1

ISOMERISM
The acorance of more than one compounds of same molecular formula is called
isomerism and such compounds are known as isomers.
eg

CH3 O CH3

and

CH3 CH2 OH

(C2H6O)
CH3CH2 CHO

and

CH3 C CH3

(C3H6O)
Since isomers are different compounds they have different physical and chemical
properties. Structural
Stereo / Space
Or constituitional

Chain

Positional

Ring chain

Functional

Metamers

Tantomers

configratinal / conformational
Geometrical

Optical

Structural versus stereo isom. Isomers differing in connectivity of atom are called
structral isomers.

eg

CH3 CH CH3

and

CH3 CH2 CH2 OH

and

CH3 CH2 OH

OH
CH3 O CH3

Isomers have same connectivity of atom but different spetial arrangement of atom or
group about a centre or bond are called stereo isomers.
Cl
CH2 CH2

and

CH3

CH3
C=C

CH2 CH2
CH3
and

H
C=C

etc.
CH3

Chain isomers: str. iso. Differing in chains of C atom.

eg

CH3 CH2 CH2 CH2 CH3

and

CH3 CH CH2 CH3

CH3

Positional isomers: differing in position of an atom / group.

2
CH3 CH CH3

and

CH3 CH2 CH2

OH

OH
CH3

CH3

CH3

OH

OH
OH

Actually only those

Str. will chain isomers in which parants chain are different otherwise positional isomers.
eg

(1) CH3 CH2 CH2 CH2 CH2 CH2 CH3

(2) CH3 CH2 CH CH2 CH2 CH3
CH3
(3) CH3 CH CH2 CH2 CH2 CH3
CH3
(4) CH3 CH CH CH2 CH3
CH3

CH3

(1) Is the chain isomer of all (2) is chain isomer of (i) and (iv) but positional isomer of
(iii).
Ring chain isomers: If one isomer has ring str. while the other has open chain str. then they
CH3 CH = CH2

or,

CH2 = CH OH

or,

CH3

and,

CH CH2 CH3
CH3

Both however can have ring but then the size of

rings is should be different.

Functional :
eg

Functional group differ.

O

CH3 C

and

H C OCH3

OH
CH3 CH2 OH

CH3 C CH3
O

CH3 CH2 CHO

CH3 C CH3

***

Metamers : functional group not monovalant. If no. of C atom differ either side at
the functional group.

eg

CH3 CH2 O CH2 CH3 and

***

Tautomers: Readily inter convertible structural isomers.

CH3 O CH2 CH2 CH3

CH3 C

and

CH3 CH2 C

CH3

II.

OH

CH3 C

CH2 = C
CH3

CH3

III.

CH2 C
H

CH3
I.

I and II one not are interconvertible therefore I and III are tautomers of each other.

Tautomers are different compels therefore they have different physical and chemical
properties. Even then it is very difficult to separate then. This is because tautomers exist
in a state of dynamic equilm. However separation is possible specially when all tautomers
are in good proportions and employed technique does not allow enter conversion.
O

OH

CH3 C
99%

CH2 = C
CH3

1%

CH3

cont be separate

If we take,
O

CH3 C CH2 C CH3

Q.

18%

H release..

can be separate.

CH3 C = CH C CH3
92%

(b) no

Tautomers can be separate

(a) yes

**

Tautomers can be easily separate.

(a) yes

Q.

OH

(b) no

Condition for tautomerism: Molecule must have at least one (=) bond and a H atom at
the conjugated position.
O
CH3 C PH

OH
CH2 = C PH

O
*

PH C H
O

PH C PH
CH3 CH = NH2

CH2 = CH NH2
OH

OH

CH3 CH2 CH2 C H

***

()
O

Percentage enol content: Percentage enol content depend upon

(a) Stablity of enol ; PEC stab of enol
(b) Acidity of enolizable H ; greater is the acidity higher will be EC.
(c) Solvent

(d) Temparature:

Stability factor:

OH

CH3 C CH3

CH2 = C CH3

C=O

C=O

CH

OH

(B E C = O + BE C H) > (BEC = C, BE O H) therefore in this case ketoform is more

stable than enol form.
O
CH3

C CH2 C

OH
CH3

CH3

O
CH

CH3

Acetyl acetone:
Stabilization energy

C=O

C = C , OH H bond extended resonance.

CH
In case of acetyl acetone enol form is more stable then ketoform.
O
CH3

O
CH3

CH3

Q. 1.
I.

CH2

CH3

II.

enol content II > I.

O

CH3

C CH2
O

O
CH2
O

OH
CH3

CH3 C = CH C CH3
OH

5
II.

PH

CH2

O
III.

CH3

O C

CH2

O
IV.

(2)

PH

C = CH C CH3

C CH3 > C OCH3

CH3

CH3O C CH2 C OCH3

enol content ; II > I > III > IV.

O
O

OH

I.

II.

enol content I > II.

(3)

CH3

CH3
C=O

C=O

CH3
I

C=O
CH3

II

III.

enol content III > II > I.

(4)

enol content III > II > I

I

II

III

Enolization; enolization can be either acid / bone catalysed

Acid catalysed process;
H+

O
CH3

CH3

OH
CH2 C

OH
CH3

CH2 = C CH3 H

H
H+ protonates carboxylic O and thus cleavage C = O and C H bond becomes very
easy.
Base catalysed process.
OH

O
CH2

CH3

O
CH2 C

CH3

H OH

CH2 = C CH3
O

6
CH2 = C

CH3 + OH
O

CH3

CH2 CH3

H+
OH
CH3 C

CH3

CH2

OH

H+

OH

OH

CH2 = C

CH2 CH3

CH CH3

O
C

CH3
OH
O

CH3 C = CH C

CH3

II.

II is more stable than I. became more substituted (=) is more stable.

CH3
C = CH2 > CH3 C = CH2
CH3
In acid catalysed process stability of enol is driving force but in base catalysed proves
acidity of enolizable H is the driving force.
***

Isotope exchange
OH

D2O

R OH D O R OD.
2

CH3COOH D O CH3COOD.
2

Mechanism : R

HO+

R
O
D+ O

D+

R
O

R
O
D

T.S.

O/H bond can be exchange but not C H because in C H bond H is not protic.
O

PH

+H

O
CH3

D2O (excess
)

PH C

CD3

Propose mechanism ?
O

OH

OD

7
PH C = CH2 D O

PH C CH3
OD
PH C

PH C

CH2

OH

CH

D 2O

PH C

CH

PH C

CH2
D

OH

PH C CD2

PH C

CD2 D O
2

H
O
PH C

OD
CD3

PH C

CD2

Effect of temperature on enol content:

O
CH3

O
CH2

OH
CH3

CH3

25oC

x%

35oC

y%

45oC

z%

CH

CH3

x > y > z . At high temperature H bond breaks therefore enol content decreases.

Solvent effect on enol content:

O
CH3

OH

C CH2 C CH3

CH3

Gas phase

x%

in H2O

y%

C CH C CH3
[x > y]

In water keto form makes H bond with water molecules, therefore need to go in enol
form decreases.
O

OH

CH3 C CH3

CH2 = C

CH3

35oC

x%

50oC

y%

[x > y]

Configurational verses conformational isomers:

If stereo isomers cannot be inter converted without cleaving any bond then they are called
confugrational isomers on the other band if this interconversion is possible without
cleaving any bond then they are called conformational isomers.
Cl
CH2 CH2

CH2 CH2

conform.

