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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
Metamers
Chain isomers
(e) Amides 1, 2, 3
Page-2
Contents
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
Isomerism Lecture Notes
Isomers:
Compounds with same general formula or molecular formula but different physical and chemical property.
Ex:- CH3 CH2 OH and CH3 O CH3
Homologs:
Compounds with same general formula differing by same structural unit CH2 or molecular weight by 14
unit.
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. C4H8
CH3
S.F. (i) CH3 CH2 CH = CH2 (ii) CH3 CH = CH CH3 (iii) CH 3 C = CH 2
These are structural isomers.
For (ii), S.C.F. are
H3C CH3 H3C H
C=C and C=C
H H H CH3
Stereocentre
These are stereoisomers.
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:-
(c) C5H12 CH3 CH2 CH2 CH2 CH3 , CH3 CH2 CH3 , CH3 CH3
(d) C6H14 (i) CH3 CH2 CH2 CH2 CH2 CH3, (ii) CH3 CH CH2 CH3,
Page-5
Ex. (i) C C C C C C (ii) C C C C C C, (iii) C C C C C C
CC C C C C
(i), (ii) Chain
(ii), (iii) Position
(1) , (2) , (3) , (4) ,
CCC CC
(5) , (6) , (7) , (8) ,
CC CC
Ex. (1) C C C C C , CC C CC
C C
(2) C = C C C , CC=CC
(3) C C C C C , CCCCC
Page-6
(4) C C C C , C C C C OH
OH
Q. Write all Positional isomers of Dichlorobenzene ?
Cl
Cl
Cl
Cl
Ans. , ,
Cl Cl
Ans. ,
Cl
Ans. , ,
Cl
Cl
Ans. , ,
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
(c) Bicyclo
(2) C C C OH CCOC
Alcohol Ethers
(3) C C CH = O C C C
O
Aldehydes Ketones
(4) C C COOH C C OC
O
Carboxylic acids Esters
..
(5) C C C NH2 (a) C C NH C 1, 2, 3 amines are functional isomers
1 amine 2 amine
..
(b) C N C
C
3 amine
Page-7
(6) CCCN C C NC
Cyanide Isocyanide
(Propanenitrile) (Ethane isocyanide)
O
Peroxy bond (unstable)
O
does not exist at room temperature.
C = C O C OH Hemiacetal
R O CH2 OH Unstable
(i) C = C OH (ii) C C OH (iii) C OH
OH
(iv) C OH (v) C O C = C (vi) Any peroxy compound
OR OH
Ans. (i) C C C C C OH, C C C C C,
C C C C C, C C C C OH,
OH OH
C C C
C C C C OH, C C C OH, C C C OH (7 alcohols)
C C
C
C C C C O C, C C C O C, C C C O C, C C O C,
C C C
C
C C C O C C, C C OCC (6 ethers).
Q. G.F. n M.F.
CnH2n + 3N (1) 3 C3H9N
R
Q G.F. n M.F.
CnH2n + 1N (1) 2 C2H5N
2
H
Q. G.F. n M.F.
CnH2n 1N 2 C2H3N
Ans. Cyanides and isocyanides
H3C C N 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.
(b) R NH R 2 Amines
(c) R N R 3 Amines
R''
(d) R S R Thioethers
(e) R C O R Esters
O
(f) R C O C R Anhydrides
O O
O
(g) R S O R Sulphonate esters
O
Ans. CC NCC
C
CCC NC
C C
C C NC
OCC OC
Q. and Show which type of isomerism ?
C
Ans. Metamerism
Q. Acyclic compound (A) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (A).
C C
Ans. 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).
C C
Ans. or
C C
C
Page-9
Q. Write structure of smallest cyclic ester (S.F.)
C O
Cyclic esters are known as lactones.
O
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 2H
(b) H3 C H2C CH3 CH3 C CH or CH2 = C = CH2 or
(DU O)
yo
(ii) CxHyOz (x + 1)
2
ys
(iii) CxHyXs (x + 1)
2
yw
(iv) CxHyNw (x + 1)
2
ys w
(v) CxHyOzXsNw (x + 1)
2
(a) C6H6O DU = 4
(b) C6H5Cl DU = 4
(c) C6Br6 DU = 4
(d) C5H11OCl DU = 0
(e) C9H12N2 DU = 5
(f) C6N6 DU = 10
C=CC=C
Page-11
C
C
CH2
2. C2H2Cl2 =1
Total isomers = 3
Cl NHOH
OH Cl
3. C6H6ClNO (Aromatic) =4
NH2
Note : If the aromatic Compounds have minimum D.E. 4. That means at least 1 Benzene ring is present.
