EXERCISE-01 CHECK YOUR GRASP

SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER)

1. Type of isomerism exists between :-

CH 3 —CH 2 —CH 2 —CN and CH3 CH CH3

CN

(A) Position (B) Chain (C) Both the above (D) None of these
2. The number of primary alcohols possible with the formula C 4 H 10 O is -
(A) 2 (B) 3 (C) 4 (D) 5
3. The total number of benzene derivatives having the molecular formula C 7 H 7Cl is -
(A) 2 (B) 3 (C) 4 (D) 5
4. Which of the following will lead to maximum enolisation :–
(A) CH 3 COCH 3 (B) CH 3 COCH 2 CHO

O
(C) CH3 C CH C CH3 (D)
O Br O

H3C H
C C H
5. H3C C Exhibits :-
H3C COOH

(A) Tautomerism (B) Optical isomerism

(C) Geometrical isomerism (D) Geometrical and optical isomerism
6. Tautomerism is not exhibited by :-

(A) (B) (CH 3 ) 2 CHNO 2

(C) (D) (CH 3 ) 3 CCHO

7. Given compound exhibits x geometrical isomers and y optical isomers

The value of x and y respectively are :-

(A) 4 and 4 (B) 2 and 2 (C) 2 and 4 (D) 4 and 2
8. The total number of cyclic compounds (neglecting stereoisomers) with the molecular formula C 5H 10 is -
(A) 4 (B) 5 (C) 6 (D) 7
9. Which of the following exhibits tautomerism ?
(A) (CH 3 ) 2 NH (B) (CH 3 ) 3 CNO 2 (C) R 3 CNO 2 (D) RCH 2 NO 2
10. The correct structure of trans–2–hexenal is -

(A) CHO (B)

CHO

(C) (D) CHO

CHO
11. The total number of benzene derivatives having the molecular formula C 7 H 8 O is -
(A) 3 (B) 4 (C) 5 (D) 6
12. Which of the following compounds does not exhibit tautomerism
(A) CH 3 NO 2 (B) CH 3 CH 2 NO 2
(C) C 6 H 5 CH=CH–OH (D) CH 3 CH 2 OH
13. The total number of benzene derivatives with the molecular formula C 6H 3 Cl 3 is -
(A) 2 (B) 3 (C) 4 (D) 5
14. Which of the following compounds is not chiral ?
(A) DCH 2 CH 2 CH 2 Cl (B) CH 3 CHDCH 2 Cl (C) CH 3 CHClCH 2 D (D) CH 3 CH 2 CHDCl

15. The total number of stereoisomers of 2,3–dibromobutane is -

(A) 2 (B) 3 (C) 4 (D) 5
16. In the structure :

CH3
H OH
H Br the configurations at the chiral centres are :
CH3
(A) 2R, 3R (B) 2S, 3R (C) 2R, 3S (D) 2S, 3S
17. Which of the following compound contains a pseudo-asymmetric carbon atom

(A) CH3CHCHCH2 (B) CH3CH–CH–CHCH3

Br Br Br Br OH Br

(C) CH3CHCHCHCH3 (D) CH3CHCHCHCH3

OHBr Br Br OHCl
18. Consider the following structures (A), (B), (C) and (D) -

CH3 C2H5

(A) Cl Br (B) Cl Br

C2H5 CH3

Cl Cl
(C) CH3 Br (D) C2H5 CH3
C2H5 Br
Which of the following statements is not correct
(A) B and C are identical (B) A and B are enantiomers
(C) A and C are enantiomers (D) B and D are enantiomers
19. The interchange of two groups (Br and CH 3) at the chiral centre of the projection formula (A) yields the
formula (B), while the interchange of another set of two groups (C2H5 and Cl) of (A) yields the projection
formula (C) -

CH3 Br CH3

Cl Br Cl CH3 C2H5 Br

C2H5 C2H5 Cl
(A) (B) (C)
Which of the following statements is not correct about the structures (A), (B) and (C) -
(A) B and C are identical (B) A and C are enantiomers
(C) B and C are enantiomers (D) A and B are enantiomers
20. How many meso stereoisomers are possible for 2, 3, 4-pentanetriol -
(A) 1 (B) 2 (C) 3 (D) none of these
21. The total number of stereoisomers of the compound