8
Br

Cl

Br

CH3

CH3
C=C

configra
H
A bond has to be cleaved

CH3

H
C=C

CH3

Geometrical isomers:
Configrational isomerism arising due to different spetial arrangement of atoms or groups
about a bond along which rotation is restricted is called geometrical isomerism these
bonds on be multiple bond or single bonds of ring.

Q.

Geometrical isomers is possible along which of the following multiple bonds.

(a) C = C

(b) C C

(c) C = N

(d) C = O

(e) N = N

Note that two isomers can be geometrical isomers only if they differ in spetial distance
between the groups.
Q.

Geometrical isomers occur with :

(a) Alkene

(b) Alkyne

(c) imines

(d) ketones

(e) hydragone.

(i) case of C = C bonds: geometrical isomers about C = C bond will be possible only if
each C of the double bonds bears two different groups.
a

C=C

a
C=C

C=C
a

CH3 CH = CH CH2 CH3

CH3CH2 CH = CH CH2 CH2 CH3
CH2 = CH CH = CH2
CH2 = CH CH = CH CH3
CH2 CH = CH CH = CH CH3
Case of C = C bond in ring :
H

H2

No geometrical isomers because trans configuration is not possible. However it becomes

possible from 8 membered ring onwards.
CH3 CH = C = CH CH3
CH3 CH = C = C = CH CH3
CH3
CH3
C=C=C
H
H
Cumelens
(i)
Even no. of C = C bond
geometrical isomers isomerism
(ii)
Odd no. of C = C bond
geometrical isomers occurs if each and bears two different ------------------.
Cabin Ingold prelog sequence rule:
(1)
The group having first atom of high atomic no (at-wt) will be of higher priority.
eg
CH3 , OH , NH2 , Cl, H
C
O
N
Cl H
Cl > OH > NH2 > CH3 > H.
(2)
If frist atom same then apply above rule on second atoms
CH3
eg
CH3, CH2 CH3, CH
, CH2 Br
CH3
CCl3 , CHBr2 respectively 3H 2H, C ; H, 2C; 2H; Br ; 3Cl ; H, 2Br H C Br Cl ;
Br > Cl > Cl > C > H
CH3
~ CHBr2 > CH2Br > CCl3 >
> CH2 CH3 > CH3
CH3
O
eg

CHO

CO

C=O

CHO ; COOH ; CH2OH ; C N ; CH2 NH2

O, O, O

HHH

HHH

CN

O
CO

N C

OH O,O,O

COOH > CHO > CH2OH > CN > CH2NH2

CH3

Q.

CH = CH2 , C CH , C CH3 , PH ;

10
CH3

Cis-trans Nomencl.
This method is applied when both atom of C = C contain at least one identical group.
CH3 C = C CH3
H

CH3 C = C C2 H5

If identical group lie on the same side of the C = C bond then it is called cis-isomer
otherwise trans isomer.
CH3 CH = CH C2 H5

CH3

CH3

C2 H 5

2 pentene.

C=C

H
C=C

C2 H 5

Cis

Trans

Br

Cl

Br

C=C

Br
C=C

Cl

Br

Cl

Trans

Cl

Cis

Br

I
C=C

Cl

solved by following method.

F

E/Z nomenclature: Top priority groups are on the same side then it is called Z isomer
otherwise E isomer
Br

Br

C=C
Cl

F
C=C

Cl

(Z)

I
(E)

This method can be apply in all cases of geometrical isomerism.

CH3

CH3

CH3

C=C
H

C=C
H

Cis/2

Cl

CH3
Trans/E

I
C=C

I
C=C

Cl

Cl

11
Number of geometrical isomers = 2n where n = the no. of C = C bonds. However if no. of
C = C bond is equal to 1 then no. of geometrical isomers is always two, but if no. of C =
C bond is more than 1 then no. of geo isomer may be 2n or < 2n.
i.e

C = C = 1 ; G.I = 2
C = C > 2 ; G.I 2n

It will be 2n when numbering of P.C is not possible from either side. On the other hand it
will be less than 2n, when numbering P.C possible from either side.
(i) CH3 CH = CH CH3

(geo.)

(ii) Cis

= 2.

(iii) trans.
Cis, trans

Cis, trans.

(ii)
CH3 CH = CH CH = CH CH 2 CH2 No. of geom isom = (4) since
numbering is possible only from left.
(I) Cis Cis (II) Cis trans (III) trans Cis IV .
(i)

H
C=C

C2H5

(ii)

CH3

C2H5
C=C

C=C
H

H
C=C

Cis Cis

C2H5

Trans trans.

H
C=C

C2H5

CH3
H

H
C=C

C=C
H

H
C2H5

C2H5
C=C

Cis trans
(ii)

Trans Cis.

CH3 CH = CH CH = CH CH3
H

H
C=C

CH3

CH3
C=C

H
H

CH3
Cis Cis I

C=C

CH3
H

C=C
H

CH3

II. Trans-trans
CH3

H
C=C

III. Cis-trans

III and IV are identical

CH3

C=C

C=C

CH3
C=C

IV Trans-Cis.
H

12
No. of geo.-isomer = 3.
(iii)

CH3 CH = CH CH CH = CH CH3

a)

CCC

CCC

b)

CCT

TCC

c)

CTC

CTC

d)

CTT

TTC

e)

TCC

CCT

f)

TCT

TCT

g)

TCT

CTT

h)

TTT

TTT

No. of geom isomers = 6

Cyclic cases: Geometrical isom. also occurs in rings. Since rotation about C C single bond of
ring is also restricted.
CH2 CH CH CH3
C2H5 C2H5
However it will be possible only if ring bears at least two groups same or different at
different position.
CH3
CH3

(1)

CH

(2)

3
Br

CH3

(3)

CH3

(4)
Br

CH3
CH3

(6)

CH3

Br

(7)

Br

(8)

CH3

CH3
Br

Cl

Br

(9)

(10)

Br

Br
CH3

(3)

CH3
CH3

(5)

Br

CH3

CH3

or,

;
Br

CH3

Br

or,

Br

13

(5)

CH3

CH3

CH3

CH3

CH3

CH3

Both are identical, therefore, no geometrical isomerism in this case.

O(sp2)

(7)
H

or,

CH3

CH3

Sp3
CH3

d1 = d2

Note geo isomers, since spetial distance does not charge.

H

Br

Br

Cis

Br
H

Br

Br

H
Br

Br

Cis

Trans.

Br

Trans

(C/T) Br

***Q.
(i)

No. of geo isomers = 4.

CH = CH CH3
(C/T)

CH3

CH3

C=N
C2H5

(Z)

OH
C=N

OH

C2H5

(Oxime)
Synethyl or antimethyl ~ Geom-isomers are possible.
*

Choose w.r.t heavier group.

(ii)

CH3 N = N CH3

CH3

2
sp2 sp

N=N

N=N
CH3

CH3

CH3
Trans/Anti ()

Interconversion of geometrical isomers :

Cis syn(2)

14
Since rotation about C = C is restricted. Interconversion of geometrical isomers is
possible only if bond is cleare. This can be done either by heating or with the help of
catalyst. Which can be an acid or base or radicals.
CH3
(i)

(cis)

CH3

A = B homo or, heterolysis.

