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(LECTURE No. 5 TO 14
TOPIC : ISOMERISM
Page-1
Contents
Lecture 5 & 6
Structural Isomerism
(a) Classification of Isomers (b) Definition of
Chain isomers
(a) Alkanes, Alkenes, Alkynes
(b) R OH, RNH2 (c) With terminal F.G.
(d) Aromatic side chains
Position isomers
(a) C C, C = C, C C, (b) OH, NH2,
SO3H
Metamers
(a) R O R
(b) R NH R, R N R
|
R
(c) R C OR , R C NH R , R C O C R
||
||
||
||
O
O
O
O
( OH, O )
(R2C = O, RCHO)
(RCOOH, R C OR )
||
O
(1, 2, 3 Amines)
(e) Amides
1, 2, 3
Page-2
Contents
Lecture 7
Lecture 8
1. Ozonolysis:
1. Structure
2. Applications:
Indentification
(a) Monochlorination
(b) Catalytic Hydrogenation
of C = C; C C
Lecture 9
Lecture 10
1. Stereoisomers
(Classification)
2. Configurational isomers
3. Conformational
isomers
4. Geometrical Isomerism
Lecture 11
Lecture 12
1. Configuration
1. Optical Isomerism
nomenclature
2. Symmetry of elements
in Optical
3. Chirality (Dissymmetry)
Isomers
and Optical Isomers
2.
R/S
Configura4. Optically Active Cartion
in Fisher
bon Compounds
Projection
5. Projection Formula of
Formula
Chiral Molecules
3. Compounds
with 2 Asymmetric Carbons
of Similar
Nature
1. Number of geometrical
isomers
2. E/Z Nomenclature :
3. Physical properties of
Geometrical isomers
(i) Dipole moment ()
(ii) Boiling Point
(iii) Melting Point:
(iv) Water Solubility
Lecture 13
1. Meso isomers
2. Properties of
Optical Diastereomers
3. Chemical method
of separation
(resolution) by
using optically
active reagent
Lecture 14
1. Conformations/conformers
2. Conformational isomers
3. Conformational energy
4. Dihedral angle of rotation
5. Strains
6. Ethane, propane, n-Butane
7. X-CH2CH2X type
(Saw horse Newman projection formula, stability, P.E. curves)
Page-3
Ex:-
Homologs:
Compounds with same general formula differing by same structural unit CH2 or molecular weight by 14
unit.
Ex:- CH3 OH and CH3 CH2 OH
Difference between isomers and homologs:-
Page-4
Structural isomers:
When two or more number of organic compounds have same molecular formula but different structural
formula these are called structural isomers.
Stereo isomers:
When two or more compounds have same Molecular Formual (M.F.) and same Structural Formula (S.F.) but
have different stereochemical formula (S.C.F.), these are called stereoisomers.
M.F.
S.F.
(i) CH3 CH2 CH = CH2
These are structural isomers.
For (ii), S.C.F. are
H3C
H
CH3
C=C
H3C
and
C=C
H
CH3
Stereocentre
These are stereoisomers.
H
Chain isomers :
They have different size of main carbon chain or side chain (of C atoms)
(i) The two chain isomers should have same nature of F.G./multiple bonds/substituents (except R group)
(ii) The position of F.G./M.B./substituent (locants) is not. considered here.
Note : (i) In almost all functional group chain isomer starts from four carbon atoms except in alkene, alkanone,
ether, ester, 2 amine and 3 amine.
Ex:-
Alkanes:(a) C1 C3
(b) C4H10
(c) C5H12
(d) C6H14
(i) CH3 CH2 CH2 CH2 CH2 CH3, (ii) CH3 CH CH2
(iii) CH3 CH2
CH3
CH3 ,
CH3
CH3
CH3,
CH3,
CH3
(iii) C C C C C C
C
C
(ii) C C C C C C,
C C
(i) C C C C C C
CC
Ex.
C6H12 (Cycloalkanes):-
(10)
Ans.
(4)
C
CC
CCC
(7)
(11)
(8)
CC
(9)
(6)
(3)
(2)
(5)
(1)
Ex.
CC
Ex.
and
Ans.
Chain Isomers
Q.
C
C C C NH2
Ans.
C C C C NH2,
Positional isomers:
They have different position of locants Functional group (F.G.) or Multiple Bond (M.B.) or substituents in
the same skeleton of C-atoms.
Nature of F.G. or M.B. should not change.
The skeleton of C-atom should not change.
CC C CC
C
(2) C = C C C ,
CC=CC
(3) C C C C C ,
CCCCC
(1) C C C C C ,
C
Ex.
Page-6
(4) C C C C ,
C C C C OH
OH
Write all Positional isomers of Dichlorobenzene ?
Cl
Ans.
Q.
Cl
Cl
Cl
,
Q.
Cl
Cl
Cl Cl
Ans.
Cl
Q.
Cl Cl
,
Cl
Ans.
,
Cl
Cl
Ans.
Cl Cl
Cl
Q.