CH3CH=CH–CH–CH=CH–CH3 is -
OH

(A) 2 (B) 3 (C) 4 (D) 8

22. The total number of aldehydes and ketones with the molecular formula C 4 H 8O is -
(A) 2 (B) 3 (C) 4 (D) 5
23. In which of the following properties do enantiomers differ from each other
(A) Solubility in an achiral solvent (B) Reactivity with an achiral reagent
(C) Melting point (D) Optical rotation
24. (+) - Mandelic acid has a specific rotation of + 158º. What would be the observed specific rotation of a
mixture of 25% (–) -mandelic acid and 75% (+) -mandelidc acid :
(A) + 118.5° (B) –118.5° (C) – 79° (D) + 79°
25. When C 6H 4Cl 2 is converted into C 6H 3Cl 3, o-isomer will give m types of C 6H 3Cl 3, and p-isomer will give
q types of C 6 H 3 Cl 3. m, n, q are respectively :
(A) 1, 2, 3 (B) 2, 1, 3 (C) 1, 3, 2 (D) 2, 3, 1

CHE CK Y OU R G R ASP ANSWER KEY E XE R CISE -1

Qu e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
An s . B A C D B D B A D B C D B A B B B D C D
Qu e. 21 22 23 24 25
An s . C B B D B
EXERCISE–02 BRAIN TEASERS

SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT ANSWERS)

1. Tautomerism is shown by :-
O O
(A) HCN (B) CH3—C—CH2—C—CH3

O
(C) CH3—CH2—N (D) CCl 3 CHO
O
2. In which of the following cases, cis-trans nomenclature can not be used :-
(A) Cl—CH=CH—Cl (B) CH 3 —CH=CH—CHO
(C) C 6 H 5 —N=N—C 6 H 5 (D) CH 3 —CH=C(Cl)C 2 H 5
3. Among the following, which are tautomers :-

(A) CH2—C—CH3 and CH2=C—CH3 (B) CH 3 —CH 2 —CH=NH and CH 3 —CH=CH—NH 2

O O

O
(C) CH3—N and CH 3 —CH=N—OH (D) glucose and fructose
O
4. Consider the following compounds :

CH3 CH3 CH3

H———OH HO———H HO———H
HO———H HO———H H———OH
CH3 CH3 CH3
(I) (II) (III)

Choose the correct statements :

(A) I and III are enantiomers (B) I and II are diastereomers
(C) II and III are diastereomers (D) I, II and III are all optically active
5. Which will show geometrical isomerism :-

(A) C 6 H 5 –CH=NOH (B)

H H
(C) C 6 H 5 –N=N–C 6 H 5 (D)
H3C CH3
6. Which statement (s) is/are correct for :-

CHO CHO
H———OH HO———H
HO———H H———OH
C6H5 C6H5
(I) (II)
(A) Both are in threo form (B) Both are enantiomers
(C) Both are diastereomers (D) Both are in erythro form
7. Which of the following compounds are chiral and resolvable :-


(A) C 6 H 5 N(CH 3 ) (C 2 H 5 ) (B) [C 6 H 5 N (CH 3) (C 2 H 5) (C 3H 7 )] Cl –

COOH

(C) CH 3 –CH 2 –CH(CH 3 ) N (CH 3 ) (C 2 H 5 ) (D)

COOH

8. Observe the following structures and pick up the correct option (s) mentioned below :-

CH3 CH3
H Cl H Cl

H H H H

CH2Cl Cl
(A) (B)
(A) The two are position isomers
(B) None of the two shows optical isomerism
(C) Only A shows optical isomerism
(D) The two are not related to each other regarding isomerism

CH3 CH3
H———Cl H———Cl
Cl———H H———Cl
9.
CH2CH3 CH2CH3
(I) (II)
(A) I and II are enantiomers (B) I is 2S, 3S; while II is 2S, 3R
(C) I is 2R, 3R; While II is 2R, 3S (D) I and II are diastereomers
10. Which of the following statements are true regarding following structures :-
COOCH3 COOH COOH
H———OH H———OH H———OH
H———OH H———OH HO———H
COOH COOCH3 COOCH3
(a) (b) (c)
(A) A and B are diastereomers (B) A and C are diastereomers
(C) B and C are diastereomers (D) A and B are enantiomers
11. The R and S enantiomers of an optically active compound differ in :-
(A) their reactivity with chiral reagents
(B) their melting points
(C) their optical rotation of plane polarized light
(D) their solubility in achiral reagents
12. Which of the following statements (s) is (are) incorrect :-

X Y

(A) X is cis- and Y is trans (B) X is Z and Y is E

(C) X is trans and Y is cis (D) X and Y are diastereomers
13. Which of the following compounds will show geometrical isomerism :-
(A) 2-butene (B) propene (C) 1-phenylpropene (D) 2-methyl-2-butene
14. Tautomerism is exhibited by :-

(A) –CH=CH–OH (B) O= =O (C) O (D) O

O O

15. Which of the following notations are correct :

Br F Br Cl
(A) C=C (B) C=C
I Cl I I
(Z) (E)