C=C
H
CH3

CH3

CC

H
CH3
(ii)

C=C
H

CH3

CH3

CH3

CH3

C=C
H

CH3

CH3

C=C
H

Io

CH3

CH3

CC

H
CH3

CCH

CH3

CH3

CC
CH3

CCH
H

CH3

CH3

CH3

CC
CH3

CC

+ H+
H

CH3

H.W

Propose mechanism for base catahysed rean

Stability of geometrical isomers:

+ Io
CH3

That geometrical isomers will be more stable in which steric repulsion is less.
CH3

CH3

C
H
Trans

CH3
C

CH3

H
Cis
CH3

CH3

15
H
H

C2H5
C=C

C2H5

C=C

CH3

C2H5

CH3
C2H5

C
CH3

CH3

Trans

<

Cis

Melting point of geometrical isomers

F2(I), Cl2(I), Br2( ), I2 ()
i.e intermolecular force of attraction
I2 > Br2 > Cl2 > F2

Polarisation of e clad.
+

eg

C=O
+

OH

CH3 CH2 CH2 CH2 CH3

CH3 CH2 CH2 CH2 CH3 n pentane Intermolecular vander walls force of alteration
is more in n pantane that in new pentane
Intermolecular vander walls force of alteration (for single molecule) is more in neo-pent.
Than in n pertane. Therefore new-pentane is more stable than n-pentane.
CH3

CH3

CH3 C CH3
CH3
CH3

CH3 C CH3 Neo-pentane

CH3

CH3

CH3

C=C
H
(Cis)

CH = CH
map

C=C
H

CH3

H
CH3

CH3

(Trans)

CH3 CH = CH CH3
map

16
intermolecular vander walls force of attraction is more in trans isomer than in cis.
Therefore map of trans 2 butane is more straight than that of cis.

Solubility
CH3 OH

H2O

O
H

H2O

H2O

H2O

OH2

Na+
H2O

OH2

OH2

OH2

Cl
H2O

H2O
H2O

H2O

H2O

CH4. O
H
Solubility of cis isomer is more then that of trans isomer.

Optical isomerism:
Plane polarised light: Ordinary light vibrates in all dir n, when pass to a nicol prism
(Made up of CalO3), it begins to vibrate in only one dirn. Then it is called plane polarized
light.
Sample tesle containing
Org. compd.
Nicol prism

Right ward
dextro.

No effect or. Compd (inactive)

(optically)

left ward
leavo.

Active

Compd

Opt-active

Opt inactive

Dextrorotatory
d or (+)

Leavorotatory
l or ()

Optical isomerism is the isomerism which deals with optically altive compds. However
either all optical isomers will be optically active or some may be active and some
inactive.
Asymmetric centre / chiral centre
The C atom bearing for different group is called asymmetric or chiral centre.

CH3 CH CH2 CH3

CH3 CH2 CH CH2 CH2 CH3
Br

* C = 1.

Br

17
CH3 CH CH CH3
Br

CH3 CH CH CH3

Br

Br

* C = 2 (Similar)

Cl

* C = 2 (dissimilar)

Br
CH3

CH

C=C
H

C=C
H

CH3

cis

trans

* C = 1.
O
O

OH
* C = 1.

OH
*C=O
CH3
CH3

* C = 2 (similar)

OH
*C=O

OH
*C=O
CH3

CH3

OH
* C = 1.

CH3
(C* = 2)

CH3

C* = O.

Presentation of asymmetric C centre and R/S configuration.

(i)

Fischer projection formula:

COOH
CH3 CH C2H5

CH3

COOH

COOH

H CH3

C2H5

1 to 3 via 2

C2H5

Clock wise R
Anti clock S.

CH3

H HOOC

C2H5

C2H5
H

CH3
H

COOH
CH3 II

C2H5

COOH II

Note: That this str. having same configuration on all respective assymetric centre will be
identical.
H

CH3
R

C2H5
S

OH

OH

OH
I.

CH3
H

H R
II

OH
C2H5

18
OH
OH

OH

CH3

C2H5

C2H5

III

IV

OH
OH

I and II are identical

I and III are identical
I and II are identical
II and III are identical
II and IV are identical
III and IV are identical
(i)

H
H

CH3

CH3
OH

(ii) HO

OH

C2H5
Cl
OH

CH3
OH

HO

Cl
H

C2H5

Cl

C2H5

OH

OH

OH

CH3 C2H5
H

Cl

Cl

C2H5 C2H5
OH

OH

CH3

OH

C2H5

HO

CH3
CH3

Cl

Cl

H
CH3

OH

Cl

OH
Cl

HO

CH3
H

COOH

COOCH3

OH

OH

OH

OH

COOCH3

Cl
H

OH

Cl

Cl

(III)

OH
C2H5

CH3
H

COOH
OH

19
COOH
H

CH

OH
OH

Cl

COOH ;

Cl

COOCH3
O

CH
OC

OH

Both are non identical.

2.

In wedge formula:

CH3 CH COOH
OH
Hs

CH3

COOH OH

C
OH

COOH

CH3
R

;
CH3

C2H5

OH

In sawhorse formula:
This formula is written it molecule has two/more assym. centre

CH3 CH CH C2H5
OH
CH3

OH
H

OH

H
OH

C2H5

C2H5

Cl

OH

vertical bond

OH

C2H5

CH3
CH3

C2H5
OH

OH

H
H

CH3
CH3

H
OH

CH3

OH
H

Cl
H

Cl

Cl
CH3

Cl

OH

20
OH
and

C2H5

R
H

H
S

CH3

OH

Plane of Symmetry:
If molecule can be divided with two equal portions One portion being the mirror image
of the other portion then it is said to have plane of symmetry.
A molecule without plane of symmetry is called dissymmetric. Note that all the
symmetric molecules are optically inactive.
Has plane of symmetry

CH3
H

OH

OH

optically inactive.

CH3
Na plane of symmetry

CH3
H

OH

HO

Molecule is dissymmetric and thus optically active.

CH3
Q.

HO
CH3

CH3

OH

CH3
OH

OH
CH3

Comparing planes of symmetry

Both are identical

Has plane of symmetry.
If C* = 1 always dissymmetric.
If

C* = 2

Dissimilar

similar

All isomers will be

Dissymmetric isomer

symmetric isomer

always dissymmetric
R

MIRROR IMAGE

If configuration on similar assym. contes are opposite

R

21
Non-super impossible

Super impossible

All dissymmetric molecules have

All symmetric molecules have super

non-super impossible mirror image

impossible mirror image

There structures will be non super impossible mirror image of each other in which
configurations are opposite on all respective asymmetric centres.
CH3

CH3

OH

HO

Br

Br

CH3

CH3

CH3

OH
OH

Br

Br

CH3

R
S

CH3
H

CH3

Dissymmetric
I & II one non-super impossible mirror

Both non-super impossible mirror

image of each other

image of each other.

Condition for optical isomers:

(i)

Presence of symmetric centres:

If a molecule at symmetric centre then optical isomerism certainly occurs. However there
are molecules which do not have any asymmetric centres but exhibit optical isomerism.

