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(iv) HC C CH = CH 2
sp
sp sp
sp 2
First atom
H
C=C
Second atom
sp3
sp2
sp
1s and 3p
1s and 2p
1s and 1p
Nil
One
Two
Four -
Three -
One -
120
Trigonal
planar
33.33 or 1/3
Two -
Two -
180
Linear
109.5
Tetrahedral
% s-character
25 or 1/4
50 or 1/2
Type of hybridisation
sp3
sp2
sp
Examples :
O
||
sp 3
sp 2
sp 2
(iii)
sp
sp 3
sp 2
sp 2
sp 2
sp 3
1
H
bp = 2
3
Number of lps can be determined as follows, bp = 3
(a) If carbon has - bonds or positive charge or odd
electron, then lp on carbon will be zero.
(b) If carbon has negative charge, then lp will be equal to
one.
Number of electron pairs (ep) tells us the type of
hybridisation as follows,
ep
Type of
hybridisation
sp
3
sp 2
4
sp 3
5
sp 3 d
sp 3 d 2
Example :
(i) CH 2 = CH
(ii) CH 2 = CH
bp = 2
lp = 0
ep = 2, sp
bp = 2
lp = 1
ep = 3, sp 2
(iii) CH 2 = C CH 3
CH 3
bp = 3
lp = 0
ep = 3, sp 2
sp 2 sp 2 sp 3
CH 3 CH = CH CH 2 C N
H C C H
(iv) CH C
bp =1
lp = 1
ep = 2, sp
(ii) CH 2 = C = CH 2
Third atom
Central atom
(v) CH 3 CH CH 3
(i) CH 3 CH = CH C CH 3
bp = 3
sp
sp
bp = 3
lp = 1
ep = 4, sp 3
(3) Applications of hybridisation
(i) Size of the hybrid orbitals: Since s - orbitals are
closer to the 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 size of the three hybrid orbitals is
1015
opposite to that of the decreasing order of s orbital character in
the three hybrid orbitals.
CH 2 = CH
sp
Electropositive carbon
Electronegative carbon
having positive charge
Bond type
(C C)
Bond
length
sp 3 s
1.112
sp 3 sp 3
1.54
(alkanes)
1.103
sp 2 sp 2
1.34
(alkenes)
(alkenes)
1.08
sp sp
1.20
(alkynes)
(alkynes)
sp 3 s
Bond
energy
(kcal/mole)
Bond type
(C C)
104
sp 3 sp 3
(in
alkanes)
sp 2 s
(in alkynes)
Bond
energy
(kcal/mole)
80 90
(in alkynes)
H O H > NH 3 > CH CH
Electroneg ativity of the atoms
Acidity of compounds in decreasing order
sp 2 sp 2
33.33
25
25
44
50
pKa
HC CH > HC C CH 3
The relative acidic character follows the order;
Steric effect
On account of the presence of bulkier groups at the
reaction centre, they cause mechanical interference and with the
result the attacking reagent finds it difficult to reach the reaction
site and thus slows down the reaction. This phenomenon is
called steric hinderance or steric effect.
(1) Tertiary alkyl halides having bulky groups form
tertiary carbocation readily when hydrolysed because of the
presence of the three bulky groups on the carbon having
halogen.
H 3 C C Cl
CH
H 3 C C CH 3
CH 3
(in alkanes)
106
123 199
Bond type
(C H)
(alkanes)
sp sp
121
pKa
sp s
sp s
% s-character 50
sp 2
sp 2 s
(in alkenes)
CH 3 CH 2
(in
alkenes)
into carbocation.
122 164
CH
|
Bulky group
3
CH 2 Cl
CH 3 C
|
CH
N H 3 > NO 2 > CN > SO 3 H > CHO > CO > COOH > COCl > COOR
> CONH
Inductive
effect
ter. alkyl > sec. alkyl > pri. alkyl > CH 3 > H
+ I power in decreasing order with respect to the reference H
+ I power number of carbon in the same type of alkyl
groups
CH 3 CH 2 CH 2 CH 2 > CH 3 CH 2 CH 2 >
CH 3 CH 2
+ I power in decreasing order in same type of alkyl
groups
(3) Applications of Inductive effect
(i) Magnitude of positive and negative charges :
Magnitude of +ve charge on cations and magnitude of ve
charge on anions can be compared by + I or I groups present
in it.
charge
charge
Magnitude
of
+ve
1
Polarisability effect
(temporary)
Mesomeric Hyperconjugative
effect
effect
(3)
Steric strain inhibits the resonance. This
phenomenon is known as steric inhibitions of resonance.
Polarisation effect
(permanent)
CH 3
Inductomeric
effect
Electromeric
effect
H 3C
CH 3
> H 3C
CH
CH 3
> CH 3
X > CH 3
C C C C Non polar
C
CH 2
1017
(b) The group or atom having I effect increases the acid
strength as it decreases the negative charge on the carboxylate
ion. Greater is the number of such atoms or groups (having I
effect), greater is the acid strength.
Thus, acidic nature is,
Dichloro
acetic acid
Monochloro
acetic acid
Acetic acid
COOH
C6 H 5
COOH
NO2CH 2COOH > FCH 2COOH > ClCH 2COOH > BrCH 2COOH .
Iso propyl
alcohol
Ethyl
Alcohol
Tert butyl
alcohol
OH > H OH > CH 3
Water
Phenol
OH
Methyl alcohol
Ethyl
amine
Methyl
amine
Ammonia
groups
(R
I group
+ I group
(CH 3 )3 C
CH 3
C2 H 5
(CH 3 )2 CH
Chloro
amine
(CH 3 )3 COH > (CH 3 )2 CHOH > CH 3CH 2OH > CH 3OH
(3 o )
(2 o )
(1o )
+ M effect groups :
..