H3C CH3 H3C CH2CH2CH3

(C) C=C (D) C=C
H H H CH3
(Z) (E)

16. For which of the following pairs of compounds are the correct notation given :-

Ph Ph Ph
N=N and N=N
(A) Ph
Anti-azobenzene Syn-azobenzene

H3C H3C OH
C=N C=N
(B) H OH and H
Syn-acetaldoxime Anti-acetaldoxime

H H
CO2H H
C=C C=C
H CO2H
and
(C)
NH2 NH2
Trans-o-aminocinnamic acid Cis-o-aminocinnamic acid

H3C CH2CH2CH3 ClCH2 CH3

C=C and C=C
(D) H CH3 BrH2C CH3
Z-isomer E-isomer
17. Which of the following statements are correct :-

CH3
(A) CH 3 CH 2 CH 2 CH 2 OH and CH3CHCH2OH represent chain isomerism
(B) CH 3 CH 2 CH 2 CH=CH 2 and CH 3CH 2CH = CHCH 3 are examples of position
isomerism
(C) C 2 H 5 OCH 3 and CH 3 CH 2 CH 2 OH represent functional-group isomerism
(D) CH 3 CH 2 NH 2 and CH 3 NHCH 3 are examples of metamerism
18. Which of the following are optically active :-

(A) H 2 C=C=CH 2 (B)

C=C=C

F F Cl
H
H —CO2H
(C) H N (D)
2 NH2
F F
19. An enantiomerically pure acid is treated with racemic mixture of an alcohol having one chiral carbon. The
ester formed will be :
(A) optically active mixture (B) pure enantiomer
(C) meso compound (D) racemic mixture
20. Tartaric acid molecule contains two asymmetric carbon atoms. The number of optical isomers of tartaric
acid is :-
(A) 2 (B) 3 (C) 4 (D) 5

BR AIN TE ASER S ANSWER K EY E XE R CISE -2

Qu e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
An s . A,B,C B,C,D B,C A ,B,C A ,B,C ,D A ,B B,C A ,C B,D B,C ,D A,C A,B A,C A,C ,D A ,C
Qu e. 16 17 18 19 20
An s . B,C ,D A ,B,C ,D B,C A B
EXERCISE–03 MISCELLANEOUS TYPE QUESTIONS
TRUE OR FAL SE :
1. Stereo-isomers which are not mirror image of each other are known as diastereoisomers.
2. In every case, a pair of enantiomers have a mirror-image relationship.
3. If a compound has an enantiomer it must be chiral.
4. If a compound has a diastereomer it must be chiral
5. Any molecule containing a stereocentre must be chiral.
6. Any chiral compound with a single asymmetric carbon must have a positive optical rotation if the compound
has the R configuration.

FILL IN THE BLANKS :

1. The possible number of dichloro derivatives of propane are ...................... .

2. Ethyl benzene is ................... isomer to xylenes.
3. The compound CHCl = CHCl can show .................... isomerism.
4. d- and - lactic acid are known as ................ .
5. Maleic and fumaric acids are a pair of ............... .

MATCH THE COLUMN

1. Match the column I with column II.

Column-I (react ion) Column-II (stereoisomer s)
(A) C H 3— C H CH—CH N—OH (p) 2

(B) (q) 4

(C) CH 3 —CH CH—CH CH—CH CH—CH 3 ( r ) 6

(D) CH 3 —CH CH—CH CH—CH CH—Ph (s) 8

2. Match the following compounds of column I with column II.

Column-I (Molecule) Column-II (Proper t y)

H H
(A) C C C (p) Chiral compound
Cl Cl
H CH3
(B) (q) Presence of stereocenter
CH3 H

Cl

Br F
(C) (r) Optically active compound
I

CH3 OH
(D) C N •
(s) Compound containing plane
•
Et
of symmetry
3. Match the column I with column II.
Column-I (react ion) Column-II (stereoisomer s)

(A) & Cl (p) Homologs

Cl

OCH2–CH3 OCH3
CH3
(B) & (q) Functional isomers

OCH3 OH
CH3
(C) & (r) Metamer

(D) CH3–CH2– –CH2–CH3 & (s) Chain isomers

CH3– –CH2–CH2–CH3

ASSERTION & RE ASON QUESTION :