(ii)

presence of dissymmetry:
Molecule with dissymmetry are always optically active therefore having dissymmetry is
the compulsory condition to exhibit optical isomerism
No. of optical isomerism = 2n
Where n = no. of assym. centre
However in some cases no. of optical isomerism will be less than 2 n. These cases will be
the cases of similar asymmetric centres.
C* = 1 No. of optical isomer = 2,
dissimilar

C* = 2

similar

No. of isomer = 4

No. of isom = 3

CH3 CH COOH
OH
COOH

COOH
OH

OH

CH3

H
CH3

Both are active and called enantiomers.

CH3 CH CH CH3
OH

Br

22
CH3

CH3

OH

HO

H A pair of enantiomers.

Br

Br

CH3

II

CH3

CH3
CH3

HO

OH A pair of enantiomers.

Br

Br

III

CH3

IV

CH3

No. of optical isomers = 4.

I is diastereomers of III and IV.
III is diastereomers of I and II.

CH3 CH CH CH3
Br

Br

CH3

CH3

Br

Br

H I and II identical called

Br

Br

CH3

II

mesomer.

CH3

CH3

CH3

Br

Br NO. of isomer = 3 because

Br

Br

CH3

I and II are identical

CH3

Both are pair of enantiomers.

Features of enantiomers:

(i)

Those two str. are enantiomers of each other which are non super impossible mirror
image of each other.

(ii)

Those two structure are enantiomers of each other which have opposite configuration on
all respective centres.

(iii)

Enantiomers are always dissymmetric and there optically active. One will be
dextrorotatory while other leavo. by same magnitude.
COOH
H

COOH
OH

CH3

HO

H
CH3

+ 20o

20o

45o

+ 45o

23
(iv)

An equimolar mixture of enantiomer is called recemic mixture, recemic mix are

optically inactive due to external compensations.

(v)
Mesomer:
(i)

Optically inactive isomers is called mesomers

(ii)

It is found only in cases of two or more similar asymmetric centres.

(iii)

That isomer will be mesomers which has plane of symmetry consequently, its mirror
image will be super impossible.

(iv)

That str. will be mesomer in which configuration are opposite on similar asymmetric
centres within the molecules.
This is the reason that mesomers are optically inactive.

CH3
H

CH3
Br

Br

C2H5

C2H5

(+ 30)

( 30)
CH3

+ 40o

OH

OH
CH3

40o

Mesomers are optically inactive is dextro while other half is leavo by same magnitude.
Diastereomers:

Those isomers are diastereomers which are not mirror image of each other.

The two str. which are neither identical nor non enantiomers are diastereomes

All chemical and physical prop. of diastereomes are different.

On the other land enantiomers have all physical properties same except their entraction
with plane polarized light which in equal and opposite.
They all chemical properties of enantiomers are same except their reactivity with chiral
reagents.

Geometrical diastereomer.
S
R

C2H5
Br

Br

C2H5
R
S

Br
R
R

C2H5

C2H5

Br
S
R

24
H

OH

CH3

HO

HO

CH3

CH3

II

III

HO

CH3
H
IV

I & II II & IV enantiomer

I & III II & III III & IV diastereomes
I & IV identical.
Q.

COOH
H

COOH

CH3

CH3

C2H5

H
C2H5

enantiomers.
This order doesnt match with experimental order. However only the position of
cyclohexane is delocated i.e theory faith of cyclohexane cense of this failure is the
assumption that all rings are planer. But cyclohexane is not planer. It exist in chair and
boat form mainly.
120o
hypothetical

Chair

Boat

form All age form = 109o 28

As = O
mp = mp

Bp = Bp

solubility = solubility
RI

but +2o
COOH
H

Br

R I.
20o / 20o
CH3OH/H+
K1

+ 20o
COOCH3
H

CH3

Br
CH3

and
COOH
Br

K2

CH3
If reagent is chiral such as
CH3
H

Br

H
CH2

K1 = K2

HO

COOCH3

CH3OH/H+

then

K1 K2

25
O
Q.

A recemic mixture of (+) 2 phenyl propanoic acid on esterification with (+) 2 butanol
gives two esters mention the stereochemistry of two esters produced cases involving both
geometrical and optical isomers.
Optical isomerism doesnt effect the no. of geoisomers. But the geometrical isomerism
effect the no. of optical isomers.

CH3 CH = CH CH CH3
OH
No. of geom.. isomers = 2
Optical isomers = 4.
H
CH3

CH3
C

CH3
OH (Trans dl-pair)

HO

H
C

CH3

H
H

CH3
C

CH3
OH (Cis dl-pair)

HO

H
C

H
C

CH3

CH3
Sterio isomers = 4
Recemic mixture = ?

Q.

CH3 CH = CH CH = CH CH CH3
Br
Geom. isomers = 4
Optical isomers = 8
Stereo isomers = 8

Q.

Recemic mixture = 4.

CH3 CH = CH CH CH CH3
OH

Br

Geom. isomers = 2
Optical isomers = 8
Stereo isomers = 8
Recemic mixture = 4
Cases of cyclanes:
Br

Cl

Br

26
CH3

CH3

C2H5

CH3

GI=2

GI=2

GI=2

GI=0

OI=4

OI=3

OI=4

OI=2

Rm=1

Rm=2

Rm=1

Meso = 1
CH3
H

C2H5

Trans dl pair

C2H5

CH3

CH3

CH3
C2H5 C H
2 5

Cis dl pair

H
H

D/L configuration:

CHO
H

CHO
OH

OH

CH2OH

H
CH2OH

D / (+) Glycerol

L / () Glycerol

i.e (+) Glycerol is assigned D configuration while () Glycerol is assigned L

configuration assignment is arbitrary
Glyceric Acid :
CH2 CH COOH
OH

OH

If D glycerol is obtained then configuration is given glyceric acid was D and it L

glycerol obtained then configuration in glyceric acid was li.
Glycerol : similar configuration Retension / Inversion in configuration.
Retension occurs if reagent attack from the front side and inversion occurs if reagent
attacks. From the back side.
CH3
H

Br
C2H5

OH

CH3

CH3

OH + OH

CH3

C2H5

Retension prd

Inversion prd.

Inversion also called Waldens inversion Erythro threo nomenclature:

27
This nomenclature is applied when molecule has two dissimilar assymetric carbon atom
containing two similar group.
CH3 CH CH C2H5.
OH

CH3 CH CH C2H5

Br

OH

OH

If similar group are same side in fisher projection formula then it is called srythro isomer
otherwise threo isomers.
CH2

CH3

OH

HO

OH

HO

C2H5

C2H5
Erythro dl pairs

CH3

CH3

OH

HO

HO

OH

C2H5

C2H5
Threo dl pair

Optical isomerism without C*

Case of cumulenes
CH3

CH3
C=C=C

H
Non-planer

The molecule is dis symmetric therefore optically active.

No. of optical isomers = 2
CH3

CH3
C=C=C=C

(No optically active)

CH3

H
C=C=C

(planer) symmetric

not planer symmetric

No optical activity.

H
Cumulenes

Even no. of C = C optical isomerism

occurs and if each bears two different

Odd no. of C = C geometrical isom.

occurs if each and every bears two

28
groups

different groups.

Case of biphenyles:
Biphenyl exhibits optical isomerism if ortho substituent are present and both ring are
optically dissymmetric.
Br Br

disymetric opticallyactive OI = 2
I

I
I

I
Br

Symmetric NO. O I .