ANS. DU = 9
or or CC=CC
Page-12
Structure Identification of Organic Compounds by Chemical Reactions:
Monochlorination:-
Cl / h
(a) (i) CH4 2 CH3Cl + HCl
Cl / Sunlight
(ii) CH3 CH3 2 CH3 CH2Cl + HCl
Cl
Cl / h
(iii) 2 + HCl
C C
Cl / h
(iv) C C C 2 C C C Cl + HCl
C C
Cl
Cl / h
(v) 2 + 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.
Monochlori nation
Ex. (a) C C C 2
Monochlori nation
(b) C C C C 2
Monochlori nation
(c) C C C C C 3
Monochlori nation
(d) C C C C 4
C
CH3
Monochlori nation
(e) 5
Cl / h
Q. X(C5H12) 2 only one monochloro isomer..
Ans. X = Neopentane
Cl / h
Q. P(C6H14) 2 Two monochloro
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 CH2Cl
Cl / h
Ex. 2
Cl / h
Q. X(C8H10) (Aromatic) 2 Two mohochloro
Cl / h
Y(C8H10) (Aromatic) 2 One monochloro
Ans.
(X) (Y)
Catalytic Hydrogenation of C = C; C C
General reaction:-
Ni
(a) R CH = CH R + H2
R CH2 CH2 R
Ni / Pt / Pd
(b) R C C R + 2H2 R CH2 CH2 R
H2
H2
R CH CH R R CH2 CH2 R
(Not isolated)
2H2 / Ni
(c) CH2 = CH CH CH3 CH3 CH2 CH2 CH3
3H2 / Ni
(d)
(e)
room temperature
CH2 CH3
H 2/Ni
(100 150C)
(f) [Reaction cannot be stopped at any intermediate stage]
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 hydrogena-
tion.
Page-14
During catalytic hydrogenation, all monochlorination and no rearrangement in carbon skeleton takes place.
Ex:- C = C C = C + Cl2 X C CC
C Cl
2H2 / Ni Cl / h
Ex. (1) 2 Y + Z
(X)
C Cl
Y = Z =
Cl
CH3 CH3
H / Ni Cl / h
(2) 2 2 5 Monochloro product
CH3 CH3
H / Ni
(3) 2 5 Monochloro product
H / Ni Cl / h
Q. X(C4H6) 2 Y 2 Z(only one monochloro product)
Identify X, Y, Z
Ans. DU = 2
Cl
X , Y , Z
Q. Identify the lowest molecular weight alkane which gives four structural isomeric monochloro products ?
Ans. C C CC
C
C5H12 = 72g
Ans. C C C C, CCCCCC
C
Ans. DU = 2
2 monochloro product
Q. Find the structural isomers of fully saturated cycloalkane of M.F. C6H12 which gives two monochloro
product?
Ans.
Cl / h
Q. A 2 C8H17 Cl
(C8H18 ) (Only one type)
Identify A ?
Page-15
C C
Ans. C C C C
C C
Q. Write all isomeric alkynes which produce an isomer of heptane which on further monochlorination gives
(a) three monochloro products.
CC C
Ans. (i) C C C C C (ii) C C C C C
C
(b) two monochloro
Ans. Nil
Q. Find the structure of lowest molecular weight hydrocarbon and maximum unsaturation which on hydrogena-
tion 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.
CH2
Ans.
CH2 CH2
C6H6 = 78g
Ozonolysis :
It tells about position of unsaturation.
Remarks:-
(1) Alkene and polyalkene on ozonolysis undergo oxidative cleavage.
(2) (a) The reagent of reductive ozonolysis is
(i) O3 (ozone) (ii) Zn and H2O or Zn and CH3COOH or (CH3)2 S
(b) The reagent of oxidative ozonolysis is O3 and H2O2.
(3) The products are carbonyl compounds (aldehydes or ketones). This type of ozonolysis is known as reductive
ozonolysis.
(4) Ozonolysis does not interfere with other F.G.s.