..
Cl , Br , I , N H 2 , NR2 ,OH ,OR, SH ,OCH 3 , S R
..
M effect groups :
O
||
NO 2 ,C N , C ,CHO ,COOH , SO 3 H
(i) H 2 C = CH CH = CH 2 H 2 C CH = CH C H 2
..
:O
||
..
..
:O:||
then
..
.- .
: Cl CH = CH 2 : Cl = CH CH 2
..
..
..
H C CH = CH 2 H C = CH C H 2
|
H
H
H
|
|
H C = CH C H
H C = CH C H
2
2
|
H
H
(ii) R C O H R C = O H
..
..
Both (i) and (ii) are the examples of mesomerism and
resonance effect. Let us consider the following example
..
H
Cl : H Cl . Such an electron displacement is the
..
example of resonance only (not the mesomerism).
Hyperconjugative effect
(1) When a H C bond is attached to an unsaturated
system such as double bond or a benzene ring, the sigma ()
electrons of the H C bond interact or enter into conjugation
with the unsaturated system. The interactions between the
electrons of systems (multiple bonds) and the adjacent
bonds (single H C bonds) of the substituent groups in
organic compounds is called hyperconjugation. The concept
of hyperconjugation was developed by Baker and Nathan and is
also known as Baker and Nathan effect.
In fact hyperconjugation effect is similar to resonance
effect. Since there is no bond between the -carbon atom and
one of the hydrogen atoms, the hyperconjugation is also called
no-bond resonance.
(2) Structural requirements for hyperconjugation
(i) Compound should have at least one sp 2 -hybrid
carbon of either alkene alkyl carbocation or alkyl free radical.
CH 3
CH 3
CH 3 > CH 3 CH 2 >
CH > CH 3 C
CH 3
CH 3
|
CH 3
1019
Electron donating power in decreasing order due to the
hyperconjugation.
(6) Heat of hydrogenation : Hyperconjugation
decreases the heat of hydrogenation.
H
HO H C Cl
H
Example,
H+
H C = O , H C CH = O H C = CH O
( = 2.27 D)
( = 2.72 D)
Cl
HO C H
Electromeric effect
(8) Orienting influence of alkyl group in o, p positions and of CCl 3 group in m -position : Ortho-para
directing property of methyl group in toluene is partly due to + I
effect and partly due to hyperconjugation.
Reverse Hyperconjugation : The phenomenon of
hyperconjugation is also observed in the system given below,
E
A = B
A B :
Reagent
X
|
C C = C ; where X = halogen
|
In such system the effect operates in the reverse direction.
Hence the hyperconjugation in such system is known as reverse
hyperconjugation.
Cl C CH = CH 2 Cl C = CH CH 2
|
|
Cl
Cl
Cl
Cl
C = CH CH 2 Cl C = CH CH 2
|
Cl
Cl
X
|
X C X
|
+ H
C+ C
|
Cl
Cl
C=C
Cl
X
|
XC
||
XC
||
XC
||
CH = CH 2 + H + CH 3 C H CH 3
Propene
C = O + CN -
X
-
CH 3
Inductomeric effect
Inductomeric effect is the temporary effect which
enhances the inductive effect and it accounts only in the
presence of an attacking reagent.
C O|
CN
The attacking reagent is not attached to that atom on
which electrons have been transferred.
(3) Direction of the shift of electron pair : The
direction of the shift of electron pair can be decided on the basis
of following points.
(i) When the groups linked to a multiple bond are similar,
the shift can occur in either direction.
(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.
C = O
C O :
A : B
carbanion
carbocatio n
A: +
A : B A + B
Free radical
Reaction Intermediates
Short lived fragments called reaction intermediates result
from homolytic and heterolytic bond fission. The important
reaction intermediates are free radicals, carbocations,
carbanions, carbenes, benzyne and nitrenes.
Table : 23.4
Characteristi
c
Free radical
Carbocation
Carbanion
Carbene
Nature
Positive charge on C
Negative charge on C
Hybridisation
sp2
sp2
Structure
Planar
Planar
sp3 (non-conjugated)
sp2 (Conjugated)
Pyramidal/Planar
Magnetism
Paramagnetic
Diamagnetic
Diamagnetic
Stability order
1 > CH 2 > CH 2 = CH
CH 2 = CH CH 2 >
Benzyne
(1) 1, 2-Didehydrobenzene, C6 H 4 and its derivatives are
called benzyne or arynes and the simplest member is benzyne.
(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.
Abnormal bond
Two sp2-orbitals
ouside the ring
1021
NH2
H
+ N H 2
NH2
..
Nitrenes (R N : )
(1) The nitrogen analogous of carbenes are called
nitrenes.
(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.
..
R .N.
These two are lone pair of electrons
H , X , R , N
, N = O, S O3 H
O ..
O
O
||
||
|| . .
Br 2 / NaOH
OH
R C NHBr
R C N Br
R C NH 2
H 2O
..
1o Amide
O
|| . .
Rearrangem ent
R C N
O = C = N R
Br
..
Isocyanate
KOH
R NH 2 + K 2CO3
(Hydrolysi s) 1o Amine
Alkylnitrene
..
(iii) Unsubstituted nitrene (H N :) can be obtained by
photolysis of (or by passing electric discharge through)
NH 3 , N 2 H 4 or N 3 H .
Attacking reagents
The fission of the substrate molecule to create centres of
high or low electron density is influenced by attacking reagents.
Most of the attacking reagents can be classified into two main
groups.
Electrophiles or electrophilic reagents and Nucleophiles
or nucleophilic reagents.