Cl
Functional isomers:
They have different nature of functional group (F.G.). The chain and positional isomerism is ignored (not
considered).
Compound
Functional isomer
CCCC
Nil
CCC=C
Ex.
(1)
Compound
CCCC
Isomer Functional
(a) C = C C = C Alkadiene
Remarks
(a), (b) are not functional isomers
Alkyne
(b)
Cycloalkene
among themselve
(c)
Bicyclo
(2)
C C C OH
Alcohol
CCOC
Ethers
(3)
C C CH = O
C C C
O
Ketones
(4)
C C COOH
Carboxylic acids
(5)
C C C NH2
1 amine
C C OC
O
Esters
..
(a) C C NH C
2 amine
..
(b) C N C
C
3 amine
Aldehydes
Page-7
(6)
CCCN
Cyanide
(Propanenitrile)
C C NC
Isocyanide
(Ethane isocyanide)
Hemiacetal
Unstable
(iii) C OH
(i) C = C OH
OH
(v) C O C = C
OR
Q.
(iv) C OH
OH
C
C C C C OH,
C C C C C,
OH
C
C C C OH
C
(7 alcohols)
C
C C O C,
C
C C C O C,
C
C C C O C C,
C
C C OCC
(6 ethers).
G.F.
CnH2n + 3N
n
(1) 3
M.F.
C3H9N
2 Amine (R NH R)
3 Amine R N R
R
G.F.
CnH2n + 1N
2
n
(1) 2
M.F.
C2H5N
1 Amine
(1) C = C NH2
Ethenamine
2 Amine
3 Amine
CC=N
CN=C
Ethanimine
N-Methylene methanamine
(Unstable at room temperature)
C C C O C,
C
C C C C O C,
C
C C C C OH,
C C C C C,
OH
C
C C C OH,
C
(i) C C C C C OH,
Ans.
1 Amine (R NH2)
Q
Q.
N
H
Q.
G.F.
CnH2n 1N
n
2
M.F.
C2H3N
Ans.
CH2 = C = NH
HC C NH2
H3C N
C
Page-8
Metamers:
When two isomers have same functional group (containing a hetero atom O, N, S) but have different nature
of alkyl or aryl (aromatic radical) group attached to hetero atom, then these are called metamers.
(a) Same functional group
(b) Chain or position isomerism is not considered.
Following functional groups show metamerism
Ethers (All isomeric ethers are metamers)
(b) R NH R
2 Amines
(c) R N R
R''
(d) R S R
3 Amines
(e) R C O R
O
Esters
(a) R O R
Thioethers
(f) R C O C R Anhydrides
O
O
(g) R S O R
Sulphonate esters
O
Q.
Ans.
Q.
Ans.
CC NCC
C
CCC NC
OCC
Q.
C C
C C NC
and
OC
Q.
Acyclic compound (A) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (A).
Ans.
C C
C C C C C8H18
C C
Q.
Cyclic compound (P) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (P).
Metamerism
Ans.
Ans.
or
Page-9
Q.
O
Q.
NH
C
Ans.
CH2 is amide. C
CH is imide
O
O
Compound X is an ether. It has 12 1 H atoms. It has 2 types of H-atoms and 3 types of C-atoms. Write it
Structural formula ?
CH3
H3C O C CH3
Q.
CH3
Page-10
STRUCTURE INDENTIFICATION
(1) Calculation of Degree of Unsaturation (DU):(a) It is the hydrogen deficiency index (HDI) or Double Bond Equivalence (DBE)
2H
(b) H3 C H2C CH3
(DU O)
2H
CH3 C CH or CH2 = C = CH2 or
(d)
G.F.
D.U.
(i) CxHy
y
(x + 1)
2
(ii) CxHyOz
yo
(x + 1)
2
(iii) CxHyXs
ys
(x + 1)
2
(iv) CxHyNw
yw
(x + 1)
2
(v) CxHyOzXsNw
ys w
(x + 1)
2
Ex
DU = 4
(b) C6H5Cl
DU = 4
(c) C6Br6
DU = 4
(d) C5H11OCl
DU = 0
(e) C9H12N2
DU = 5
(f) C6N6
DU = 10
DU = 8
DU
S.F.
H
1.
C4H6
CC=C=C
H
H
H H
CCCC
CCCC
C=CC=C
Page-11
C
CH2
2.
C2H2Cl2
=1
Total isomers = 3
Cl
3. C6H6ClNO (Aromatic)
NHOH
OH
=4
Cl
NH2
Note : If the aromatic Compounds have minimum D.E. 4. That means at least 1 Benzene ring is present.
Q.
ANS.
DU = 9
or
or
CC=CC
Page-12
Monochlorination:(a)
Cl / h
CH3Cl + HCl
(i) CH4 2
Cl / Sunlight
(ii) CH3 CH3 2 CH3 CH2Cl + HCl
Cl
Cl / h
2
(iii)
+ HCl
C
C
Cl / h
C C C Cl + HCl
(iv) C C C 2
C
C
Cl / h
2
(v)
Cl
+ HCl
Remarks:- When an alkane or a cycloalkane is treated with halogen (Cl2, Br2, F2, I2), a photochemical reaction takes
place and a C H bond cleaves and a C Cl bond is formed. So, on H-atom is substituted by one halogen
atom. This is known as monohalogenation reaction.