These questions contains, Statement-I (assertion) and Statement-II (reason).
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
1. Statement-I : Staggered and eclipsed ethane can not be separated.
Because
Statement-II : Energy barrier between staggered and eclipsed form of ethane is 12.6 kJ/mole.
2. Statement-I : All double bond containing compounds show geometrical isomerism.
Because
Statement-II : Alkenes have restricted rotation about the double bond.
3. Statement-I : Meso-tartaric acid is optically active.
Because
Statement-II : Optically active molecule is a molecule that cannot be superimposed on its mirror image.
4. Statement-I : Cyclohexanone exhibits keto-enol tautomerism.
Because
Statement-II : In cyclohexanone, one form contains the keto group (C=O) while other contains enolic
group (–C=C–OH).
5. Statement-I : Staggered form is less stable than the eclipsed form.
Because
Statement-II : The conformation in which the bond pairs of two central atoms are very far from one
another is called staggered from.
6. Statement-I : Trans-isomers are more stable than cis-isomer.
Because
Statement-II : The cis-isomer is the one in which two similar groups are on the same side of double
bond.
7. Statement-I : Propadiene is optically inactive.
Because
Statement-II : Propadiene has a plane of symmetry.

COMPREHENSION BASED QUESTIONS :

Comprehension # 1
Geometrical isomerism is a kind of stereoisomerism which is present in the compounds containing a double
bond (C=C, C=N, N=N) and arise due to the restricted or frozen rotation about the double bond. The atoms
or groups attached to the doubly bonded carbons must be different. In aldoximes, the isomer is named as
syn if hydrogen and hydroxyl groups are on the same side of C=N bond and if these are on opposite sides,
the isomer is named as anti. In ketoximes, the prefixes syn and anti indicate which group of ketoxime is syn
or anti to hydroxyl group.
1. Which of the following does not show geometrical isomerism ?
(A) 1,2-Dichloropent-1-ene (B) 1,3-Dichloropent-2-ene
(C) 1,1-Dichloropent-1-ene (D) 1,4-Dichloropent-2-ene
2. On treating with NH 2OH, which can form two products ?
(A) Acetaldehyde (B) Acetone
(C) Formaldehyde (D) Benzophenone
3. Number of stereoisomers of the compound 2-chloro-4-methylhex-2-ene is/are
(A) 1 (B) 2 (C) 4 (D) 16
4. The correct structure of trans-2-hexenal is -
CHO
(A) (B)
CHO
CHO
(C) CHO (D)
5. The geometrical isomerism is shown by :

CH2 CHCl
CH2 CHCl
(A) (B) (C) (D)

Comprehension # 2
The optical isomers rotate the plane of plane-polarised light. A sp3-hybridised carbon atom attached to four
different atoms or groups is called an asymmetrical centre or chiral centre. Chiral molecules do not possess
any of the elements of symmetry. A chiral molecule cannot be superimposed on its mirror image. These
stereoisomers are called enantiomers. Molecules having a plane of symmetry or centre of symmetry are
superimposable on their mirror images and are achiral. The stereoisomers that are not mirror images of
each other are called diastereomers. A mesoisomer has a plane of symmetry and is optically inactive due to
internal compensation.
1. Which of the following has a meso isomer also ?
(A) 2-Chlorobutane (B) 2-3, Dichlorobutane
(C) 2, 3-Dichloropentane (D) 2-Hydroxypentanoic acid
2. Which of the following compounds is not chiral ?
(A) DCH 2 CH 2 CH 2 Cl (B) CH 3 CH 2 CHDCl
(C) CH 3 CHDCH 2 Cl (D) CH 3 CHClCH 2 D
3. The total number of acylic isomers including the stereoisomers (geometrical and optical) possible with the
molecular formula C 4 H 7 Cl is :
(A) 12 (B) 11 (C) 10 (D) 9
4. Which among the following compounds will be dissymmetric but not asymmetric :

COOH OH

(A) H—C—OH (B) CH3—C—COOH

H—C—OH C2H5
CH3

COOH
CH3 CH3
(C) H—C—Br (D) C=C=C
H H
H—C—Br

COOH

5. Two isomeric alkenes A and B have molecular formula C 5H 9Cl. On adding H 2, A gives optically inactive
compound while B gives chiral compound. The two isomers are :
(A) A is 3-Chlorpoent-1-ene and B is 1-chloropent-2-ene
(B) A is 2-Chloro-3-methylbut-2-ene while B is 1-Chloro-3-methylbut-1-ene
(C) A is 3-Chloropent-2-ene and B is 2-Chloropent-2-ene
(D) A is 4-Chloropent-2-ene and B is 4-Chloropent-1-ene

Comprehension # 3
Different spatial arrangements of the atoms that result from rotation about a single bond are conformers.
n-Butane has four conformers eclipsed, fully eclipsed, gauche and anti. The stability order of these conformers
are as follows :
Anti > gauche > Partial eclipsed > Fully eclipsed
Although anti is more stable than gauche but in some cases gauche is more stable than anti.