- -
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 octet, has at least one lone pair of electrons and all
atoms present on central atom should not be electronegative, is
neutral nucleophile.
..
..
..
.. ..
..
N H 3, R N H 2 , R2 N H , R3 N, N H 2 N H 2 (Nitrogen nucleophile)
..
..
..
..
..
..
H O H , R O H , R O R (Oxygen nucleophiles)
..
..
..
..
..
..
H S H , R S H , R S R (Sulphur nucleophiles)
..
..
..
..
P H 3 , R P H 2 , R2 P H , R3 P
(Phosphorus nucleophiles)
CH 2 = CH CH = CH 2 , CH 2 = CH C CH
(iii) Ambident nucleophiles : Species having two
nucleophilic centres out of which, one is neutral (complete octet
and has at least one lone pair of electrons) and the other is
charged (negative charge) behaves as ambident nucleophile
..
||
||
||
||
||
||
Br
Cl
Increasing basicity
R C H , R C R, R C OH , R C Cl ,
1
Basicity of the group
R C OR, R C NH 2 , R C N, R N C
||
CF3 S O > Br
S O > CH 3
||
||
F < OH <
NH 2
<
||
||
||
||
O
O
CH 3 CH 2 Br + NaOH CH 3 CH 2 OH + NaBr
||
||
OH
Example : R Cl
R OH + Cl .....(A)
( NaOH )
Cl .
Cl
R OH
R Cl + OH ......(B)
E Nu
R L
R Nu + L ; R L + Nu R Nu + L
(v) In SN reactions basicity of leaving group should be
Ethyl alcohol
Substitution reactions
Ethyl bromide
||
C6 H 5 S O > CH 3 S O
CH 3
Leaving group
S O >
Examples :
||
X-
Leaving group
R OH +
Nucleophil e
C N, O N = O, O S OH
nucleophile
R X + OH -
Substrate
..
( HCl )
1023
bonded directly with aromatic ring do not undergo nucleophilic
substitution reaction under ordinary conditions.
The reason for this unusual reactivity is the presence of
lone pair of electron or bond on the key atom of the functional
SN2 Reactions
Number of steps
SN1 Reactions
One: R : L + : Nu R : Nu + : L
(ii) R+ + : Nu R : Nu
First order:
Rate [Substrate] or Rate = K 1 [ RL ]
Fast
Second order:
Rate [Substrate] [Nucleophile] or Rate =
K 2 [ RL ][: Nu - ]
Molecularity
TS of slow step
Bimolecular
Unimolecular
: Nu C : L
The nucleophile attacks the carbon of the
substrate exclusively from the back side.
: Nu C L Nu :
The nucleophile can attack the carbon of the
substrate both from the back and front sides
although the back side attack predominates.
Rearrangement
Nature of nucleophiles
Polarity
Reacting nucleophile
Stereochemistry
Reactivity
halides
Reaction
factor
order
rate
of
alkyl
determining
By steric hindrance.
Catalysis
+E
Benzene
+
+ H+
hydrogen : R M + H R H + M
MgBr
e.g., CH 3 CH 2 MgBr CH 3 CH 2 CH 3 CH 3
H
CH 3 CH 2 MgBr + H Br CH 3 CH 2
CH 3 CH 3 + MgBr2
CH 3 CH 2 Na + C6 H 6 CH 3 CH 3 + C6 H 5 Na
In halogenation; Cl Cl + FeCl 3 Cl + Fe Cl 4
O
R3C Br + CO2 + AgBr
||
||
R H + D R D + H
R H + T R T + H
light
Methyl chloride
C6 H 5 H +
C6 H 5 N 2 X
Benzene diazonium halide
Alkali
C6 H 5 C6 H 5 + N 2 + HX
Diphenyl
CH 2 CO
CH 3 CH = CH 2 +
Propene
CCl 4
N Br
CH 2 CO
NBS
CH 2 CO
Br CH 2 CH = CH 2 +
Allylbromide
NH
CH 2 CO
Succinimid e
Addition reactions
These reactions are given by those compounds which
have at least one bond,
O
||
1025
Types of addition reactions : Addition reactions can
be classified into three categories on the basis of the nature of
initiating species.
(1) Electrophilic additions
(2) Nucleophilic additions
(3) Free radical additions
(1) Electrophilic addition reactions
(i) Such reactions are mainly given by alkenes and
alkynes.
(ii) Electrophilic addition reactions of alkenes and
alkynes are generally two step reactions.
(iii) Alkenes and alkynes give electrophilic addition with
those reagents which on dissociation gives electrophile as well as
nucleophile.
(iv) If the reagent is a weak acid then electrophilic
addition is catalysed by strong acids (Generally H 2 SO 4 ).
(v) Unsymmetrical alkenes and alkynes give addition
reactions with unsymmetrical reagents according to
Markownikoffs rule.
The negative part of the addendum adds on that doubly
bonded carbon of the alkene which has least number of
hydrogen atom.
This rule can be used only in those alkenes which fulfil
the following conditions:
(a) Alkene should be unsymmetrical.
(b) Substituent/substituents present on doubly bonded
carbon/(s) should only be +I group.
(c) If phenyl group is present on doubly bonded carbon,
then both doubly bonded carbons should be substituted by
phenyl groups.
For example, the following alkenes will give addition
according to the Markownikoffs rule.
CH 3
CH 3 CH = CH 2 ,
CH 2 CH 2 CHO
CH 2 = CH CHO + HCl
C=C
Olefin
Electrophi le
C C E +
Nucleophil e
Slow
C C E
|
Carbonium ion
|
Fast
C C E
|
Addition product
C=O
C O
C O
CH 3
CH 3
C = O+ HCN
CH 3
OH
C
CH 3
Acetone
CN
Acetone cyanohydri n
C6 H 5
C = CH C6 H 5, C6 H 5 CH = CH 2
C6 H 5
Following alkenes will not give addition reaction
according to Markownikoffs rule.