Application:- If a molecule has more than one type of H-atom, then on monochlorination, it forms a mixture of
monochloroisomers. All these isomers are position isomers.
Conclusion:- Hence, it can be concluded that the total no. of position isomers (structural) of monochloro compounds
is equal to the number of different types of H-atoms present in the reactant. The different type of H-atoms are
also known as non-identical Hydrogens or non-equivalent Hydrogens or chemically different Hydrogens.
Ex.
Monochlori nation
(a) C C C 2
Monochlori nation
(b) C C C C 2
(c) C C C C C
Monochlori nation
3
Monochlori nation
(d) C C C C 4
C
CH3
Monochlori nation
5
(e)
Q.
Cl / h
only one monochloro isomer..
X(C5H12) 2
Ans.
X = Neopentane
Q.
Cl / h
Two monochloro
P(C6H14) 2
C C
C C C C only one isomers
Remark : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated, but H-atoms of Benzene
ring are stable. In pure benzene, no monochlorination
Page-13
CH3
Cl / h
2
Ex.
Q.
CH2Cl
Cl / h
Two mohochloro
X(C8H10) (Aromatic) 2
Cl / h
One monochloro
Y(C8H10) (Aromatic) 2
Ans.
(X)
(Y)
Catalytic Hydrogenation of C = C; C C
General reaction:Ni
R CH2 CH2 R
(a) R CH = CH R + H2
Ni / Pt / Pd
R CH2 CH2 R
(b) R C C R + 2H2
H2
H2
R CH2 CH2 R
R CH CH R
(Not isolated)
2H2 / Ni
H2 / Ni
room temperature
H 2/Ni
(100 150C)
(f)
CH2 CH3
CH = CH2
(e)
CH2 CH3
(d)
Remarks:(a) Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pd at room temperature.
(b) All C C bonds(C = C, C C) are hydrogenated. The reaction cant be stopped at any intermediate stage.
Exceptions:Aromatic bonds which are stable at room temperature but can be hydrogenated at high temperature.
The no. of moles of H2 consumed by 1 mole of compounds is equal to the no. of bonds presents.
All positional isomers of alkenes or alkynes (due to multiple bond) always give same product on hydrogenation.
Page-14
During catalytic hydrogenation, all monochlorination and no rearrangement in carbon skeleton takes place.
Ex:- C = C C = C + Cl2 X
Ex.
C CC
C Cl
2H2 / Ni
(1)
C Cl
Y =
Cl / h
2
Y + Z
(X)
Z =
Cl
CH3
CH3
H / Ni
2
(2)
CH3
CH3
H / Ni
2
(3)
Q.
Cl / h
2
5 Monochloro product
5 Monochloro product
H / Ni
Cl / h
Z(only one monochloro product)
X(C4H6) 2 Y 2
Identify X, Y, Z
Ans.
DU = 2
Cl
Identify the lowest molecular weight alkane which gives four structural isomeric monochloro products ?
C C CC
Q.
Ans.
C5H12
= 72g
Ans.
C
C C C C,
C
Q.
Ans.
DU = 2
Q.
CCCCCC
2 monochloro product
Find the structural isomers of
product?
Q.
Q.
Ans.
Cl / h
2
A
C8H17 Cl
(C8H18 )
(Only one type)
Identify A ?
Page-15
Q.
Ans.
C C
C C C C
C C
Write all isomeric alkynes which produce an isomer of heptane which on further monochlorination gives
(a) three monochloro products.
CC
(i) C C C C C
(b)
Ans.
two monochloro
Nil
Q.
Find the structure of lowest molecular weight hydrocarbon and maximum unsaturation which on hydrogenation produce such an alkane which gives two monochloro products ?
Ans.
C = C = C or C C C
Q.
Determine the M.W. of maximum unsaturated hydrocarbon which on hydrogenation gives C6H12 which on
further chlorination gives two monochloro.
C
(ii) C C C C C
C
Ans.
CH2
Ans.
CH2
CH2
C6H6 = 78g
Ozonolysis :
It tells about position of unsaturation.
Remarks:(1)
(2)
(3)
The products are carbonyl compounds (aldehydes or ketones). This type of ozonolysis is known as reductive
ozonolysis.
(4)
(1) O3
General Reaction:- R CH = CH R
R CH = O + O = CH R + ZnO + H2O
(2) Zn/H O
2
Ex:-
(1) O3
CH2 = O + CH2 = O
(2) Zn/H2O
(1) O3
CH3 CH2 CH = O + O = CH2
(2) Zn/H2O
O3 / Zn
O / Zn
3 + OHC CH2 CHO (Propandial)
Page-16
Applications:
The process is used to determine the position of C = C in a molecule.