1. Which one of the following is most stable conformer :

Cl Cl Cl Cl
H3C H Cl CH3 H Cl Cl
H
(A) (B) (C) (D) H
H CH3 H CH3 H CH3
Cl H CH3
H H3CCH3
2. Which one of the following is the most stable conformer ?

CH3 CH3 CH3

HO H CH3 OH
H H OH H CH3
(A) H (B) (C) (D)
OH H OH H OH H CH3
CH3 OH CH3 OH
3. Number of possible conformers of n-butane is :
(A) 2 (B) 4 (C) 6 (D) infinite

M ISCEL L AN E OU S TYP E Q U ESTION ANSWER KEY E XE R CISE -3

 Tr u e / Fals e
1. T 2. T 3. T 4. F 5. T 6. F
 F i ll i n t h e B lanks
1. four 2. chain 3. geometrical 4. enantiomer
5. geometrical
 Matc h th e C o lu mn
1. (A) q ; B p ; (C)  r ; (D) s 2. (A) p, q, r ; (B) q, s ; (C)  p, q, r ; (D) q, s
3. (A) p ; (B) r ; (C)  q ; (D) r, s
 A s s er ti o n - R eas o n Qu es ti o ns
1. A 2. D 3. D 4. B 5. D
6. B 7. A
 C o mp rehe ns i o n B as ed Qu e st i o ns
C o mp re he ns i o n # 1 : 1. (C) 2. (A) 3. (C) 4. (B) 5. (D)
C o mp re he n s i o n # 2 : 1. (B) 2. (A) 3. (C) 4. (D) 5. (C)
C o mp re he ns i o n # 3 : 1. (A) 2. (C) 3. (D)
EXERCISE–04 [A] CONCEPTUAL SUBJECTIVE EXERCISE

SUBJECTIVE QUESTIONS :

1. How many isomers are there corresponding to the formula C 4H 10 O ?

2. If the bonds in dichloro benzene, C6H4Cl2, were localized between specific carbon atoms, how may isomers
of this compound would exist ? How many isomers actually exists.
3. Which of the following compounds can exist as geometric isomers ?
CH 2 Cl 2 , CH 2 Cl—CH 2 Cl, CHBr = CHCl, CH 2 Cl—CH 2 Br.
4. How will you distinguish between Maleic acid and Fumaric acid ?
5. Why does cyclopentene not exhibit geometric isomerism though it has a double bond.
6. Why does 2-butene exhibit cis-trans isomerism but 2-yne does not ?
7. Which of the following pairs show tautomerism.

O HO
+
(a) OCH3 and OMe (b) and

H3C—C—NMe2 H3C—C—NMe2 N N
H

8. Write structural isomer of C 6H 14. What is relation between them ?

9. Arrange the following in the order of their enolic content :

O O O
O

O
O O IV
I II III

10. Which of the following does/do not exhibits tautomerism.

O O O
(i) CH3—C—CH3 , (ii) CH3—C—CH2—C—OC2H5

O
(iii) CH2=CH—C—H (iv) —OH
 CON CEP TUAL SU BJ ECTIVE E X ER CISE ANSWER KEY E XE R CISE -4 (A)

1. There are 7—1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, diethyl ether, methyl propyl
ether, and methylisopropyl ether.
2. If the bonds were localized, there would be 4 isomers ; actually there are only 3 of the following, the first two
are identical, because the bods are not localized.

Cl Cl Cl Cl
Cl Cl

Cl
Cl
3. Only CHBr = CHCl can exist as geometric isomers :

Br Cl Br H
C C and C C
H H H Cl

In CH 2Cl— CH 2Cl and CH 2Cl—CH 2Br, the carbon atoms are connected by a single bond about which the
groups can rotate relatively freely. Thus any conformation of the halogen atoms may be converted into any
other simply by rotation about the single bond. In CH2Cl2, the configuration of the molecule is tetrahedral and
all interchanges of atoms yield exactly equivalent configurations.
4. Maleic acid forms an anhydride where as fumaric acid does not.
O

CO2H H C H CO2H
CH
H  O H 

CH   H   no anhydride.

 C 
CO2H CO2H H
O
H H

5. This is cis form. Two H atoms on the same side. To get trans, ring must be twisted.

Double bond becomes severely twisted-destabilized. Effective overlap of P orbitals is missing, so does not exist.
6. The Pz orbitals forming -bonds and the empty Pz orbital of the carbon with +ve charge are parallel. So the
electrons may be delocalized. The +ve charge is effectively spread out over two carbons; delocalized.
-orbital
H empty orbital
C C
H C+ H
H
 
CH 2 =CH— C H 2  C H 2 —CH= CH

In n-propyl cation, + I effect of R increases the stability.