(1) O3
General Reaction:- R CH = CH R R CH = O + O = CH R + ZnO + H2O
(2) Zn/H O 2
(1) O3
Ex:- (1) CH2 = CH2 CH2 = O + CH2 = O
(2) Zn/H2O
(1) O3
(2) CH3 CH2 CH = CH2 CH3 CH2 CH = O + O = CH2
(2) Zn/H2O
O3 / Zn
(3) CH2 = CH CH2 CH = CH CH3
O / Zn
(4) 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
aromatic ones) undergo oxidative cleavage under normal conditions.
At higher temperature, the aromatic double bonds can also undergo ozonolysis.
C O3
(1)
O = C C C C C = O + O = CH2
Zn
O
C
O ()
(2) 3
Zn
CH = CH CH3 CH = O
low temperatur e
(3)
+ O = CH CH3
O3 / Zn
CH = CH O3
(4)
C6H5 CH = O
Zn
H / Ni Cl / h
Q. (P) 2 CnH2n 2 2 CnH2n1Cl
CnH2n 2 ( Q) (m products )
Single Compound m3
(no isomer )
H2O2 O3(oxidative)
CH3
Ans. P=
Find the structure of the hydrocarbon and the no. of monochloro products formed by hydrogenation.
Ans. , 5 monochloro product
X H / Ni Cl2
Q. 2 m products
(Unsat. hydrocarbon) h
(m 3 )
O 3 (Zn/H2O)
identify structure of X ?
O
Ans. X =
Page-17
H / Ni Cl / h
Q. X 2 2 m products
(Unsat. H.C.) (m 7 )
O 3 (Zn/H2O)
Ans. X
C=CC
Q.
Identify structure of X ?
Ans. X is
H2
Q. X CCCCCC
O3 (Zn)
Identify structure of X ?
Ans. X is C C = C C = C C
Q.
CH
3 O3
Q. 2 +
CH3 Zn, H2O
CH
3 CH3 CH3
O3
C C
Q. +2
CH3 Zn, H2O
O O
Page-18
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.
I, III Positional
II, III Positional
I, II 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. Cause of Geometrical isomerism :
Geometrical isomerism arises due to the presence of a double bond or a ring structure
C = C, C = N, N = N, or Ring structure (Stereo centres)
Due to the rigidity of double bond or the ring structure to rotate at the room temperature the molecule exist
in two or more orientations.
This rigidity to rotation is described as restricted rotation/hindered Rotation/No rotation.
E.g. a a
C=C
b (I) b
a a a a
b (I) b b b
(II)
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.
H2C = CH
(7) Phenyle thene (8) Buta-1, 3-Diene C = C C = C
Ans. 4, 5, 6
Nil
and By E / Z
(a) Imine ( )
Imine compounds are produced from carbonyl compounds on reaction with ammonia.
Page-20
Q. Which of the following compounds show geometrical isomerism after reaction with NH3.
O O O
|| || ||
(a) CH3 C CH3 (b) H C H (c) H C D
O
||
(d) CH3 C H (e) Ph C CH3 (f) Ph C Ph
|| ||
O O
Ans. c, d, e, g, i
(b) Oximes C = N OH :
They are prepared by reacting carbonyl compuond with hydroxyl amine (NH2 OH)
R R
H2O C = NOH
C=O + H2 NOH
H H
(Aldoxime)
R R OH
C=N C=N
and
H OH H
(I) (II)
(syn) (anti)
Syn and anti in aldehyde only not for ketones.
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. 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 ?
Ans. 3
R R
H2O
C = O + H2N.NH2 C = NNH2
H hydrazine H
R R NH2
C=N + C=N
H NH2 H
(I) (II)
(Geo. diastereomers)
Q. 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 ..
Ans. O + + H2N NH2 + +
NH2
CH O CH3 CH 3
3
Number of isomer = 3
(i) H N = N H (H2N2)
N=N N=N
Ph Ph .. Ph
syn anti
(i)
Restricted rotation
(ii)
(iii)
Page-22
(5) Geometrical isomerism in cycloalkenes across double bonds :
In cycloalkenes, G.I. exists across double bonds with ring size equal to or greater then 8 carbon atoms (due
to ring strain)
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
Ex.