If the products are rejoined, the position of C = C can be determined in the reactant molecule. All C = C (except
O3
O = C C C C C = O + O = CH2
(1)
Zn
O ()
3
(2)
(4)
Q.
CH = CH CH3
low temperatur e
(3)
Zn
CH = O
O3 / Zn
CH = CH
+ O = CH CH3
O3
C6H5 CH = O
Zn
H / Ni
Cl / h
2 CnH2n 2 2
CnH2n1Cl
(P)
CnH2n 2
( Q)
(m products )
Single Compound
m3
(no isomer )
H2O2 O3(oxidative)
CH3
HCOOH + CH3 C COOH
CH3
Identify P ?
Ans.
P=
Q.
Ans.
Find the structure of the hydrocarbon and the no. of monochloro products formed by hydrogenation.
,
5 monochloro product
X
H / Ni
2
(Unsat. hydrocarbon)
Q.
Cl2
m products
h
(m 3 )
O 3 (Zn/H2O)
identify structure of X ?
O
Ans.
X =
Page-17
Q.
H / Ni
2
X
(Unsat. H.C.)
Cl / h
2
m products
(m 7 )
O 3 (Zn/H2O)
C
X
Ans.
C=CC
Q.
Identify structure of X ?
Ans.
X is
Q.
H2
CCCCCC
X
O3 (Zn)
X is C C = C C = C C
Q.
CH3
CH
3
Q.
CH3
Q.
O3
Zn, H2O
O3
Zn, H2O
CH3
CH3
C C
+2
CH
3
Q.
O O
Stereoisomers (Classification)
Steriosomers :
The stereoisomers has different orientation of groups along a stereo centre. A stereocentre can be C = C
(any double bond), a ring structure, asymmetric carbon atom (*Cabcd). These isomer has same general
formula, structural formula and molecular formula but different stereochemical formula.
E.g.
CH3
C=C
H
CH3
(I)
CH3
H
H
(II)
C=C
H
CH3
CH3CH2CH=CH2
I, III
II, III
I, II
(III)
Positional
Positional
Stereoisomer
Configurational isomers :
Configurational isomerism arises due to different orientations along a stereocentre and these isomers can
be seperated and these isomers do not convert into one-another at room temperature. Therefore, they are
true isomers. They can separated by physical and chemical method.
E.g.
Cis2Butene
Trans-2-Butene
Conformational isomers :
When different optical orientations arise due to the free-rotation along a sigma covalent bond. Such isomers
are called conformational isomers.
E.g.
eclipsed ethane and
staggered ethane
These change into each other at room temperature and can never be isolated. So these are not considered
as true isomers.
Geometrical Isomerism
1.
C=C
(I) b
a
b
(I)
a
(II)
b
Page-19
Condition
(i) The two groups at each end of restricted bond must be different.
1
3
C=C
2
4
Caa Caa
X
Caa Cbd
X
Cae Cb2
X
Cab Cab
Cab . Cbd
Cab Cde
(ii) In two geometrical isomer the distance between two particular groups one the ends of the restricted bond
must be changed.
Q.
(2) Propene
(6) 1, 2-Dideuteroethene
H2C = CH
4, 5, 6
Nil
and
By E / Z
Q.
Which of the following compounds show geometrical isomerism after reaction with NH3.
O
||
(a) CH3 C CH3
O
||
(d) CH3 C H
(g)
Ans.
O
||
(b) H C H
O
||
(c) H C D
(e) Ph C CH3
||
O
(f) Ph C Ph
||
O
(h)
(i)
c, d, e, g, i
(b) Oximes
C = N OH :
They are prepared by reacting carbonyl compuond with hydroxyl amine (NH2 OH)
R
H
C = NOH
H
(Aldoxime)
OH
C=N
H
H2O
+ H2 NOH
C=O
(I)
(syn)
OH
C=N
and
(II)
(anti)
CCCC=O
H
(3) 3-Pentanone
CCCCC
O
(4) Acetophenone
C 6H 5CCH 3
O
(5) Benzophenone
C 6H 5CC 6H 5
O
O
(6) Cyclo hexane
O
Me
(7)
Methyl Cyclohexanone
Ans.
1, 2, 4, 7
Page-21
Q.
Ans.
The lowest molecular weight of acyclic ketone and its next homologue are mixed with excess of NH2 OH
to react. How many oximes are formed after the reaction ?
3
(c) Hydrazones
C = N NH2 :
H2O
C = O + H2N.NH2
H
hydrazine
C = NNH2
H
R
NH2
R
+
C=N
H
(I)
NH2
C=N
H
(II)
(Geo. diastereomers)
Q.
Ans.
Two chain isomer of a cycloalkanone which are next higher homologue of lowest molecular weight,
cycloalkanone reacted with hydrazine. Identify the structure and number of isomer of hydrazones prepared ?
..
..
N
NH2
NH2
N
N ..
O +
+ H2N NH2
+
+
NH2
CH 3
CH3
O
CH
3
Number of isomer = 3
(3) Geometrical isomerism across azo compounds ( N = N )
(i) H N = N H (H2N2)
..