CH 2 = CH 2 , R CH = CH R,
R
C=C
C6 H 5
CH 3
CH 3
CN
CH 3
C=C
C6 H 5
Cl
|
C = CH 2 ,
CH 3
C6 H 5
Example:
C6 H 5
CX 3 , NO 2, CN ,CHO ,COR,COOH , C Z
(Z = Cl , OH , OR, NH 2 )
CH 3
C O+ H NC C OH or
|
OH
C
CH 3
CN
CH 3
In
CN
+ H
C = O
( A.R.)
(AN)
H 3C
C
CN
reactions
on
carbonyl
H 3C
C=O >
H
C=O >
H
C=O
H 3C
||
||
> CONH
> COOH
Elimination reactions
Elimination reactions are formally the reverse of addition
reactions 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 linkage or centre.
Elimination reaction is given by those compounds which
have a nucleophilic group as leaving group,
R, S
R
CH 3
|
CH 3 C Cl
|
CH 3
C H O/
25
CH
=C
+ C2 H 5 OH + Cl
CH 3
CH 3
is
carbocation,
..
CH 3 CH 2 CH 2 L CH 3 CH = CH 2 + H + L
OH
CN
Nucleophilic addition
compounds will be in order:
CN
C O
CH 3
| +
Slow step
CH 3 C Cl CH 3+ C - - - - - Cl
CH 3 C CH 3 + Cl
CH 3
CH 3
CH 3
(TS1 )
( RI )
Step 2.
B + H CH 2 C CH 3 B - - - - H - - - -CH 2 - - - - C CH 3
|
|
CH 3
CH 3
TS 2
..
CH 3
B H + CH 2 = C
fast
CX 2 + X + H
CHX 3
CH 3
(ii) E2 (Elimination bimolecular) reaction : Consider
the following reaction,
Base ( B)
CH 3 CH 2 CH 2 Br
CH 3 CH = CH 2 + H + Br
1027
(b) Since the reaction is a bimolecular reaction, the
product formation will take place by formation of transition
state (TS).
(c) Rearrangement does not take place in E2 reaction but
in case of allylic compound rearrangement is possible.
(d) Reaction is carried out in the presence of polar
aprotic solvent.
(e)
..
The
E2
reaction
occurs
in
one
B - - - - H +
|
|
Slow step
CH 3 C C H CH 3 C
|
|
|
H Br
TS
fast
CH 3 CH = CH 2 + BH + Br
Cl
|
Alc.KOH /
CH 3 C = CH CH 3
CH 3 CH CH CH 3
|
CH 3
HCl
CH
Br
|
CH 3
CH 3
Hofmann product
( HX )
2- Butene (Major)
X
CH 3 CH 2 CH = CH 2
1- Butene (Minor)
H 2 C = CH 2
( H 2 O)
CH 3 CH = CH 2
( H 2O)
Propan - 1- ol
Dehydration
of
alcohols
Propene
is
in
the
order:
(2)
(1)
OH
CH 3 CH 2 CH CH 3 and so
|
OH
OH
OH
>
OH
>
CH 3 C CH 2 CH CH 3 CH 3 C CH 2 CH = CH 2
|
Propene
Alc.KOH
CH 3 CH 2 CH CH 3
CH 3 CH = CH CH 3 +
CH 3
Alc.KOH /
( HX )
Ethene
CH 3 CH CH 3 CH 3 CH = CH 2
3
Saytzeff product
CH 3
( HX )
Alc.KOH
step,
|
C H
Br
Alc.KOH
CH 3 CH 2 X
H 2 C = CH 2 ;
e.g.,
in CH 3 OH , heat
CH 2 CH 2 + Zn dust
H 2 C = CH 2
|
Br
Br
(-ZnBr2 )
Ethylene
Ethylene bromide
CH 3 C CH 3
|
( H 2 )
OH
Isopropyl alcohol
||
Acetone
Rearrangement reactions
The reactions, which involve the migration of an atom or
group from one site to another within the molecule (nothing is
added from outside and nothing is eliminated) resulting in a
new molecular structure, are known as rearrangement reactions.
The new compound is actually the structural isomer of the
original one.
B: |
|
|
|
|
|
Y
C C C C C C
|
X:
Y
+
Bridged or
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.
(3) Rearrangement or migration to free radical
species (Free radical rearrangement) : Those rearrangement
reactions in which the migrating group moves to a free radical
centre. Free radical rearrangements are comparatively rare.
Isomerism
Organic compounds having same molecular formula but
differing from each other at least in some physical or chemical
properties or both are known as isomers (Berzelius) and the
phenomenon is known as isomerism.
The difference in properties of isomers is due to the
difference in the relative arrangements of various atoms or
groups present in their molecules. Isomerism can be classified
as follows:
Isomerism
Constitutional or structural
isomerism
Without referring to space, the isomers differ in
the arrangement of atoms within the molecule is
called structural isomerism. Thus structural
isomers have:
Chain
Position
isomeris
isomerism
m
Constitutional or
Ring chain
isomerism
Functional
isomerism
Meta
merism
structural isomerism
(i)
: CH 3 CH 2 CH 2 CH 3 ,
n Butane
CH 3 CH CH 3
|
CH 3
Tauto merism
Geometrica
Optical
Conformational
l
isomeris
isomerism
Chain
isomers differ
isomerism
m in the nature of carbon chain, i.e.,
Isobutane
CH 3
|
CH 3 C H CH 2 CH 3 , CH 3 C CH 3
|
CH 3
Isopentane
CH 3
Neopentane
1,1Dichloro propane
(gemdihali de)
CH 3 C H C H 2 , C H 2 CH 2 C H 2
|
Cl
Cl
Cl
Cl
1, 2 Dichloro propane
(Vicdihalide)
1029
Structural isomers which differ in the position of the
functional group are called regiomers. For example, (i)
CH 3 CH 2 CH 2 OH (ii) CH 3 CH CH 3
|
OH
(3) Functional isomerism : This type of isomerism is
due to difference in the nature of functional group present in the
isomers. The following pairs of compounds always form
functional isomers with each other.