Ans. Stereocentre = 2
Geometrical isomerism = 4
(a) (b)
(c) (d)
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.
n 1
No. of Geometrical isomerism = 2n1 + 2 2
Ex.1 CH CH = CH CH = CH CH = CH CH3
Ans. Stereocentre = 3
Geometrical isomerism = 6
E/Z Nomenclature :
Rules :(i) The group with the first atom having higher atomic number is senior.
Thus F > CH > NH2 > CH3
(ii) If the first atom is identical, then second atom is observed for deciding the seniority of the group.
(a)
(b) <
(c) <
(d) >
Ex. Z
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 com-
pared with other group for seniority.
(1)
CH 2 = CH C(CH3)3
C == C
Ex. (1) HC C E
CH CH = CH2
(2) Z
N C CH2 C(CH3)3
C == C
(3) H2C = C = CH E
C CH
(3) Z
(4) E
(5) E
Page-25
Physical properties of Geometrical isomers :
The physical properties of organic compounds can be compared through the knowledge of their molecular
formula, structural formula and stereochemical formula (S.C.F.)
The organic molecules are composed of covalent bonds, every covalent bond has its own dipole moment
which is known as bond moment.
=qd
Where q is partial charge on individual atoms A and B whose value increases with increase in E.N. difference
between A and B. and d is the internuclear separation.
(ii) S = C = S Non-Polar
(iii) Polar
(iv) Polar
(v) Polar
> COX > COOH > OH > NH2 > R X > ROR
(2.8 3 D) (X = Cl, Br, I)
Page-26
Dipole moment for Geometrical isomerism :
(A)
(cis) (trans)
= cis> trans (= O)
(i) <
(ii) <
(iv) >
If two isomers have different dipole moments then their all physical properties are different. (melting point,
boiling point, solubility, refractive index, density)
All structural isomers have different , and thus different physical properties.
In case of stereoisomers, all diastereoisomers have different dipole moments and thus different physical
properties.
All geometrical isomers are diastereoisomers and thus posses different diople moment and Physical prop-
erties.
Separation of isomers : The isomers having different physical properties can be separated by normal
physical methods of separation.
(2) Boiling Point :
Intermolecular forces of attraction :
H bond > Dipole Dipole interaction > Vander-wall force.
The boiling point of a compound depends on the intermolecular forces of attraction existing between two
molecule. If a compound has strong forces of attraction, then the B.P. is high.
Among homologs, molecular weight increases, Vander Wall force increases, Boiling point also increases
(1) Functional isomers (H-bond > Dipole Dipole > Vander Wall force)
COOH > OH > NH2 > > R X > ROR > R C CH > R CH = CH2 > R CH2 CH3
(b) C = O, R X, R OR, R C CH Dipole Dipole
In chain isomers, as branching , surface area of molecule VDW forces Boiling Point
Thus, BP 1 > 2 > 3 (OH, NH2)
(ii) C4H10O C C C C OH > C C C OH > C C C C > C C C
C OH OH
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
OH
OH
OH OH
Ortho OH OH
Less More
5-membered Intermolecular
Intramolecular Intermolecular
H-bonding H-bonding
H-bonding
Page-28
(3) Melting Point:
The melting point of an organic compound depends upon its packing in solid state. The packing depends on
following factors:-
(i) Intermolecular forces of attraction:- (H-bond > Dipole Dipole > Vander Wall force) in structural
isomer.
(ii) Symmetry of the molecule:- More symmetrical molecules are more closely packed.
In geometrical isomers the trans isomers are more symmetrical than cis isomers (Cab = Cab type of alkenes)
So trans form have higher M.P. than cis isomers.
Eg:- (I) (a) CH2 = CH2 < CH3 CH = CH2 < CH3 CH2 CH = CH2
Homologues: Molecular weight increases vander wall force increases melting point increases.
CH3 Et
(c) < < <
H-attached to O H with R
(ii) CH3 CH2 CH2 CH2 OH > CH3 CH2 O CH2 CH3
(H-bond) (No H-bond)
(iii) CH3 CH2 CH2 CH2 NH2 > CH3 CH2 CH2 NH CH3 > CH3 CH2 N(CH3)2
(1) (2) (3)
(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
Neopentane (spherical) (Close-packing)
For B.P.:- n > iso > neo
For M.P.:- neo > n > iso
a b a a
.C
C= C=C
b * a b b
Plane of Symmetry (P.S.) :- It is defined as any plane in the molecule which bisect the molecule into 2
equal halves, which should be mirror images of each other. A molecule can have more than one P.S.