..
N=N
Ph
syn
Ph
..
Ph
..
N=N
anti
Ph
(i)
Restricted rotation
(ii)
(iii)
Page-22
Stereocentre
An atom or bond across which stereoisomerism exists (either G.I. or optical isomerism)
These compounds which are not mirror images of each other are diastereomers. These compounds which
are non-superimponsible mirror-images of each other are enantiomers
are enantiomers
Stereocentre = 2
Geometrical isomerism = 4
(a)
(b)
(c)
(d)
Ex.1
Ans.
Page-23
Ex.2
Cl CH CH
CH CH
Ans.
Stereocentre = 4
Geometrical isomerism = 23 + 21 = 10.
Case III : Compounds with similar ends but odd number of stereocentre.
No. of Geometrical isomerism = 2n1 + 2
Ex.1
Ans.
n 1
2
CH CH = CH CH = CH CH = CH CH3
Stereocentre = 3
Geometrical isomerism = 6
E/Z Nomenclature :
Z (Zussamen = together) a > b and e > d
(a)
(b)
<
(c)
<
(d)
>
Ex.
Ex.
E
(iii) If the first atom has same atomic number but different atomic mass, that is isotopes. Then heavier
isotope has higher seniority.
Page-24
(iv) If the group has unsaturation, then a hypothetical hypothetical equivalent in drawn for it and it is compared with other group for seniority.
(1)
(2) CH = CH2 < C CH
Ex.
(1)
HC
C == C
C(CH3)3
E
CH CH = CH2
(2)
N
(3)
CH2 C(CH3)3
H2C = C = CH
C == C
CH
(3)
(4)
(5)
Page-25
()
()
(i) O = C = O
Non-Polar
(ii) S = C = S
Non-Polar
(iii)
Polar
(iv)
Polar
(v)
Polar
3 F
but
Thus,
But,
H F > H Cl.
dCH3 Cl dCH3 F
> ROR
(X = Cl, Br, I)
(A)
(cis)
(trans)
(i)
<
(ii)
<
(iii)
(iv)
>
Page-27
O ------ H O
CR
RC
dimer
O H ------ O
(i) C3H8O
C C C OH
> C C C
Eg:-
OH
(ii) C4H10O
Among stereoisomers:-In geometrical isomer, the dipole moment of geometrical isomer is always different.
More polar geometrical isomer has higher B.P.
(a) Cab = Cab
B.P.cis > B.P.trans
(b) R CH = CH X
COOH
H
H
>
C=C
C=C
H
COOH HOOC
COOH
Fumaric acid (trans)
Maleic acid (Cis)
H
(c)
CH3
CH3
H
C=C
(d)
+CHO
CH3
(e)
H
NH2
CH3
C=C
>
C=C
CHO
C=C
>
NH2
OH
OH
Less
Intermolecular
H-bonding
Ortho
5-membered
Intramolecular
H-bonding
OH
OH
OH
More
Intermolecular
H-bonding
Page-28
<
Et
(c)
CH3
<
<
>
H C OR
O
(No H-bonding)
(H-bonding)
H-attached to O
(ii) CH3 CH2 CH2 CH2 OH
(H-bond)
H with R
CH3 CH2 O CH2 CH3
(No H-bond)
>
C
(i) C C C C > C C C
CH3
|
**Exception :- (ii) CH3 C CH3 > CH3 CH2 CH2 CH2 CH3 > CH3 CH CH2 CH3 (M.P.)
.)
|
|
CH3
CH3
.C
C=
*
a
a
C=C
b
Page-29
Centre of Symmetry (C.S.) :- If we start from one point of the molecule, reach to centre and then go to
equal and opposite distance (in same direction), then if similar point is obtained, then the molecule has a
C.S.
(It should be applicable to all the points of the molecule).
The trans isomers has more no, of symmetry elements than cis isomer; so it is more closely packed in solid
state and has higher M.P.
Me
(2)
>
C=C
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
(m)
(o)
(p)
less polar
more polar
Most symmetric
para > ortho > meta (we see polarity now, if H-bonding doesnt exist)
(1)
OH
OH
OH
OH
OH
(p)
(2)
Symmetrical
H-bond
(intermolecular)
OH
(m)
Intermolecular
H-bond
(o)
Intramolecular
H-bond
Ex:-
(I)
>
Me >
(iii) Formic acid > Acetic acid > Propanoic Acid > Butanoic acid
(II)
(b)
(c)
(d)
(2) Chain isomers (Effect of Branching):As branching (in Hydrocarbon) , Surface Area of hydrocarbon so, water solubility (as area repelling
water decreases)
Degree:- 3 > 2 > 1 (OH)
C C C OH < C C C.........Solubility
OH
C C C OH > C C C.........B.P..
OH
Ex:-
(ii) C4H10O
C
C
C C C C OH < C C C OH < C C C C < C C C
OH
OH
CH3
|
CH3 CH CH C O H
O
<
>
(ii)
<
COOH
COOH
C=C
(iii)
H
COOH
H
C=C
>
COOH
Optical Isomerism
Some organic compounds can rotate the plane of plane-polarised light. Such compounds are called
optically active compounds.