CH 3
CH 3 C H CH 3 ; CH 3 CH 2 N
|
CH 3
NH 2
N , N Dimethyl methanamin e
Propan - 2- amine
OH
CH3
C7 H8 O ;
Examples :
o-Cresol
Benzyl alcohol
Dimethyl ether
||
C3H8O : CH 3 CH 2 CH 2 OH ; C 2 H 5 O CH 3
n propyl alcohol
C4H10O
Acetaldoxi me
CH 3 CH 2 CH 2 CH 2 OH ;
C2H5NO : CH 3 CH = NOH ; CH 3 C NH 2
n Butyl alcohol
C2 H 5 O C2 H 5
H2
C
Diethyl ether
O
C3H6O : CH 3 CH 2 CHO ; CH 3 C CH 3 ;
H 2C
CH 2
1, 2 Epoxy propane
carbonyl
Methyl formate
C
H2
CH 2 CH 2
Cyclohexan e
Allyl alcohol
Methyl acetate
O
||
CH 3 C HCHO ; CH 3 C CH 2 OH
|
CH 2
Acetone
CH 2 CH CH 3 ; CH 2 = CH CH 2 OH
Acetic acid
H 2C
|
||
Propionald ehyde
Acetamide
C H 2 CH 2
CHCH 3
1 Hexene
OH
Methyl cyclopenta ne
CH 3
; C2 H 5 N
CH 3
2 Hydroxy propanal
C2 H 5
CH 3
(ii) C6H15N : C3 H 7 NH C3 H 7 ; C2 H 5 NH C4 H 9
Dipropyl amine
1,3 Butadiene
1 Butyne
CH 3 C C CH 3 ; H 2C = C = CH CH 3
1, 2 Butadiene
2 Butyne
O N = O )
O
C2H5NO2 : C2 H 5 N
; C2 H 5 O N = O
Ethyl nitrite
Nitro ethane
CH 3 CH 2 C CH 2 CH 3
(Pentan 3 one)
(b) CH 3 C CH 2 CH 2 CH 3 ;
||
(Pentan 2 one)
CH 3 C C H CH 3
CH 3 CH 2 N
CH 3
||
N Methyl ethanamine
(Pentan 2 one)
||
O CH 3
(3- Methylbuta n- 2- one)
O H
||
OH
|
C C C = C
|
|
(Keto)
(Enol)
OH
||
CH 3 C CH 2COOC 2 H 5 CH 3 C = CHCOOC 2 H 5
Acetoacetic ester gives certain reactions showing the
presence of keto group (Reactions with HCN , H 2 NOH ,
OH
O
|
CH 3 C = CH R CH 3 C = CH R
H 2O
OH -
(Enol)
H O N =O
HN
nitrite form
O
O
Nitro form
CH 3 CH 2 N
O
O
CH 3 CH = N
O
OH
For example
Enolisation is in order
CH 3 COCH 3 < CH 3 COCH 2 COOC 2 H 5 < C 6 H 5 COCH 2 COOC 2 H 5
O
||
Keto
OH
OH
CH 3 C C H R CH 3 C = CH R
(Enol form)
H
(Intermedi ate)
O
||
CH 3 C CH 2 R
Keto form
OH H2O
O
||
CH 3 C C H R
-
Number of isomers
C4 H10
Two
C5 H12
Three
C6 H 14
Five
C7 H16
Nine
C8 H18
Eighteen
C9 H 20
Thirty five
1031
C10 H 22
Seventy five
Aromatic
compounds
Alkenes and
cycloalkanes
C8 H 10
Four
C3 H 6
C9 H 12
Nine
C4 H 8
C7 H 8 O
Five
C5 H 10
Nine (Five
cycloalkanes)
alkenes
Alkynes
C3 H 4
Two
C4 H 6
Six
Monohalides
C3 H 7 X
Two
C4 H 9 X
Four
C5 H 11 X
Eight
Examples :
H C COOH
Dihalides
C2 H 4 X 2
Two
C3 H 6 X 2
Four
C4 H 8 X 2
Nine
C5 H 10 X 2
Twenty one
||
H C COOH
Maleic acid (cis)
H 3C C COOH
||
H C COOH
Citraconic acid (cis- isomer)
Alcohols and
ethers
C2 H 6 O
C3 H 8 O
C4 H 10 O
Seven (Four
ethers)
C5 H 12 O
alcohols
and
three
Aldehydes and
ketones
C3 H 6 O
C4 H 8 O
Three (Two
ketone)
C5 H 10 O
aldehydes
and
one
Monocarboxylic
acids and esters
C 2 H 4 O2
C 3 H 6 O2
C4 H 8 O2
C5 H 10 O2
Aliphatic amines
C2 H 7 N
C3 H 9 N
C4 H 11 N
H C COOH
||
HOOC C H
Fumaric acid (trans)
H 3C C COOH
||
HOOC C H
(b)
frozen rotation about carbon, carbon single
bond in cycloalkanes.