In allyl + M effect increases the stability. But + M effect in allyl cation is more effective. So allyl > propyl.
A group with + M effect stabilizes cation; destabilizes anion.
7. Lone pair - p conjugation between fluorine and carbon will be more effective than between chlorine and
carbon.
9. III > IV > I > II
EXERCISE–04 [B] BRAIN STORMING SUBJECTIVE EXERCISE

SUBJECTIVE QUESTIONS :

1. What is relation between (a), (b), (c) ?

–
O O
OH
+ +
HN NH HN NH
N N
(a) (b) (c) +
N – N –
O O O O
HO N OH
H H

2. Which side is favoured at equilibrium, provide quantitative explanation :

O O O O


H 2 O + HO –
O O O O
pK a  16 pKa =13
3. (+) 2-butanol has specific rotation of + 13.9° when measured in pure form. A sample of 2-butanol was
found to have an optical rotation of –3°. What is the stereomeric composition of this mixture ?

4. N-methylethenamine as such does not show any stereoisomerism but one of its resonance form exhibit
stereoisomerism. Explain.

5. Assign Cahn-ingold prelog priorites to the following sets of substituents :

(i) —H, —Br, —CH 2 CH 3 , —CH 2 CH 2 OH (ii) —COOH, —COOCH 3 , —CH 2 OH, —OH

(iii) —CN, —CH 2 NH 2 , —CH 2 NHCH 3 , —NH 2 (iv) —Br, —CH 2 Br, —Cl, —CH 2 Cl

6. Identify whether the stereogenic centre is present or not :

(i) 2-Cyclo penten-1-ol (ii) 3-cyclo penten-1-ol (iii) 2-bromopentane (iii) 3-bromopentane

7. Discuss the optical activity of tertiary amines of the type R 1R 2R 3N :

8. Draw the enantiomer of the following structure :

CH3

H C
Cl C2H5

9. 2,4-Hexadiene has three geometrical isomers. Draw their structures.

10. Assign R and S configuration to the chiral carbons in the following :

CH3 CH3
HO———H H———OH
(i) (ii)
H———OH H———OH
CH3 CH3
 BRAIN STOR MIN G SUBJ ECTIVE E X ER CISE ANSWER KEY E XE R CISE -4 (B)

1. a & b are tautomers and a & c are resonating structures.

3. Let x is the % of (+) 2-butanol.
13.9 x – 13.9 (100 – x) = – 300.
x = 39.2, % of d form = 39.2, % of  form = 60.8.
:

CH2 =CH — NH—CH3

4.

:

CH2 —CH = NH—CH3 (this shows Geometrical isomerism)

5. (a) —Br > —CH 2 CH 2 OH > —CH 2 CH 3 >— H, (b) —OH > —COOCH 3 >—COOH >—CH 2 OH
(c) —NH 2 >—CN >—CH 2 NHCH 3 >—CH 2 NH 2 (d) —Br >—Cl >—CH 2 Br >—CH 2 Cl
4=3 3=4

5=2 2=5
6. (i) Hydroxyl bearing carbon is stereogenic centre., (ii) It has no stereogenic centre.
H OH H OH

Br

(iii) CH3—C—CH2—CH2—CH3 bromine bearing carbon is stereogenic centre.

H
Br

(vi) CH3—CH2—CH—CH2—CH3 It has no stereogenic centre.

••
7. Tertiary amines have pyramideal geometry with sp 3-hybridization at nitrogen.
N
It should be a chiral molecule (assuming lone pair to be a substituent). Thus, R1 R3
R2
tertiary amines exist as racemic mixture but they cannot be resolved.

This is due to the reason that the energy difference between the isomer is very small (25 kJ mol –1). Hence,
rapid nitrogen or amine inversion takes palce.
2
sp -hybridized 2
2
R1 sp
R1 sp R1
R2
••

R2 N N
•

N
••

R3 R3
R2 R3
Planar transition state
Enantiomers
Tertiary amine N-oxide has four group hence nitrogen inversion is not possible, thus tertiary amine -N-oxide
can be resolved.
CH3

8. Cl C
H C2H5

10. (i) 2R, 3R (ii) 2S, 3R

EXERCISE–05(A) PREVIOUS YEARS QUESTIONS

1. Recemic mixture is formed by mixing two- [AIEEE-2002]

(1) isomeric compounds (2) chiral compounds
(3) meso compounds (4) enantiomers with chiral carbon
2. Geometrical isomerism is not shown by- [AIEEE-2002]
(1) 1,1–dichloro–1–pentene (2) 1,2–dichloro–1–pentene
(3) 1,3–dichloro–2–pentene (4) 1,4–dichloro–2–pentene
3. Following types of compounds I and II [AIEEE-2002]
(I) CH 3 CH=CHCH 3