The optically active compound can show optical isomerism.
Measurement of optical activity
It is measured by an instrument called polarimeter.
=
(1)
(3)
(5)
(6)
Recorder
(8)
Page-31
Inference
Compound is optically inactive.
Optically active, dextrorotatory or d or (+).
Optically active, laevorotatory or l or ().
Specific Rotation:- The specific rotation of a compound indicates the optical rotation of unit concentration (1 g/mL)
present in a sample tube of 1 dm of path-length at given temperature and given wavelength of light. It is
represented as follows:-
t 25 C
[ ] 580 nm
where
Q.
Compound X has = +70 for 2 g/mL solution in sample tube of = 1 dm. Calculate ?
Ans.
(1)
(2)
70
= +35
2
Its concentration is made twice, the observed rotation() will be 140 but = 35
If = +70, it will be a
(i) d compound or (ii) compound of = (360 70) = 290
It can be decided by changing the concentration or by changing the length of the tube (c or ).
If concentration is reduced to half, d will have +35 and will have 145 (not distinguish) still halfed, it will
give +17.5 and 72.5 to distinguish.
(I)
(II)
With symmetrical
With asymmetric
molecule
molecule
[] = 0
[] 0
Optically inactive compounds:These compounds have symmetrical molecule, so the optical rotation observed after interaction of light is
zero.
But in case of optically active compounds. The molecules are asymmetric in nature and show non-zero
optical rotation.
Cl
H
R
C=C
Ex:-
H
R
Centre of symmetry
Cl
Centre of symmetry
Page-32
Dissymmetry:- The molecules or objects in which minimum two elements of symmetry (Centre of symmetry and
Plane of symmetry) are absent are called dissymetric molecules/objects.
Asymmetry:- When all the elements of symmetry (23 including Centre of symmetry and Plane of symmetry are
absent) the molecule is said to be asymmetry.
So, all asymmetric molecules are always dissymmetry, but the reverse is not true.
Dissymmetry and chirality:- All dissymmetric molecules are chiral and are optically active.
Dissymmetry, Chirality and Optical Activity:- Dissymmetry/Chirality is the minimum and sufficient condition for a
molecule to be optically active. So, if in a molecule, a C.S. and P.S. are absent, the molecule will be optically
active. All asymmetric molecules are also optically active.
Chirality (Hand-like property or Handedness):- The human hand does not have Centre of symmetry and Plane
of symmetry , so it is dissymmetry. It does not have any element of symmetry, so it can be called
asymmetry. Any molecule which has this property is called chiral.
Note : All dissymmetric compounds are chiral.
The dissymmetric molecules have two orientations in space. These two orientations are called
stereoisomers, optical isomers, enantiomers.
These are mirror images (enantiomers).
Non-superimposability of enantiomers:- The dissymmetric molecules are always non-superimposable
on their mirror-image orientations.
The non-superimposable orientations are non-identical orientations, so are called isomers.
Because of dissymmetry, these two isomers are capable of rotating plane-polarised light. So, these are
called optical isomers.
Optically Active Carbon Compounds:If a carbon-atom is attached with four different group, then if does not have any element of symmetry. It is
known as asymmetric carbon atom, which is represented as *Cabde.
a
C*
e
d
If a molecule contains only one asymmetric carbon atom, then the molecule as a whole becomes chiral and
optically active and show optical isomers.
b
Centre of symmetric
Plane of symmetric
Optical active
H
C
(1)
H
Absent
Yes
No
Absent
Yes
No
H
C
(2)
H
Cl
Page-33
H
C
(3)
Br
Cl
Absent
Yes
No
Absent
No
Yes
H
C
(4)
Br
Cl
(iii) Letter A
(iv) Letter G
(v) Fan
(vi) Door
Ex:-
(i) Butan-2-ol
CH3
C
H
OH
C2H5
Ex:-
OH
CH3
H
OH
CH2CH3
Ex:-
///////////////////////
(1) 2-chlorobutane
(2) Pentan-2-ol
Page-34
*
(3) CH2 CH CH
OH OH O
*
*
(4) CH3 CH CH CH2 CH3
OH OH
CHO
CHOH
CHOH
CHOH
CHOH
CH2 OH
(5) Glucose
OH
OH
OH
OH
Configuration nomenclature in Optical Isomers :Relative configuration : The experimentally determined relationship between the configurations of two
molecules, even though we may not know the absolute configuration of either. Relative configuration is
expressed by D-L system.
Absolute configuration : The detailed stereochemical picture of a molecule, including how the atoms are
arranged in space. Alternatively the (R) or (S) configuration at each chirality centre.
(I) D - L System (Relative configuration) : Application on correct Fisher Projection Formula
This method is used to relate the configuration of sugars and amino acids to the enantiomers of glyceraldehyde. The configuration of (+)-glyceraldenyde has been assigned as D and the compounds with the same
relative configuration are also assigned as D, & those with (-) glyceraldehyde are assigned as L.