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 H
(2) > C=C
Cl Cl
Cl
(1) Cl Cl
(p) (m) (o)
Most symmetric less polar more polar
para > ortho > meta (we see polarity now, if H-bonding doesnt exist)
OH
OH OH
OH
OH OH
(2) (p)
Symmetrical (m) (o)
H-bond Intermolecular Intramolecular
(intermolecular) H-bond H-bond
(I) Homologs:-
Hydrophilic water loving H-bond
Hydrophobic water repelling Hydrocarbon
As M.W.. , solubility .
(iii) Formic acid > Acetic acid > Propanoic Acid > Butanoic acid
Page-30
(b)
OH
C C C OH > C C C.........B.P..
OH
C C
(ii) C4H10O C C C C OH < C C C OH < C C C C < C C C
OH OH
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.
(1) (5)
(3) (6)
Recorder
(8)
Page-31
(1) Source of light
(2) Polychromatic Non-polarised light
(3) Slit (Monochromator)
(4) Monochromatic Non-polarised light
(5) Polariser (Prism-setting)
(6) Monochromatic plane-polarised light
(7) Sample tube ( = path length)
(8) Recorder for measurement of optical rotation
Observations:- When plane polarised light is passed through sample tube, then following changes can be observed
in the recorder:-
Angle of rotation () Inference
(1) = 0 Compound is optically inactive.
(2) = +x (clockwise rotation) Optically active, dextrorotatory or d or (+).
(3) = x (anticlockwise rotation) 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
c
where = observed angle of rotation
c = concentration in g/mL (or density)
= Path length of Sample tube in dm
Q. Compound X has = +70 for 2 g/mL solution in sample tube of = 1 dm. Calculate ?
70
Ans. = = +35
2
(1) Its concentration is made twice, the observed rotation() will be 140 but = 35
(2) 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.
Symmetry of elements :-
(1) Centre of symmetry (C.S.)
(2) Plane of symmetry (P.S.)
Cl
R H
C=C
H H
Ex:- H R
Cl
Centre of symmetry 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.
Optical Isomers:-
Enantiomers:- The mirror-image stereoisomers are called enantiomers.
Two types:-
(a) Dextrorotatory (b) Laevorotatory
C*
b 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.
up
C
H OH
C2H5
(ii) Fisher Projection formula
Ex:- (i) Butan-2-ol (CH3 CH2 CH CH3)
OH
CH3
H OH
CH2CH3
(1) 2-chlorobutane
(2) Pentan-2-ol
Page-34
*
(3) CH2 CH CH
OH OH O
1 2 3 4 5
* *
(4) CH3 CH CH CH2 CH3
, ,
OH OH
CHOH
CHOH
CHOH
CHOH
CH2 OH
H OH
H OH
H OH
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 D-
sugar, one whose highest numbered chiral centre has the same configuration as L-glyceraldehyde is desig-
nated as an L-sugar.
e.g.
R Rectus S Sinister
Examples :
c
a d
(3) 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
Q. Cl Cl
I I
F F
(R) (S)
Page-36
If the juniormost group is at horizontal line clockwise S
anticlockwise R
If juniormost at vertical line, then
clockwise R
anticlockwise S
Q. (1) Ans. R
(2) Ans. R
(3) Ans. S
Properties of enantiomers :-
One chiral carbon :
(i) Number of optical isomer = 2 (d or )
(ii) Number of Racemic Mixture Equimolar mixture of d and . [] = 0 due to external compensation of
optical rotation.
Properties:-
Cl Cl
n 2
(ii) Optical isomer = 2 = 2 = 4
Page-37
(iii) Stereochemical Formula:-
H Cl Cl H; Cl H H Cl
C2H5 C2H5 C2H5 C2H5
I II III IV
[] = +x x +y y
Analysis:-
(a) I, II Enantiomers III, IV Enantiomers
I, III Diasteromers I, IV Diasteromers
II, III Diasteromers II, IV Diasteromers
Cl Cl Cl
Calculate total number of optical isomer.