Resolution: Seperation of enantioment or recemic mix is called resolution

That since phy.prop of enantiomers are same they can not be separate by ordinary
methods like fractional distillation or cyotellisation. However it is possible through
conversion cnto diastereomers.

CH3
H

C2H5
COOH

C2H5

COOH
CH3

PH
H

HO

H
D

O
H

PH

CO

C2H5
H

PH

CO
CH3

H3O+

H3O+

D1

D2
Fractional distillation
CH3

D1 =

D2 =

PH
COOH + HO

C2H5

C2H5

PH
COOH + HO

29
CH3

D
O

RCOOH + CH3OH ( H ) R C CH3 ] H3O+

RCOOH + CH3OH

Conformational isomerism:

New man projection formula :

a
l
m
c
c
b
n
c

l
b

New man

Staggred form
a
l
m

b
*

Elips formula

Dihedral angle : interplaner angle is called dihedral angle defined by

abcd

180o
F

F
I
Cl

OH
H

OH
Br

Cl

Br

Dihedral angle

Stg.

eclipsed

H C C F 180

120

H C C Br 60

120

H C C Cl 60

Condition for conformational iso.

30
Molecule must have an unit like a b c d and rotation should be free. No. of
conformers will be infinite and a dynamic state of egutn. They are not be separated.
NH3

H
N
H

H2O

CH3OH

H
C=C

HOOH
CH3 CH3

CH2 = CH CH2 CH3

Conformational analysis of ethno.

H
H

H
H
H

H
H

H
H

Staggred form

H
H
Eclipsed form

No. B.P, B prepulsion:

BP BP repulsion
2 . 6 Kcal / mol

Rotation / divedral angle.

*

Heat of combustion is stability.

RH + O, CO2 + H2O + Heat
Using heat of combustion relative stability can be derived if molecular formula is same
CH3 CH2 CH2 CH3
CH3 CH CH3 +
CH3

13
O2 HCO2 + xKCal/mol
2

13
O2 HCO2 + 3H2O + yKCal/mol
2

[x > y]

Therefore isobutene is more stable than H butane

Rule is that branched alkane is more stable than unbranched.

H/CH2

31
166.6

157.4

164.0
158.7
Deyers strain theory :
109 o 28' actualangle
& stability 1/angle strain
2

Angle strain =

Angle strain, =

109 o18'60
2

= 24o44

109 o 28'90
9 o 44'
2

109 o 28'108 o
44'
2

109 o 28'108
5 o 44'
2

stability order on the basis of angle strain is

This order doesnt match with experimental order. However only the position of
cyclohexane is delocated. It means that this theory fails at cyclohexane cause of failure is
the exemption that ally ring are planer. But cyclohexane is not planer. it exist in chair and
boat forms mainly
120o
Hypothetical ; All angle = 109o 28
Strain = 0.
**

Conformation analysis of butane CH3 CH2 CH3

CH3
CH3
H
H
60o
H
H
H

CH3

CH3

(I) Anti form

CH3
CH3
H

60o

(II) Partially eclipsed.

CH3 CH3

H
H

H
H

32

(III) Gauche

(IV) Fully eclipsed.

(I)

Anti form : No BP DP repulsion No steric / venderwall repulsion ; (Most stable)

(II)

Partially eclipsed :

BP BP repulsion

Some venderwall repulsion

(III)

No BP DP repulsion some steric repulsion

(IV)

DP BP repulsion on maxn steric repulsion

Stability order :
Anti > Gauche > Partially eclipsed > fullyed
Energy profile :

Fully eclipsed
Partially eclipsed
PE
Anti

Gauche

Anti

Dihedral angle

Subtituent effects:
OH

OH

Substituent Acidity
NO2
NaOH
O Na+

NaOH
O Na+
+H2O

+H2O
NO2

Readily.

The atom or group which itself doesnt participate inren but effect reactivity of the
molecule is substituent and its effect is called substituent effect.
Depending upon the modes of transmittance substituent effect is classifies as
Substituent effect

Inductive

steric

33

Imesomeric

Hyperconjugation

electromeric

Hyperconjugation :
Transmittance of substituent effect through conjugation is known as
hyperconjugation. It occurs in
(a) Alkenes.

(b) Alkynes.

(c) Cations.

(d) Radicals.

Provided that there is at least one hydrogen at the conjugated position.

Sp3

CH2 CH = CH2 H2C

CH CH2

3
Sps
H
CH2 CH CH2

Sp2

H+

CH2 CH CH2
H+

Write structures in all and hyperconjugation:

CH2 = CH2
CH3 CH = CH CH3
CH3
C = CH CH2 CH3
CH3
CH3
CH3 CH2 CH2 CH2 CH2 = CH2
H

CH3 CH CH2 CH3

CH3 CH2

CH3 CH CH3

CH2 CH2 CH2 = CH2

In the structure arising from hyper conjugation are C H bond is cleaved. That is why
hyper conjugation is also called no bond resonance.

Total no. of structures will be equal to no. of hyper conjugable H atom + 1.

34
However these structures are imaginary or real.
Ha
Hb

C CH = CH2

Hc

CH2 = CH CH2
Ha

CH2 = CH CH2

CH = CH CH2

Hc

Hb
Ha+
Hb+

C CH CH2

Hc+

Hybrid.

As shown C H bond is actually not cleaved but elongated such that C H bond pair
electron are shifted more towards carbon.
Therefore hyper is a method of electro donation In other words an alkyl group donates
electron by way of hyper and this e donating power is directly proportional to no. of
hyper conjugable H atoms.
CH3
CH3 > CH2 CH3 > CH
1o

2o

CH3
>C

CH3

CH3
CH3

(Zero no. of H atom)

CH3
CH2 = CH C

CH3

(=) bond is added

CH3
Therefore in general, electron donating power of alkyl groups through hyper conjugation
is
CH3 > 1o R > 2o R > 3o R.
Since hyper conjugation involves delocalisation of e it increases stability of the
molecules
I

CH2 = CH2

0H

II

CH3 CH = CH2

3H

III

CH3 CH = CH CH3

6H

IV

CH3
C = CH CH3

9H

35
CH3
V.

CH3

CH3
C=C

CH3
Stability

12 H
CH3

V > IV > III > II > I

Rule is that more substituted alkene is more stable than less substituted alkene.
Hyperconjugation is heat of hydrogenation :
Extent of heat of hydrogenation 1/extent of hyperconjugation
Order of heat of hydrogenation is
I > II > III > IV > V.
CH3 CH3 CH2 F

Magnitude of I effects
+I

O
COO CH2 D

(i)

O > COO > CH3 > D

(ii)

NO2 > F

(iii)

I > OH
O

C >>> N O ; NH 3 > NO2

***

A general order of I magnitude NH3 > NO2 > CN > COOH > F Cl > Br
> I > OH.
CH3

+ I effect.
CH3

CH3

CH2 CH3 C(CH3)3 > CH > CH

3o

CH3 2o

CH3

CH2 CH3 > CH3

1o

CH3
C CH3
CH3
Gen. order of magnitude of + I effect among alkyl group is 3o > 2o > 1o CH3
Note : that this order is just opposite to the order of e donating power through hyperconjugation
which is ml > 1o > 1o > 3o.