Page-35
Examples :
Sugars have several asymmetric carbons. A sugar whose highest numbered chiral centre (the penultimate
carbon) has the same configuration as D-(+)-glyceraldehyde ( OH group on right side) is designated as a Dsugar, one whose highest numbered chiral centre has the same configuration as L-glyceraldehyde is designated as an L-sugar.
e.g.
S Sinister
Examples :
a
b
(3)
Q.
c
a
d
Now go from a to b, b to c.
(i) If it follows clockwise route, it is (R).
(ii) If it follows anticlockwise route, its configuration is (S).
Br
Br
Cl
Cl
F
(S)
(R)
Me(c)
Ex:-
H(d)
Et(b) (d)
Pr
(a)
(b)
abc
Clock wise
(a)
Page-36
Q.
(1)
Ans. R
(2)
Ans. R
(3)
Ans. S
same
same
same
same
different
Molecules with more than one chiral carbons:(I) Calculation of No. of optical isomer :Case I:- When all Chiral carbon atoms are differently substituted (all are dissimilar C*)
optical isomer = (2)n
Case II:- When all the Chiral carbon atoms are similar at ends.
n
(i) n = even
x = 2n 1 + 2 2
(ii) n = odd
x = 2n 1
Molecules with two Asymmetric Carbon Atoms of Dissimilar Nature:(i) Structural formula
CH3 CH CH CH2 CH3
Cl
Cl
n
2
(ii) Optical isomer = 2 = 2 = 4
Page-37
CH3
CH3
CH3
Cl
Cl
H H
Cl
Cl
H; Cl
C2H5
C2H5
I
[] = +x
CH3
Cl
Cl
C2H5
II
x
Cl
C2H5
III
+y
Analysis:(a)
I, II Enantiomers
I, III Diasteromers
II, III Diasteromers
IV
y
III, IV Enantiomers
I, IV Diasteromers
II, IV Diasteromers
n = 3,
x = 23 = 8 (4 d- pairs)
Ans.
Q.
(i)
(ii)
(ii)
(iii)
(iv)
OH
OH
Me
(I)
(II)
In (I and II)
Plane of symmetry present.
Superimposable on its mirror image.
Thus, I and II are identical.
[] = 0, optically inactive.
Meso isomer
(III)
(IV)
Page-38
Meso isomers: The optical stereoisomers which have more than one no. of asymmetric carbon atoms but have a plane of
Q.
COOH
OH
(1)
(2)
H
Ans.
OH
COOH
Cl
Me
Cl
(3)
(4)
Me
OH
H
(5)
*
OH
\\\\\\\\\\\\\\\\\\\\
(I)
2S
3S
4R
(II)
2S
3R
4R
(III)
2S
3 achiral
4S
(IV)
2R
3 achiral
4R
Optically active
Properties of Optical Diastereomers:The optical isomer which are neither mirror image nor superimpossible to each other are called optical
diastereomers.
Conclusion:- Optical Diastereomers have different physical properties, so these can be separated by normal
physical methods of separation.
(i) By fractional distillation (different B.P.)
(ii) By fractional crystallization (different solubility)
(iii) Chromatography (different solubility)
(iv) Differential Melting (M.P. diff.)
Page-39
Assertion:- All diastereomers have different polarities (Both Geometrical and Optical) True
Assertion:- Geometrical isomer are always diastereomers True
Resolution of d mixture (Racemic Mixture):- The enantiomers in a d pair have identical physical properties, so these cannot be separated by using normal physical methods of separation. The special methods
used for separation of d pair is known as resolution.
Chemical method of separation (resolution) by using optically active reagent: General scheme of resolution:-
d+
+ d'
Racemic Optically
mixture
active
Reagent
Hydrolysis
Hydrolysis
d + d'
Example:-
Esterifica tion
COOH
(d)
Me
Et
Et
+ OH
H
D
(d')
COOH
( )
H + H
(dd')
CO
O
(d')
O
D
( d ')
(dd')
Me
H
( d' )
CO
Me
Et
Me
Et
Me
Me
Pair of Diastereomers
Ester upon still hydrolysis will give back the carboxylic acid and alcohol.
(II) Separation of (d ) pair of alcohol by using optically active acid:D
Ph
+
H
(dd')
OC
O
Me
Me
Ph
Me
CO
O
( d' )
Me
Page-40
(obs)
100%
[]specific
Asymmetric N:R' N
N R'
R''
R''
A nitrogen atom attached with 3 different groups (sp3) is chiral, asymmetric.
In case of acyclic compounds, the Nitrogen, having trigonal pyramidal shape undergoes rapid inversion of shape
at room temperature. So at room temperature, everytime a racemic mixture of d and forms exists.
This racemic mixture can never be resolved at room temperature.
Nitrogen converts into its enantiomer..
So, acyclic molecules with chiral nitrogen are chiral but optically inactive ([] = 0) and are non-resolvable.