(II) CH3 CH OH, are studied

CH2CH3

in terms of isomerism in-

(1) chain isomerism (2) position isomerism
(3) conformers (4) stereo isomerism
4. Among the following four structures I to IV [AIEEE-2003]

H
C2H5 CH C3H7 C2H5 C CH C2H5 + C2H5 CH C2H5
H C
CH3 O CH3 CH3
H
(I) (II) (IV)
(III)

It is true that-
(1) All four are chiral compounds
(2) only I and II are chiral compounds
(3) only III is a chiral compound
(4) only II and IV are chiral compounds
5. Which of the following will have a meso-isomer also- [AIEEE-2004]
(1) 2–chlorobutane (2) 2,3–dichlorobutane
(3) 2,3–dichloropentene (4) 2–hydroxy propanoic acid
6. Amongst the following compounds, the optically active alkane having lowest molecular mass is
(1) CH3 CH2 C CH [AIEEE-2004]

CH3

(2) CH3 CH2 CH CH3

(3) CH3 C

C2H5
(4) CH3 CH2 CH2 CH3
7. Which of following compounds is not chiral [AIEEE-2005]
(1) 1–chloropentane
(2) 2–chloropentane
(3) 1–chloro–2–methyl pentane
(4) 3–chloro–2–methyl pentane
8. Of the five isomeric hexanes, the isomer which can give two monochlorinated compounds is-
(1) 2-methyl pentane [AIEEE-2005]
(2) 2,2–dimethyl butane
(3) 2,3–dimethyl butane
(4) n-hexane
9. Which types of isomerism is shown by 2,3–dichloro butane- [AIEEE-2005]
(1) structural (2) geometric
(3) optical (4) diastereo
10. Increasi ng order of stabi lit y among the three mai n conformat ions (i.e. Eclipse, Ant i, Gauche) of
2-fluoroethanol is [AIEEE-2006]
(1) Gauche, Eclipse, Anti
(2) Eclipse, Anti, Gauche
(3) Anti, Gauche, Eclipse
(4) Eclipse, Gauche, Anti
11. Which one of the following conformations of cyclohexane is chiral ? [AIEEE - 2007]
(1) Twist boat (2) Rigid
(3) Chair (4) Boat
12. Which of the following molecules is expected to rotated the plane of plane-polarised light ?

CHO

HO H
(1) (2) [AIEEE - 2007]
SH
CH2OH

COOH
H 2N NH2
(3) H H (4) H2N H
Ph Ph

HO2C CO2H
13. The absolute configuration of is [AIEEE - 2008]
HO H H OH

(1) S, S (2) R, R (3) R, S (4) S, R

14.   D      glu cos e and   D      glu cos e are [AIEEE - 2008]

(1) conformers (2) epimers

(3) anomers (4) enantiomers
15. The alkene that exhibits geometrical isomerism is :- [AIEEE - 2009]
(1) 2–butene (2) 2–methyl–2–butene
(3) Propene (4) 2–methyl propene
16. The number of stereoisomers possible for a compound of the molecular formula
CH 3 –CH = CH–CH(OH)–Me is :- [AIEEE - 2009]
(1) 4 (2) 6 (3) 3 (4) 2
17. Out of the following, the alkene that exhibits optical isomerism is :- [AIEEE-2010]
(1) 2-methyl-2-pentene (2) 3-methyl-2-pentene
(3) 4-methyl-1-pentene (4) 3-methyl-1-pentene
18. Identify the compound that exhibits tautomerism :- [AIEEE-2011]
(1) 2-Pentanone (2) Phenol
(3) 2-Butene (4) Lactic acid
19. How many chiral compounds are possible on monochlorination of 2–methyl butane ? [ A I E E E - 2 0 1 2 ]
(1) 6 (2) 8 (3) 2 (4) 4
20. Which branched chain isomer of the hydrocarbon with molecular mass 72 u gives only one isomer of mono
substituted alkyl halide ? [AIEEE-2012]
(1) Neohexane (2) Tertiary butyl chloride
(3) Neopentane (4) Isohexane
21. How many cyclic structures are possible for C 4 H 6 :- [AIEEE-2012(Online)]
(1) 3 (2) 5 (3) 4 (4) 6
22. Maleic acid and fumaric acids are :- [AIEEE-2012(Online)]
(1) Tautomers (2) Chain isomers
(3) Geometrical isomers (4) Functional isomers