(c)
C = N frozen rotation about carbon, nitrogen
double bond in oxime and imine.
(ii) Both substituents on each carbon should be different
about which rotation is frozen.
If these two conditions are fulfilled, then compound will
show geometrical isomerism.
The compounds of the following type will not show
geometrical isomerism.
a C a x C a a C a
||
||
||
x Cy aCa x C x
(2) Distinction between cis- and trans- isomers
(i) By cyclization method : Generally, the cis-isomer
(e.g. maleic acid) cyclises on heating to form the corresponding
anhydride while the trans-isomer does not form its anhydride.
H C COOH
||
H C COOH
Maleic acid( cis)
Heat
H C CO
||
H C CO
Maleic anhydride
CH 3 C H
b.p
m.p.
||
H C COOH
OH
H
H
OH
COOH
COOH
H C COOH
||
HOOC C H
OH
H
HOOC
KMnO 4
OH
COOH
H
(+ ) Tartaric acid
HOOC
H
OH
OH
H
COOH
() Tartaric acid
(iii) By studying their dipole moments: The cisisomer 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, 1,2dichloroethylene and butene-2.
H C CH 3
H C Cl
H C Cl
H C CH 3
||
||
||
||
H CCl
Cl C H
CH 3 C H
H C CH 3
cis Dichloroet hylene
( =1.9 D)
cis Butene 2
trans Butene 2
( = 0.0 D)
H 3C
H
C=C
CH 2 CH 2 CH 3
H
H
CH 3
C=C
||
CH 3 C H
HOOC C H
H C COOH
CH 3 C H
||
Heat
No anhydride
CH 2 CH 2 CH 3
H
H C CH 3
cis 2 Butene
4 C
139 C
trans 2Butene
1 C
106 C
H C Cl
H C Cl
H C Cl
Cl C H
||
||
a
b
C=C
d
e
C=C
E isomer
C=C
Z isomer
1
2
( D)
priority in comparison to hydrogen ( H ) .
2
1
is assigned higher
1033
(iii) In the groups, the order of preference is also decided
on the basis of atomic number of first atom of the group. For
example, in the following set,
Cl ,OH ,COOH , NH CH 3 ,SO 3 H .
The order of the precedence is :
Cl > S O3 H > O H > N HCH 3 > C OOH
( at.no17)
(at.no.16)
(at.no.8)
(at.no.7)
||
Anti benzaldoxi me
Syn - benzaldoxi me
(at.no.6)
||
HO N
N OH
(at.no. 6)
(at.no.8)
(at.no.1)
N OH
Syn methyl ethyl ketoxime
or Anti ethyl methyl ketoxime
||
||
C6 H 5 N
Syn - azobenzene
C N is equal to C N .
N
(4) Number of geometrical isomers in polyenes
(i) When a compound has n double bonds and ends of a
polyene are different, the number of geometrical isomers = 2n
C6 H 5 CH = CH CH = CH CH = CH CH = CH Cl
The given compound has four double bonds and the two
ends are different (One is C6 H 5 and other is Cl). Therefore,
number of geometrical isomers = 2n = 24 = 16 .
(ii) When the ends of polyene are same.
Case I : When number of double bonds (=n) is even then
the number of geometrical isomers = 2n 1 + 2[(n / 2)1]
Cl CH = CH CH = CH CH = CH CH = CH Cl
Number of geometrical isomers = 2n1 + 2(n / 2)1 = 23 + 21
= 8 + 2 = 10 .
Case II : When number of double bonds (=n) is odd.
n+1
Anti azobenzene
(6)
Geometrical
isomerism
show
by
cumulatrienes : Cumulatrienes (Trienes with three adjacent
double bonds) show only geometric isomerism. This is because
their molecule is planar, as such the terminal CH 3 groups and
H- atoms lie in the same plane. Therefore, in this case their
planar structure can exist in two diastereoisomeric forms, cisand trans- but no enantiomeric forms are possible.
H 3C
CH 3
C=C=C=C
H
H
cis Hexa 2,3,4 triene
H 3C
H
C=C=C=C
trans Hexa 2,3,4 triene
n = 4, even
N C6 H 5
H
CH 3
Trans-1,2-cyclopent
anediol
Optical isomerism
(1) Compounds having similar physical and chemical
properties but they have the ability to rotate the plane of
polarised light either to the right (Clockwise) or to the left
(Anticlockwise) are termed as optically active or optical isomers
and the property is called optical activity or optical isomerism.
obs
l C
COOH
|
H C OH
|
H C OH
|
COOH
(b) Centre of symmetry : It may be defined as a point in
the molecule through which if a line is drawn in one direction
and extended to equal distance in opposite direction, it meets
another similar group or atom, eg.
CH 3
Non-superimposable
(Chiral or dissymmetric)
NH CO
Mirror
Superimposable
(Achiral or non-dissymmetric)
Plane of symmetry
CH 3
CH 3
C
CO NH
Centre of symmetry
NH CO
and C
|
CO NH
CH 3
H
cis Dimethyl diketo piperazine
Cl
H
H
F 180o rotation
H
Cl
H
F
H
H
Dissymmetric
F
Cl
H
Cl
around axis
H
F
Cl and
H
(iii) Symmetric, Asymmetric
H
Cl
F
H
molecules
(a) Symmetric molecules : If any symmetry is present in
the molecule then molecule will be symmetric molecule.
(b) Dissymmetric molecules : Molecule will be a
dissymmetric molecule if it has no plane of symmetry, no centre
of symmetry and no alternating axis of symmetry.
(c) Asymmetric molecules : Dissymmetric molecule
having at least one asymmetric carbon is known as asymmetric
molecule. All asymmetric molecules are also dissymmetric
molecules but the reverse is not necessarily true.