If asymmetric Nitrogen atom is present in ring structure, then inversion does not take place and such molecules are
optically active [] 0 . (otherwise ring will break)
Ex:-
Me
N
[ ] 0
CCC CC
(Conjugated double bond)
Alternate
C CCC C
(Isolated double bond)
Separated
e.g.
Page-41
e.g.
The groups at the end of allene structure lie in same plane (ZX plane). Therefore it will have a plane of
symmetry (ZX plane). The molecules lacks molecular dissymmetry & it will not show optical activity hence
optical isomerism. But the compound will exist in two geometrical diastereomeric forms.
(II) Case of spiranes : A similar case like allenes is observed in spiranes. The spiranes with even rings and
different groups at terminal carbons show optical activity & optical isomerism, while the spiranes with odd
rings shows geometrical isomerism.
(a) spiranes with even rings :
shows optical isomerism.
Page-42
Lecture # 14
CONFORMATIONAL ISOMERISM :
1.
Free Rotation : A sigma covalent bond undergoes free rotation at room temperature.
(CC, C O, CN, NN, OO)
2.
Conformers / Rotamers or conformations : The infinite number of spatial oreintation of molecule is arise
due to free rotation along a sigma covalent bond or rotamers.
3.
Conformational Isomers : The conformations of extreme energy different are called conformational isomers but these are not true isomers and can never be isolated.
4.
Conformational energy : The potential energy different b/w 2 conformational isomer is called conformational energy. It has very low value i.e. (1020 kJ/ mole) which is available at room temperature.
Projection formula
(a) Saw horse Projection formula
Ex.
CH3 CH3
rotation
Eclipsed
Staggered
1
12.5 kJ / mol
Page-43
Ex.
CH3CH2CH3
Eclipsed
Staggered
CH3
H
60
H
H
II
Staggered
Eclipsed
120
HH
H
III
Eclipsed
CH3
H
H
H
H
H
IV
Staggered
Propane :
Butane :
Ex.
CH3
CH3
60
H
H
HH
(I)
CH3
CH3
120
H
(II)
180
CH3
H
H
240
CH3
(IV)
H CH3 H H
(V)
Page-44
300
360
Conformational Isomers : Due to free rotation from 0 to 360 those conformations which are most stable
and have minimum P.E. are defined as conformational isomers. They maay have same energy and such
isomers are called degenerate isomers or equienergic isomers.
The conformational isomers with different energies are called non-degenerate isomers.
The conformational isomes lie at the P.E. minima in the P.E. diagram with respect to rotational angle.
Conformational Energy (C.E.)
The rotational energy barrier is known as conformational energy. It is the P.E. difference between conformational at potential energy minima and maxima.
Angle of rotation/Dihedral Angle (D.H.A.)/Torsion Angle :
The interfacial angle between the groups attach at two -bonded atoms is defined as dihedral angle.
Strains :
(i) Torsional Stran (eclipsing strain) :
It is defined as the electronic repulsion between the bond-pairs of two adjacent eclipsed bonds. It is active at
torsional angles 0, 120, 240 which the molecule has eclipsed conformation. It is considered almost zero
in the staggered conformation. (D.H.A. = 60, 180, 300)
(ii) Vander Wall strain :
It is the repulsion between the group attached at adjacent bonds. The vander wall strain is maximum in
eclipsed conformation, and minimum in anti conformation, while intermediate in gauche (skew) conformations.
It is almost zero for H-atom since the sum of vander wall radii is less than internuclear distance between two
H atom.
(iii) Angle Strain :
It arises due to distortion in normal bond-angles. In acyclic compounds, there is no distortion of bond-angle
due to free rotation. So, all conformational have angle strain zero.
Page-45
Page-46
CH3
Ques. Draw conformation isomers of following compound CH3 CH CH CH3 with respect to C2 and C3 carbon
CH3 CH3
atoms.
H
H
H
60
180
CH
CH3 CH3 3
Eclipsed
CH3
CH3
H3CCH
CH3
CH3
CH3
120
H3C
H3C
CH3
H3C
CH3
H
Staggered
CH3
CH2OH (Glycol).
CH2OH
OH
OH
H
H
(II) Gauche
OH
H
H
Gauche form most stable due to hydrogen bonding.
Stability Order : II > IV > III > I
H
Example 2.
Page-47
Example 3.
Tartaric Acid :
COOH CHOH CHOH COOH
Sterioisomers : 3
1. Meso
COOH
H
OH
OH
COOH
2. d/
COOH
COOH
H
Meso
COOH
H
OH
OH
COOH
OH
OH
H
H
COOH OH
COOH
COOH
COOH
H H
COOH
OH
OH
COOH
OH
OH
OH
d/
COOH
COOH
COOH
OH
H
OH
COOH
H OH
OH
COOH
COOH
OH
HH
COOH H
OH
COOH
COOH
OH
OH
COOH
COOH
OH
H
COOH OH
OH
Conformation isomers of cyclohexane : Superficial idea of chair & boat form (This is discuss in orientation class)
Page-48
H
OH