five or six membered
rings.
The German chemist Baeyer was the first to suggest that the
instability of these small rings compounds was due to angle strain. This
theory is known as Baeyer-strain theory.
–1

higher than that in ethane. Baeyer strain theory was based upon the assumption that when an
CH 3
CH open chain organic compound having the normal bond angle 109.5° is
convert into a cyclic compound, a definite distortion of this normal angle
3

H H H
takes place leading to the development of a strain in24.44°
the molecule.
H H H H deviation
H H H
Staggered propane Eclipsed propane
Newman projection of propane
(iii) Conformations of butane : As the alkane molecule becomes 109.5° 60°
larger, the conformation situation becomes more complex. In butane
109.5°
(CH 3  CH 2  CH 2  CH 3 ) , for example, the rotation about the single
24.44°
bond between two inner atoms ( C 2 and C 3 ) is considered. In this case, all deviation
the staggered as well as eclipsed conformations will not have same stability Baeyer assumed that cyclic rings are planar. Assuming that the rings
and energy because of different types of interaction between C  C (of are planar, the amount of strain in various cycloalkanes can be expressed in
methyl) and C  H bonds. terms of angle of deviation (d).
The lowest energy conformation will be the one, in which the two 1  2(n  2)  1
methyl groups are as far apart as possible i.e., 180° away form each other. d 109.5   90  or d [109.5   ]
2  n  2
This conformation will be maximum staggered, most stable and is
Where n = number of carbon-carbon bonds in cycloalkane ring; 
called anti or trans conformation (marked I). Other conformations can be
= inner bond angle in the cycloalkane ring.
obtained by rotating one of the C 2 or C 3 carbon atoms through an angle
1 1
of 60° as shown ahead. Anglestrain  d  ; Stability  inner angle( )
inner angle d
CH 3
CH 3
CH 3

H CH Now let us take the case of three to eight membered cyclic

H H H  
3

compounds.
HC 
H H
3
H H H
H H
CH H
3
Cyclopropane Cyclobutane Cyclopentane
I II III  = 60°  = 90°  = 108°
Anti Eclipsed Skew or Gauche d = 22.44° d = 9.4° d = 0.44°

CH3 CH 3 CH 3
 
CH3 H CH 3 H

H H H H H
H
H H H CH Cyclohexane Cycloheptane Cyclooctane
H 3

IV V VI  = 120°  = 128.6°  = 135°

Fully eclipsed Skew or Gauche Eclipsed d = –5.16° d = –9.33° d = –12.46°
As is clear from the (same
aboveasNewman
III) projection(same
the as
Gauche
II) or Skew The positive and negative values of (d) indicate whether the inner
conformations (III and V) are also staggered. However, in these angle is less than or more than the normal tetrahedral value.
conformations, the methyl groups are so close that they repel each other.
Beayer thus predicted that a five membered ring compound would
This repulsion causes gauche conformations, to have about 3.8 kJ mol more -1

be the most stable. He also predicted that six membered ring compounds
energy than anti conformation. This conformations II and VI are eclipsed
would be less stable and as the cyclic compounds become larger than five
conformations. These are unstable because of repulsions. These are 16 kJ
membered ring, then they would become less and less stable.
mol less stable than anti conformation. Conformation IV is also eclipsed and
-1

it is least stable having energy 19 kJ mol more than anti conformation. This
-1
Contrary to what Baeyer predicted, however cyclohexane is more
is because of repulsion between methyl-methyl groups which are very closed stable than cyclopentane. Furthermore, cyclic compounds do not become
together. It is called fully eclipsed conformation. less and less stable as the number of sides increase. Thus Baeyer strain
The order of stability of these conformations is, Anti > Skew or theory is applicable only to cyclopropane, cyclobutane and cyclopantane.
Gauche > Eclipsed > Fully eclipsed. The mistake that Baeyer made was to assume that all cyclic
(5) Conformations in cycloalkanes compounds are planar. But only cyclopropane is planar and other
cycloalkanes are not planar. Cyclic compounds twist and bend in order to