Ans. n = 3,
x = 23 = 8 (4 d- pairs)
OH OH
(i) n = 2
n
1
(ii) x = 2n 1 + 2 2 = 3 (Optical stereoisomers).
(iii) Stereo chemical formula :-
Me
H OH
H
OH
Me
(I) (II) (III) (IV)
In (I and II) Plane of symmetry present.
Superimposable on its mirror image.
Thus, I and II are identical.
[] = 0, optically inactive.
Meso isomer
In (III) Specific rotation [] = +x
In (IV) Specific rotation [] = x
No. of d pairs = 1 (III + IV) = No. of Racemic mixtures
COOH H
H OH Cl Cl OH
(1) (2) (3) (4) H
(5)
H OH Me Me *
COOH OH
Ans. (1) (2) (4) and (5)
Cl Cl Cl
n=3
x = 2n 1 = 4 stereoisomers.
\\\\\\\\\\\\\\\\\\\\
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
Resolution of d mixture (Racemic Mixture):- The enantiomers in a d pair have identical physical proper-
ties, 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.
d+ + d'
Racemic Optically
mixture active
Reagent
Hydrolysis Hydrolysis
d + d'
Example:- (I) Resolution (by using Esterification) of RCOOH and R'OH
Esterifica tion
General Reaction:- R C O H + H O R ' R* C O R'
(H2 SO 4 )
O O
H2O
Me
H COOH
(d)
Me Me Me Et Me
Et
+ OH H H CO H + H CO H
Et
O (dd') O ( d' )
(d')
H COOH D Et D Me D
( ) (d') (dd') ( d ')
Me
Pair of Diastereomers
Ester upon still hydrolysis will give back the carboxylic acid and alcohol.
Ph D
+ H OC H
O (dd')
Me Me
Me Ph
+ H CO H
O
D ( d' ) Me
Page-40
Optical Purity or Enantiomeric Excess (O.P. or E.E.):-
Ex:- Compound X has [] = 70
(obs)
We have mixture of enantiomers in different percentage. %E.E. 100%
[]specific
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)
Me
N
Ex:- [ ] 0
Since the groups at the end of allene are in perpendicular plane, it will not show geometrical isomerism. The
molecule lacks centre of symmetry as well as plane of symmetry. Overall the structure has molecular
dissymmetry which is the sufficient condition for optical activity. The molecule will exist in two enantiomeric
forms.
Page-41
(b) Allenes with odd bonds : 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 :
repulsion among the substituent. In this orientation (phenyl planes perpendicular to each other) the free
rotation of C C single bond is restricted and molecule shows optical activity due to molecular disymmetry.
e.g.
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 iso-
mers 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 conforma-
tional energy. It has very low value i.e. (1020 kJ/ mole) which is available at room temperature.
Projection formula
(a) Saw horse Projection formula
rotation
Eclipsed Staggered
1
12.5 kJ / mol
Page-43
Ex. CH3CH2CH3
Eclipsed Staggered
H
60 H H 120
HH H
H H
H H H
II III IV
Eclipsed Staggered Eclipsed Staggered
Propane :
Butane :
Ex.
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 conforma-
tional 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)
Page-45
Page-46
Ques. Draw conformation isomers of following compound (a) CH3 CH CH3 (b) CH3 (CH2)3 CH3
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 H H
H
H3C CH3
CH3 CH3
60 120 180
H3C CH
CH3 CH3 3 CH3 H H3C CH3
CH3 H3CCH CH3 H
CH3 3
Eclipsed Staggered
OH
H OH
H H
H
(II) Gauche
OH
H OH
H H
H
Gauche form most stable due to hydrogen bonding.
Stability Order : II > IV > III > I
Page-47
Example 3. Tartaric Acid :
Sterioisomers : 3
1. Meso COOH
H OH
H OH
COOH
2. d/
COOH
COOH COOH
H OH H OH
Meso COOH H
H OH H OH H
OH COOH COOH OH
COOH COOH
COOH COOH OH
OH
H H OH H OH
H
d/
COOH COOH
COOH COOH
COOH OH H OH
OH COOH
OH COOH H
H OH OH
H H OH H HH OH
COOH
COOH COOH
H
COOH H
OH
H OH
OH H COOH OH
Conformation isomers of cyclohexane : Superficial idea of chair & boat form (This is discuss in orientation class)
Page-48