36

Mesomeric effect or (Resonance effect)

Transmittance of substituent effect through bond is called mesomeric effect (M/R
effect) therefore this effect operates only in molecules undergoing Resonance.
CH3 substituent.
CH2 = CH O

CH2 CH = OCH3
M effect
( + M)

( M)

If substi. donates a pair of e

If substi. withdraw e in

in resonance. Such grps one called donar

resonance. Such grps are called accepter

eg :

O CH3 ( + M, I)
NH2 ( I, + M)
NO2 ( I, M)
X ( I / + M)
CN ( I / M)
COOH ( I / M) ; CHO ( I / M)
CH = CH2 + M / M I ; NO
COCl ( I / M)
COCl ( I / M)

= O
N

+ M M / I.

COOR ( I / M)
C CH

+M/M/I

PH

+ M / M / I.

eg :
I

II
NO2

III
O CH3

+M/M?

eg:

+M

III > I > II

II > I > III.

O

O CH3 , O C CH3 , O CH = CH2

37
I

II

III

+M

I > III > II

O CH3 > PH
+M

+M

CH

CH = O > PH
M

C NH2

C O CH3

M ; I > III > II.

Groups
I/M

+ I, + M (O)

I/+M

i.e accepter as well as i.e donar as well as accepter donar both

accepter
donar i.e donar
effectance operating then
mesomeric effect is favoured
Accepter
therefore
such
groups
effectively acts as donar
COOH

COOH

NO2

OCH3

I/M
Accepter

I/+M
donar

: Electromeric effect :
Polarisation of bond caused by the approach of reagent
eg.

CH2 = CH2 A non polar bond.

H+
+

CH2 CH2
H

Therefore this effect is temporary and operates only in excited state.

: Alkone :

38
Preparation :
(1)

C = C N:/ NH C C
2

+ H1

C C ' C C + H2
Exothermic :
+ H (wrong)

C = C H C C
2

Eact of hydrogenation = high so a catalyst is regd to lower the eact

Catalyst
Homogeneous

Heterogeneous

RhCl (PPH3) chlorotris triphenyl plusphine Ramey Ni, pt, pd (p 2) lindlar catalyst
( Ni Al ) agNaOH
rhodium, or willkinson catalyst.
Raney Ni Ray Ni finally
Alloy
worom
divided into Ni Particles

p 2 is Ni2 B (Nickel boride)

Ni (OAC ) 2

NaBH
4 Ni2 B

( Nickel aectate ) ( sod .borohydrid e )

Lindlars cat. is pd/BaSO4/Quinoline or, pd/CaCO3/Qwaoline

Quinoline

The role of catalyst.

C=C

+ H H Ni C C

HH

H H
Active sites

Catalyst help to cleave H H bond through adsorption process.

not only = / but other grps abo reduced.

C = C Ni / H CH CH
2

CC

CH2 CH2

R CHO

R CH2 OH

"

"

39

"

C=O

CH OH

R
O

R C O R RCH2 OH + R OH

"

R CN

R COCl

RCH2 NH2

"

R CH2OH

R
C = N OH

"

CH NH2

R CH = O
HH
R CH2 OH
O
R C O R Ni / H R CH2OH + ROH
2

O
R CH OR R CH = O+ + ROH
Ni/H2
R CH2 OH
OH
C

C = NH + H2O

NH2
O

OH

H2
R C NH2 H / NI R CH N
..
2

R CH2 NH2 Ni / H R CH = NH
2

R CH = NH2

An ester :
(i)

ester ? H / Ni
2

OH = CH3 CH CH3
1o

OH

40
O
Ans

PH C

CH3
O CH
CH3
2o OH

(ii)

ester ? H / Ni
2

1o

OH
O

C=O
Imp.

O
R C O R 1o / 2o / 3o
R CH2OH only 1o (always)

? How many esters Ni / H CH3 OH + C2H5OH

2

1o
Ans

1o

H C O C2H5

CH3 C O CH3
CH3

? How many hydrocarbons for For C 7 H12

Ni / H 2

Ans

Hydrogenation syn radical addition

C=C
H

CH3

catalyst
Reactivity

CH3

yne > ene

-------------------------------------CH3
(ii)

CH2 = CH2 >

C = CH2
CH3

CH3

CH3

cis, meso only

41

SELECTIVITY
CH2OH

CH = O

CH2OH
NaBH4

Ni/H2

(willkinsons cat)

So, wiliumsons
aplnopriste for
genation of

cat (wc) is selective

hydro C = C bonds.

CHO

RCCR

Ni/H2

p2

R CH2 CH2 R

Lindlars catalyst

R
C=C

(only cis) so both p 2 and L cat are selective rid agent of / =.

R

M/NH3

**

C=C

RCCR

Lindlars

(Trans)

R
C=C

Catalyst

(cis )

(nice) Mechanism : Li Li + e
RCCR

RC=CR

=C
R

--------------------------------------R

H
C=C
R
NH3

H
C=C

By divide (HN = NH)

(hydrogine) NH2 NH2 H O HN = NH (divide)
2 2

H
N = H only cis divide is used for hydrogenation

42
R

R
RCCR
H
H
N=N

+ N2

C=C
H

cis.

By hydroboration :
H2C = CH2
BH3 : THF

(T H F)

Mech
CH3 CH2

CH2 = CH2

H B

Electrophilic addition.
Markonicov rule is obeyed.
Syn addition.

CH3
C = CH2
B2H6

CH3

CH2

CH2

CH2

CH2

CH3
C = CH2
CH2 H

Q.

CH3 CH = CH2
BH3 : THF
CH3 CH2 CH2
B2H6 / 2CH3COOH

B
CH3COOH+
CH3 CH2 CH3

Imp

catalytic hydrogenation of Benzene.

H2/Ni

(only product)
H2/Ni

H2/Ni
H2/Ni

Li/NH3

These two cant be isolated so only product is cycloxe.

43
Called Birch reduction which gives 1, 4 cyclohexadiene not 1, 3 cyclohexadiene even
though caber is more stable than former. Came (not clear)

Kolbe electrolysis
is R R
R COONa Electrolys

mech
O
R C O Na+

Anode :

R C O + e

Cathode :

Na+ + e

Na

Na + H2O

NaOn + H2

RCO

R + CO2

2R

R R.

As reacn move pH of soln inc. due to the formation of NaOH.

CH3COONa

e CH3

CH3

Decarboxylation of fatly acids.

CH3COONa

NaOH / CaO / Sodaline

O

sodaline CH3 C
CH4

CH3 + CO2 ( H O) CH4 .

2

Carbanion is the intermediate therefore eB withdrawing grp. increases the ease of

decarboxylation
I. CH3 COOH
II. CH3 CH2 COOH
III.

CH3
CH COOH
CH3

ease : I > II > III.

Key:

Just remove CO2 from compd.

O

CH3 C

C OH CH3 C CH3
CH2

C H6
CH2 COOH CH3 COOH sodaline

44
COOH

COOH
COOH

COOH

Mech:

COOH

COOH
+ CO2or,

COOH

C OH CH3 C CH2 + CO2

CH3 C
CH2
O

HO

CH3 C

C=O

CH2

CH3

OH

CH3

CH3 C = CH2 + CO2

O
COOH

CH2

CH2

COOH

H
C
OH
CH2 = C

= O

O H

+ CO2

O
CH3 C OH

OH

Mech :

Na / ether
Wurtz reaction : R I R R.