achieve structure that minimises the three different kinds of strain and that
can destabilise a cyclic compound.
(a) Angle strain is the strain that results when the bond angle is
different from desired tetrahedral bond angle of 109.5°.
(b) Torsional strain is caused by repulsion of the bonding electrons
of one substituent with bonding electrons of a nearby substituent.
(c) Steric strain is caused by atoms or groups of atoms approaching
each other too closely.
(ii) Conformation of cyclohexane : Despite Baeyer’s prediction that
five-membered cyclic compounds would be the most stable, the six
membered cyclic compound is the most stable. Six membered cyclic
compound are most stable because they can exist in a conformation that is
almost completely free of strain. This conformation is called the chair
conformation. In a chair conformation of cyclohexane all bond angles are
109.38° which is very close to the 109.5° and all the adjacent carbon-
hydrogen bonds are staggered.
a a
c H
c c H CH
a a
H CH
c 2
General Organic Chemistry 1041
 As a result of rotation about carbon-carbon single bonds
cyclohexane rapidly interconverts between two stable chair conformations.
This interconversion is known as ring –flip. When the two chair forms
interconvert, axial bonds become equatorial and equatorial bonds become
axial.
Flipping
 Cyclohexane can also exist in a boat conformation. Like the
chair conformation, the boat conformation is free of angle strain. However,
the boat conformation is less stable than the chair conformation by 11
kcal/mole. Boat conformation is less stable because some of the carbon-
hydrogen bonds in boat conformation are eclipsed.
The boat conformations is further destabilised by the close proximity
of the flagpole hydrogens. These hydrogens are 1.8 Å apart but the vander
H Waal’s radii is 2.4 Å. The flagpole hydrogens are also known as trans
2
H nuclear hydrogens.
H  The relative stabilities of the four conformations of cyclohexane

c c H H decrease in the order:

a a Newmann projection of the Chair > twist boat > boat > half chair.
chair conformation
Chair conformation of
cyclohexane
 Each carbon in chair conformation has an axial bond and an
equatorial bond.
 Axial bonds are perpendicular to the plane of the ring and
equatorial bonds are in the plane of the ring.
 If axial bond on carbon-1 is above the plane of the ring then
axial bond on carbon-2 will be below the plane of the ring. Thus
C  1, C  3 and C  5 axial bonds are above the plane

C  2, C  4 and C  6 axial bonds are below the plane

a a
1
6 5
a a

2 3 4
a a
 Thus C  1 axial and C  2 axial are trans to each other.
Similarly C  1 and C  5 axials are cis to each other.
 If axial bond on carbon-1 will be above the plane then
equatorial bond on this carbon will be below the plane.

(a) Above

(e) Below 1

(e) Above 2

(a) Below

(a) Thus C  1 equatorial and C  2 equatorial bonds are trans.

(b) C  1 axial and C  2 equatorial will be cis.
 General Organic Chemistry 1043
1. In methane molecule, the hydrogen atoms around carbon are arranged
as [DPMT 1980; MNR 1981; MP PET 1997, 99]
(a) Square planar (b) Tetrahedral
(c) Triangular (d) Octahedral
2. In carbon tetrachloride, four valence of carbon are directed to four
corners of [CPMT 1973, 77]
(a) Rectangle (b) Square
 Wohler synthesised the first organic compound urea in the (c) Tetrahedron (d) None of these
laboratory.
3. In alkene (ethene) number of sp 2 hybrid carbon atoms are
 The number of optical isomers of a compound depends on its (a) 1 (b) 2
structure and number of asymmetric carbon atoms present in its (c) 3 (d) 0
molecule.
4. Each carbon atom in benzene is in the state of hybridization
 Stereoisomers that are not mirror images of each other are called [CPMT 1973, 83, 89; MP PMT 1993;
diastereomers. KCET (Med.) 1999; DCE 2001]