1035
(iii) Number of racemic mixture = a / 2
COOH
CHO
H C OH
H C OH
H C OH
CH 3
No plane of symmetry
Dissymmetr ic molecule
Asymmetric molecule
C6 H 5
No plane of symmetry
Dissymmetr ic molecule
Asymmetric molecule
CH 3
HO C H
d C b
|
c
Lactic acid
COOH
Lactic acid
Carbons that can be chirality centres are sp 3 hybridised carbons; sp 2 and sp -hybridised carbons cannot be
chiral carbons because they cannot have four group attached to
them.
Isotopes of an atom behave as different group in
stereoisomerism.
H1
|
*
H C T
|
Cl
35
C Cl
|
37
H2
Lactic acid
O
||
CH 3 , CH 2OH , CHX 2 , CHO , C Z
Maleic acid (HOOC CH = CH COOH )
geometrical isomerism while malic acid
show
Glyceralde hyde
C6 H 5 C HCl CH 3
1- chloro -1- phenyletha ne
COOH
COOH
H C OH
Br
CH 2 OH C HOH CHO ;
HO C H
CH 3
CH 3
(I)
(II)
(I) and (II) have the same molecular formula, the same
structure but different configurations, hence (I) and (II) are
known as configurational isomers. (I) and (II) are
nonsuperimposable mirror images, hence (I) and (II) are optical
isomers. Configurational isomers which are nonsuperimposable
mirror images are known as enantiomers. Thus (I) and (II)
are enantiomers. Pair of (I) and (II) is known as enantiomeric
pair.
(i) Properties of Enantiomers : All chemical and
physical properties of enantiomers are same except two physical
properties.
Mode of rotation : One enantiomer rotates light to the
right and the other by an equal magnitude to the left
direction.
(ii) Racemic Mixture : An equimolar mixture of two
enantiomers is called a racemic mixture (or racemate, form,
(dl) form or racemic modification). Such a mixture is optically
inactive because the two enantiomers rotate the plane polarised
light equally in opposite directions and cancel each others
rotation. This phenomenon is called external compensation.
Racemic mixture can be separated into (+) and ()
forms. The separation is known as resolution.
The conversion of (+) or () form of the compound
into a racemic mixture is called racemisation. It can be caused
by heat, light or by chemical reagents.
Racemic mixture is designated as being ( ) or (dl).
C=C=C
Allenes exhibit optical isomerism provided the two
groups attached to each terminal carbon atom are different, i.e.,
a
C=C=C
x
C=C=C
or
(ii)
Alkylidene
cycloalkanes
and
spiro
compounds : When one or both of the double bonds in allenes
are replaced by one and two rings, the resulting systems are
respectively known as alkylidene cycloalkanes and spirans.
H 3C
H
=C
COOH
CH 2
C
CH 2
C
CH 2
a
C
CH 2
Spirans
F HOOC
NO2 HOOC
COOH F
The above discussion leads to the conclusion that the
essential 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.
By convention, the following points are followed in
writing the Fischer formula.
(i) The carbon chain of the compound is arranged
vertically, with the most oxidised carbon at the top.
(ii) The asymmetric carbon atom is in the paper plane
and is represented at the interaction of crossed lines.
Asymmetric
Carbon atom
C
(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 present behind the plane of the paper.
(iv) Horizontal lines represent bonds coming towards the
observer, i.e., groups attached to the horizontal lines are
understood to be present above the plane of the paper.
(10) Name of optical isomers : Following three
nomenclatures are used for optically active compounds,
(i) D,L. System of nomenclature : This
nomenclature is mainly used in sugar chemistry or optically
active polyhydroxy carbonyl compounds. This nomenclature
1037
was given by Emil Fischer to designate the configurations of
various sugars relative to the enantiomeric (+) and () glucose
as reference.
All sugars whose Fischer projection formula shows the
OH group on the chiral carbon atom adjacent to the terminal
CH 2OH group on the right hand side belong to the D -series.
Similarly if OH is on the left hand side, then the sugars belong
to the L -series.
HO C H
H C OH
CH 2 OH
CH 2 OH
L series
Examples :
CHO
CHO
H C OH
HO C H
CH 2 OH
CH 2 OH
D(d ) glyceraldehyde
L (l ) glyceraldehyde
or
or
L () glyceraldehyde
D(+ ) glyceraldehyde
Cl
CH 3
CH 3
aCb
H C Cl
H C Cl
cCb
H C Br
Br C H
R
Erythro form
|
D series
C6 H 5
Erythro form
C6 H 5
Threo form
F C I 4 C1
|
|
2
Br
F Cl Br I
COOH
|
H 2 N C Br
4
|
3C1
2
OH
C N O Br
Increasing
priority
3
2
3
|
2 H and Br
I H 2 C H 2 C C C H 2 Br
2 H and C
CH 2 CH 2 CH 3
2 H and C
I CH 2 CH 2 C CH 2 Br
(A)
(B)
1
Second
i t h
between remaining
groups, i.e., 1 and
CH 2 CH 2 CH 3
1 C 2
3
First
i t h
Between 2 and 4
1 C 2
|
||
4
(B)
3 C 2
|
(A)
Arrangement of 1 , 2 and 3 are
clockwise, hence configuration is R
Example :
C = O C O ; C N C N ; C OH C OH
|
CH = CR2 ,
Increasing
Step 2 : The molecule
i itis then visualised so that the group
of lowest priority (4) is directed away from the observes (At this
position the lowest priority is at the bottom of the plane). The
remaining three groups are in a plane facing the observer. If the
eye travels clockwise as we look from the group of highest
priority to the groups of second and third priority (i.e.,
1 2 3 with respect to 4) the configuration is designated as
R. If arrangement of groups is in anticlocwise direction, the
configuration is designated as S.