R I Na R Na + NaI
R I R R + NaI
1o , 2o , 3o halide undergo this reacn. Not 3o due to ------------------------------CH3

CH2 H

CH3 C I

Na

CH3 C

CH3

CH3

CH3
C = CH2
CH3

In wurtz reac only that alkane is formed in good yield which requires only one R X
which is net 3o.
CH3 I + CH3 CH2 I
Na
CH3 CH2 CH3 + CH3 CH3 + CH3 CH2 CH2 CH3
Q.

Wurty reacn is suitable for making which of the following alkanes.

CH3 CH2 CH2 CH2 CH3

45
CH3 CH2 CH2 CH2 CH2 CH3
CH3 CH3
CH3 C C CH3
CH3 CH3

Frankland reacn : ller as wurt except Na is replaced by Zn.

R I Zn R Zn I R I R R + ZnI2
Zn
RR

Corey house alkane synthens :

betterthan wurtz.
R I Li R Li
CuI
R R R2Culi + RI

eg

CH3 CH CH2 I ( CH CH ) Culi

CH3 (CH2)3CH3

From Grignard reagent R X Na / Ethen R Mg X (G-R)

**

own

2 2

R Mg X

i.e compd

H 2O RH

relearning H+

NH 3 RH

will give RH

CH
3 OH
RH

with G-R

R NH 2 R H
CH
3COOH
R H
DiO
RD

(1)

1R .Mgx
CH3 CH = O 2.H CH3 CH OH

R
CH3

CH3
1R .Mgx
C = O 2.H

(2)
CH3

OH
C

CH3

O
(3)

RMgx ( excess )
CH3 C OCH3 H CH3 C R

46
O

OH

1 R.Mgx

(4)

2. H

O
(5)

RMgx
PH C OCH3 (1 g ) PH C R

Infact GR + H+ alk.

own

So in reacn not add

R H+ or multiple bond for product
Q-1

? An ester

Q-2

? An ester

1. Ph Mg x (exe)

1. Ph MgBr (exe)

2. NH4 Cl

2. NH4 Cl
ph

OH

OH

ph

OH

C2H5 C Ph
Ph

Ans

+ CH3OH

Ans

O
CH3 CH2 C OCH3
CH3

Q-3

1. PhMgBr
An amide 2.NH 4 Cl

CH +

NH

O
Ans

CH3

CH3

HCN
CH3
Mech:

Ph
O

Ph- MgBr

O MgBr
O

Ph
O MgBr
Ph MgBr

Ph
Ph

O MgBr
OH

OH

NH4Cl

Ph
Ph
O MgBr

47
O

OH

1.CH 3MgBr
R C OCH3 2 . R C CH3 + CH3

O
R C OR
OH

CH3OH

R C CH3
CH3
Imp.

O
R C OR
3o alc.

1o, 2o, 3o

Note: That G.R cant be prepared from i.e. dilalids. added to this it cant be prepared if
molecule contains one or more reactible group.
Br

Br

CH2 CH2

CH2 CH2

mg

Br

Mg

CH2 = CH2
Br
Br
Br

Mg

Br

Bengyne.
Q.

An ester
NH4Cl CH3 Mg Br (excess)
OH
CH3 OH + CH3 CH CH3

Ans

O
H C O CH3
Cl

NH2

Cl

or,

NH2

NaNH2

Sp2

48

Clemenson and wolf kishner reduction

Zn/Hg

pure
C=O
(any)

(ket or ald.)

> CH2
> CH2

N2H4
KOH (W.K)

R
H
C=O+ N
3

mech: (w.k red) (i)

R
R

OH

C
R

O
C

N H2

..

NH3

R
C = NH2

C = NH

Note: CR acidic med.

Both are complementary to each other

wk basic med.
i.e It ketone / ald gas acid -----------------------------------------------carried at, it base semitive then CR is carried out
R
(ii)

H
C=O+

R
N NH2

(hydrazine)

C H2
R
R

C = N NH2 + H2O
R

KOH

C H + N2
R

R
H
C=N N
2

CH N = N + H2O

R
C N = NH

H 2O

KOH
CH N = NH

49

Zn / H
Conc HCl

Cl

N2H4/OH
Cl
OH
O

N2H4/conc KOH
OH

Zn / H
conc HCl

OH

Cl

Properties :
Halogenation :
R H + X2

R X + HX

Light / heat

mech: X X 2X

X + H R r . d .s HX + R
R + X X

(i)

(iii)

(ii)

RX+X

Relativity of x2 F2 > Cl2 > Br2 > I2

Relativity of H atom 3o H > 2o H > 1o Cl
~ 3o R > 2 o R > 1 o R
Selectivity :

CH3 CH2 CH3

Cl2 / light

CH3 CH CH3 + CH3 CH2 CH2

Cl 56% (maj) 44%

Cl (min)

Selectivity ratio = Reactivity probab ratio

3o H

2o H

1o H

Cl2

3.8

Br2

1600

8.2

Selectivity ratio =

3.8 2 3.8

1.26 3 / II .
1
6
3

I + II = 100 %

% I = 56%

% II = 44%

CH3 CH2 CH3 Br / light

CH3 CH CH3 + CH3 CH2 CH2 Br
2

50
Br

96%

4%

All H atom of alk. Can be replaced

CH4 Cl / CH3Cl CH2Cl2 CHCl3 Cl
2

CH3Cl (Mej)
CH4 (Exl.) + Cl2 (exe)
CXCl4 (Maj)
Q.

CH3 CH3 Cl / How many prd.

Ans

= 9.

Combustion : Heating alkanes in atm. Of O2

CH4 + 2O2 CO2 + H2O + heat
CH3 CH3 + 9/2 O2 9 2CO2 + 3H2O + heat
In asscence of sufficient amount of O2 in complete combustion occurs
CH4 + 3/2 O2 CO + 2H2O
CH4 + 3O2 C + 2H2O
Lamp black.
Pyrolysis: Heating alkanes in total absence of O 2 is called pyrolysis or cracking which
produces lower alkanes from higher ones
CH3 CH3 2 . CH3
500oC
CH4

ALKENE
Preparation:
(1)

From alcohol:
C=C

H 2 SO4
orH

CH C HCl CH C
OH

Cl

Case: Cl is much better nu than HSO4

CH C

mech:

OH
conc H2SO4
H
CC
E1

OH

E2

51
CC
HSO4

C=C

C=C

+ H2SO4.

1o alc follow E2 pathway, while 2o and 3o alcohol follow E1 pathway.

1o

Cause :

is not so stable.

CH3 CH2 CH2 CH2 OH

H2SO4
CH3 CH2 CH = CH2

CH3 CH = CH CH3

CH3 CH2 CH2 CH3

(Major)

CH3 CH2 CH CH3

CH3 CH2 CH CH3

How many products

-------------------------------------------CH3
CH3 C CH = CH2

CH3
CH3

CH3

CH3 C = C

CH3

CH2 = C CH CH3

CH3

OH

CH3
+

H /

: Pinacol pinacolone rearrangement :

O
R CH CH R R C CH2 R
H 2 SO

Mech:

H
R CH CH R
OH

R C CH R

OH

OH

OH2

R C CH2 R

R C CH R
OH

Imp.