 Order of priority for both asymmetric carbon atoms using (a) sp 3 (b) sp 2
sequence rules is (c) sp (d) s 3 p
–OH > – COOH > –CH(OH)COOH > –H 5. Which of the following hybridisation has highest percentage of s-
character [BHU 1986]
 The nitration and sulphonation of alkanes involve free radicals.
(a) sp 3 (b) sp 2
 Carbenes undergo insertion reactions.
(c) sp (d) None of these
 Alkanes usually undergo free radical substitution when hydrogen is
6. The hybridisation present in C 2 H 2 is [EAMCET 1993]
replaced by a halogen. It is catalysed by benzoyl peroxide (C H COO) .
6 5 2

2
 The polymerisation of alkenes is free radical addition reaction. (a) sp (b) sp
3
 Allyl free radical (CH = CH – CH ) is more stable than n-propyl (c) sp (d) dsp 2
2 2

free radical (CH CH CH ). 7. What hybrid orbitals will form the following compound
3 2 2

H 3 C  CH  CH  CH 2  CH 3 [AFMC 1991]
 The stability of free radicals is explained on the basis of
hyperconjugation or conjugation. (a) sp and sp 3 (b) sp 2 and sp 3
 Propene is more reactive than ethene towards electrophilic addition (c) sp and sp 2 (d) Only sp 3
reaction due to the formation of more stable 2° carbocation.
8. The compound in which carbon uses only its sp 3 hybrid orbitals
 The reactivity of alkyl halides in SN is 3°> 2°>1°>methyl while SN is
1 2

for bond formation is [IIT-JEE 1989]

methyl > 1°> 2°> 3°. (a) HCOOH (b) (NH 2 )2 CO
 Polar solvents favour SN while non polar solvents favour SN
1 2

(c) (CH 3 )3 COH (d) (CH 3 )3 CHO

reactions.
9. A straight chain hydrocarbon has the molecular formula C 8 H 10 .
 Dipole moment of CHCl is less than that of CH Cl . This is because
3 2 2
The hybridisation for the carbon atoms from one end of the chain to
in CH Cl all bond moments reinforce each other while in CHCl the bond
the other are respectively sp 3 , sp 2 , sp 2 , sp 3 , sp 2 , sp 2 , sp and
2 2 3

moment of one of the Cl opposes the net moment of the other two.
sp . The structural formula of the hydrocarbon would be[CBSE PMT 1992]
 Low concentration of nucleophiles favour SN while high 1

(a) CH 3  C  C  CH 2  CH  CH  CH  CH 2
concentration favour SN . 2

(b) CH 3  CH 2  CH  CH  CH 2  C  C  CH  CH 2
 In SN the attack of the nucleophile may be from either side and so
1

recimization takes place. However, in SN the attack of the nucleophile

2
(c) CH 3  CH  CH  CH 2  C  C  CH  CH 2
takes place from back side. So it leads to inversion of configuration. (d) CH 3  CH  CH  CH 2  CH  CH  C  CH
 Hunsdieker reaction proceeds via free radical mechanism. 10. Which of the following has a bond formed by overlap of sp  sp 3
 Propene reacts with chlorine at 673 K to form allyl chloride and hybrid orbitals [MNR 1993; UPSEAT 2001, 02]
the intermediate is allyl free radical.
(a) CH 3  C  C  H
(b) CH 3  CH  CH  CH 3
(c) CH 2  CH  CH  CH 2
(d) HC  CH
11. The bond between carbon atom (1) and carbon atom (2) in
compound N  C  CH  CH 2 involves the hybridised carbon as[IIT-JEE 198
Bonding and hybridisation in organic
compounds (a) sp 2 and sp 2 (b) sp 3 and sp

(c) sp and sp 2 (d) sp and sp