For example:
2
1 C 3
|
3 C 1
methane.
F
|
Br C H
|
Cl
3
|
1 C 4
|
O
O
|
H C OH
CHO
H C OH
CH 2OH
2
CH 2OH
First interchange
D-glyceraldehyde
|
C 1
Between 3 and
HO C H
L -Glyceraldehyde
1
2
3
2
Clockwise
Rconfiguration
2
|
CH 2OH
Second
i t h
Between 1 and
CHO
C 1
and 4
and 2
1
3
2
4
Anticlockwise
S-configuration
CHO
|
H C OH
|
CH 2OH
( R) glyceral dehyde
(I )
CHO
|
HO C H
|
CH 2OH
(S) glyceral dehyde
(II)
1039
different. But if the two differ by an even number of
interchanges (2, 4, 6, ..) they are identical.
For example :
CHO
CHO
|
H C OH
|
H , CH 2OH
Second interchang e
CH 2OH C H
between OH , CHO
First interchang e
CH 2OH
H
( II )
(I )
OH
|
Third intrerchan ge
CH 2OH C CHO
CH 2OH , OH
H
( III)
CH 2OH
CH 2OH
HO C CHO HO C H
Fourth interchang e
H ,CHO
CHO
( IV)
(V )
Thus (I), (III) and (V) are identical. Similarly (II) and
(IV) are identical.
(11) Resolution of racemic modifications : The
separation of racemic mixture into its enantiomers is known as
resolution.
Group X reacts with group O to give new group W.
(12) Asymmetric synthesis and Walden inversion
(i) Asymmetric synthesis : The synthesis of an
optically active compound (asymmetric) from a symmetrical
molecule (having no asymmetric carbon) without resolution to
form (+) or () isomer directly is termed asymmetric
synthesis. For example the reduction of pyruvic acid
O
||
CH 3
Conformational isomerism
(1) Definition : The different arrangement of atoms in a
molecule which can be obtained due to rotation about carboncarbon single bond are called conformational isomers
(conformers) or rotational isomers (rotamers). This type of
isomerism is found in alkanes and cycloalkanes and their
substituted derivatives.
It may be noted that rotation around a C C sigma bond
is not completely free. It is in fact hindered by an energy barrier
of 1 to 20 kJ mol1 in different bonds. There is a possibility of
weak repulsive interactions between the bonds or electron pairs
of the bonds on adjacent carbon atoms. Such type of repulsive
interaction is known as torsional strain.
(2) Difference between conformation and
configuration : The term conformation should not be
confused with the configuration which relates 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
arrangements in conformation are changed simply by rotation
about a single bond.
(3) Representation of conformations : Conformers
can be represented in two simple ways. These are : (i) Saw horse
representation and (ii) Newman projection
(i) Saw horse representation : In this projection, the
molecule is viewed along the axis of the model from an oblique
angle. The central 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 hand carbon and the rear
carbon is shown as the upper right hand carbon. The three
bonds around each carbon atom (C H in ethane or C C in
higher alkanes) are shown by three lines.
H
CH 3
Back carbon
2H
H C OH + H C H
' Ni '
CH 3
() Lactic acid
Reduction
mixture
C
|
HO C H
2H
COOH
() Lactic acid
H C OH
PCl 5
Cl C H
CH 2COOH
AgOH
HO C H
|
CH 2COOH
(+ ) Malic acid
CH 2COOH
() Malic acid
COOH
COOH
|
H C Cl
PCl 5
CH 2COOH
H C OH
AgOH
Front
b
Back carbon
H
Front
Hcarbon
H
H
Newman
Saw horse
(ii) Newman projection : This
is a simple method to
i
Yeast
H
H
CH 3
(Pyruvic acid)
(2-Keto propanoic acid)
COOH
(+ ) Lactic acid
C=O
|
COOH
COOH
CH 2COOH
(+ ) Malic acid
60
Staggered
conformation
CH3
H
H
H
Staggered propane
Eclipsed propane
Newman projection of propane
the rotation about the single bond between two inner atoms (
C2 and C3 ) is considered. In this case, all the staggered as well
as eclipsed conformations will not have same stability and
energy because of different types of interaction between C C
(of methyl) and C H bonds.
The lowest energy conformation will be the one, in which
the two methyl groups are as far apart as possible i.e., 180 away
form each other.
This conformation will be maximum staggered, most
stable and is called anti or trans conformation (marked I).
Other conformations can be obtained by rotating one of the C2
or C3 carbon atoms through an angle of 60 as shown ahead.
CH3
H
H
CH3
I
Anti
H
H
CH3
CH3
H
H3C
H
CH3
CH3
H
IV
Fully
III
Skew or Gauche
CH3
II
Eclipsed
H
H
V
Skew or Gauche
(same as III)
H
H
109.5
H
CH3
VI
Eclipsed
(same as II)
60
109.5
24.44
deviation
d=
CH3
CH3
CH3
24.44
deviation
1
2(n 2)
109 .5
90
n
2
or
d=
1
[109 .5 ]
2
Angle strain d
1
1
; Stability inner angle( )
d
inner angle
Cyclopropane
= 60
d = 22.44
Cyclobutane
= 90
d = 9.4
Cyclopentane
= 108
d = 0.44
Cyclohexane
= 120
Cycloheptane
= 128.6
Cyclooctane
= 135
1041
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
a
c
c
a
a
c
c
a
Chair conformation of
cyclohexane
CH2
CH2
H
H
H
H
Newmann projection of
the chair conformation
a
5
4
3
a
a
(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.
Flipping