Migratory aptitude:
H > PH3 > 3o R > 2o R > 1o R > CH3
PH

Q.

CH3

PH C C CH3
OH OH

PH O

PH C C CH3
CH3

Major

52

Q.

OH (Hon)

CHO

OH
eg

C2H5 C2H5
CH3 C C CH3
OH

OH
H+

C2H5 C2H5

(L.S) so not

CH3 C C CH3

possible

OH
OH

C2H5

C2H5

CH3 C C C2H5 (M.S)

CH3 CH2 C C CH3

CH3
O

(C.S)

OH

C2H5

CH3
C2H5

CH3 C C C2H5

C2H5 C C CH3

CH3

CH3

: Dehydrohalogenation :
CC
H

Ex:

AlC .KOH
,

C=C

Base is strong, path is E2

No C+ ion rearrangement

Zaisev rule is followed for orientation

It is not reversible because HX is neutralized by base.

Find the major product

Alc.kon
CH3 CH CH2 CH3 CH3 CH = CH CH3

Br
Br
CH3 CH CH CH3
CH3

Alc. Icon,

53

CH3
Alc
Br kon

C = CH CH3 (Maj)
CH3

Because path is E2 in which there is no C+ rearrangement.

: Dehalogehation :
Br
CC

Zn

KI

Br Mg
CC

C = C (Maj)

+ ZnBr2

+ MgBr2

CC

Mechanism :
Br

Br

Br

CC

CC

CC

Br

Br

Br

Zn
Br

Br

CC

CC

Zn Br
C = C + Zn Br
Imp.

Br
C=C

Mg Br

+ IBr + KBr.

C = C + Mg Br2

Br
C=C

I
but

CC

Br (stable)
CH = CH Br Zn HC CH
Br
Br

Zn

Br
Zn

Br
Imp.
Q.

PH

I (not stable)

Br
Q.

Mg

Br

C = C + I2

54
C=C
PH

Br
PH
Zn

C=C
PH

PH C C PH
Q.

CH2 CH2 CH2 2 H

Br

Br

[own: make bond between C having Br or X grp]

Q.

CH2 C C CH2 Zn CH2 = C = C CH2

Br

Imp.
Q.

Br
H

Br

Br

Br

Br

(Mech = ?)
Antie lim ination

( Zn )

K1

Syn e lim ination

( Zn )
K2

Br
Br
Br
Zn

OIs/OAC/OEt

Properties:

1. Hydrohalogenation.
C = C HX CH C
Mech.

X
X

C=C

CH C

Sluthophilic addso
Menken acid is followed
Reactivity of HX:
HI > HBr > HCl > HF

CH C

C+ con rearrangement possible

55
Case: HI is strongest acid and I is a good Nu

Cl
CH3 CH CH = CH2 CH3 C C2H5
HCl

CH3

both enahtiomer

CH3
Cl

and CH3 CH CH CH3

(Major)

CH3

(PEROXIDE EFFECT)
HBr
CH3 CH = CH2 R O CH3 CH2 CH2
CH3 CH CH3 HBr
2 2

Br

Br

Markon addition

Antimark addition

R O O R 2RO
RO

H Br ROH + Br
CH3 CH = CH2
(2)

Br

CH3 CH CH2 (L.S)

CH3 CH CH2 (MS)

Br H

(1)

Br

Br

CH3 CH2 CH2 + Br

Br
Peroxide effect works only on HBr not on HCl and HI.
Cause: Both step (1) and (2) are exothermic in case of HBr not in case of HI and HCl now
peroxide effect separates also on other types of molecules like CCl4, CHCl3. ICBr3 etc.
Ex:-

Cl
CCl4
CH3 CH = CH2 RO X CH3 CH CH2 (not formed)

CCl4 . peroxide
CH3 CH CH2 CCl3.
Cl
Cause:- first CCl3 attacks
R O + Cl CH3 R OCl + CCl3

56
R O CCl3 + Cl Not permicible
Cl CCl3
H CCl3

First attacking franquent

I CBr3
: Halogenation :
Br
Br / CCl C C
C = C Room
temp .
2

Electrophilic addition

Occurs through. Mech: -

C=C
Br Br

cyclic bromoaion cyclic bromination

CC

intermediate became
it is more stable than C

Br
Br

CC
Br

CC
(MS)

CC

Br

(L.S)

Complete octet of

In complete octet

all 3 atoms

octet of canbon.

Q.

Br

Anti addition due to cyclicintessmer

Write the product:

ICl

CH3 CH = CH2

Br2/H2O

NaCl/Br2
Cl
CH3 CH- CH2
Cl

OH

CH3 CH CH2
(Maj)

CH3 CH CH2 (Maj)

Br

Br

CH3 CH CH2 Br

CH3 CH CH2

Br

Br
Br

Br2

2.
Q.

CH3

CH3

(Trans only Both ehantiomer)

Br

CH3

CC
H

H
C=C

H
Br2/CCl4

CH3
Br2/CCl4

57
Br

CH3

Br

CH3

CH3

CH3
H

i.e

Br

ehantiomers (Active)

Br

Mes

CH3

CH3

CH3

Br

Br

Br

Br

Br

Br

CH3

CH3

CH3

Hydration
CH3 CH = CH2

OH
CH3 CH CH3

H / H 2O

1 .Hg (OAC )2 / H 2O CH3 CH CH3

2. BaBH 4
OH
OH

1 . B2 H 6

CH3 CH2 CH2

2. H 2O2 / OH

(1)

Acid catalyse hydration:

CH3 CH = CH2 CH3 CH CH3

Electrophilic addition
Markohikotts rule followed.
C interus. So rearrangement is possible.

OH
CH3 CH CH3
OH2
CH3 CH CH2
OH

(a)

CH3 CH CH = CH2
CH3

CH3

H2SO4/H2O

OH
CH3 C CH2 CH3

H+ / H2O

CH3 (Major)
+

CH3 (Maj)

CH3 CH CH CH3
CH3 OH (Minor)

Via oxymercuration / demercunation.

CH3 CH = CH2

CH3

CH3 CH CH3

58
Hg(OAC)2 oxymercuration.

OH

----------------------------------------------------------Mech: CH3 CH = CH2

OAC
Hg
OAC

Electrophilic addition

H2O

M value followed

CH3 CH CH2

No C+ ion rearrangement.

Hg

OAC

OH
CH3 C CH2
Hg OAC.
Q.

(a)

CH3 CH CH = CH2
CH3
*
1 .Hg (OAC ) CH3 CH CH
CH3
H 2O

CH3 OH (only)
CH3

CH2

1.Hg ( OAC )

(b)

OH

2
2. NaBH 4 / H 2O

Note: Even if H2O is present the attack of OH molecule of the compd itself will be more
preferable.
c)

Via hydration:

this is antimarkonikoff is

CH3 CH = CH2
BH3 (addition)

hydration without disdeiying

CH3 CH2 CH2

M. rule

It is syn- addition.

H
H2O2 / H+ oxid.

CH3 CH2 CH2

OH
H

CH3

H2O

1. BH3 : THF
2. H2O2 / OH

1. HI2 (OAC)2/H2O
2. NaBH4

59
CH3

CH3

60