PREVIOUS YEAR QUESTIONS ANSWER KEY EXERCISE-5(A)

Q u e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans 4 1 4 2 2 3 1 3 3 2 1 1 2 3 1
Q u e. 16 17 18 19 20 21 22
Ans 1 4 1 4 3 3 3
EXERCISE–05(B) PREVIOUS YEARS QUESTIONS
MCQ's WIT H ONE CORRECT ANSWER
1. The enolic form of acetone contains : [IIT-90]
(A) 9 bonds, 1 bond and 2 lone pairs (B) 8 bonds, 2 bonds and 2 lone pairs
(C) 10 bonds, 1 bonds and 1 lone pair (D) 9 bonds, 2 bond and 1 lone pair

2. An organic molecule necessarity shows optical activitiy if it : [IIT-93]

(A) Contains asymmetric carbon atoms (B) is non polar
(C) is non superimposable on its mirror image (D) is superimposable on its mirror image
3. The compound which is not isomeric with diethyl ether is : [IIT-93]
(A) butan–1–ol (B) butanone
(C) 2–methyl propan–2–ol (D) n–propyl methyl ether
4. Ordinary light can be converted into plane polarized light with the help of a : [IIT-93]
(A) Nickel prism (B) Nicol prism (C) Diffraction grating (D) Quartz cell
5. The structure shows : [IIT-95]
H3C H
C=C H
H3C C
COOH
CH3
(A) Geometrical isomerism (B) Optical isomerism
(C) Geometrical & optical isomerism (D) tautomerism
6. How many optically active stereoisomers are possible for butane –2,3–diol : [IIT-97]
(A) 1 (B) 2 (C) 3 (D) 4
7. Isomers which can be interconverted through rotation around of single bond are -
[IIT-97]
(A) Conformers (B) Diastereomers (C) Enantiomers (D) Positional isomers

8. The number of possible enantiomeric pairs that can be produced during monochlorination of
2–methyl butane is : [IIT-97]
(A) 2 (B) 3 (C) 4 (D) 1
9. Tautomerism is not exhibited by : [IIT -98]

O
(A) CH=CH–OH(B) O O (C) (D) O
O
O
10. Rotation of polarised light can be measured by : [IIT-98]
(A) Monometer (B) Galvanometer (C) Polarimeter (D) Viscometer

11. The optically active tartaric acid is named as D–(+) tartaric acid because it has a positive : [IIT -99]
(A) optical rotation and is derived from D–glucose
(B) pH in an organic solvent
(C) optical rotation and is derived from D–(+)– glyceraldehyde
(D) optical rotation only when substituted by deuterium
12. The enol form of acetone, after treatment with D 2 O gives [IIT-99]

OD O
(A) CH3–C=CH2 (B) CD3–C–CD3

OH OH
(C) CH2–C=CH2D (D) CD2=C–CD3

13. Which of the following compound will exhibits geometrical isomerism : [IIT-2000]
(A) 1–phenyl–2–butene (B) 3–phenyl–1–butene
(C) 2–phenyl–1–butene (D) 1, 1–diphenyl–1–propene
14. The number of isomers for the compound with molecular formula C 2 BrCIFI is : [IIT-2000]
(A) 3 (B) 4 (C) 5 (D) 6
15. Which of the following exhibits stereoisomerism– [IIT-2000]
(A) 2–Methylbutene–1 (B) 3–Methylbutyne–1
(C) 3–Methylbutanoic acid (D) 2–Methylbutanoic acid
16. Hydrogen of the following compound in the presence of poisoned palladium catalyst gives : [IIT-2002]

Me H Me

H
Me H

(A) optically active compound (B) an optically inactive compound

(C) a racemic mixture (D) a diastereomeric mixture
17. Which of the following has the lowest dipole moment :
[IIT-2002]

CH3 CH3
(A) C=C (B) CH 3 –CC–CH 3 (C) CH 3 CH 2 CCH (D) CH 2 =CH–CCH
H H

18. If C 2 in below compound is rotated by 120º angle in anticlockwise direction along C 2–C 3 , which of the
following form will be produced : [IIT-2004]
1
CH3
H H
2
3

H H
CH3
4
(A) Partial eclipsed (B) Per fectly eclipsed (C) Per fectly staggered (D) Gauche conformation

CH3
Cl2/hv
19. CH3–CH–CH2–CH3 N  no. of isomers  
Fractional distillation
  F  ,  (N) and  (F) are :

[IIT-2006]
(A) 6, 4 (B) 4, 4 (C) 6, 6 (D) 3, 3
20. The number of structural isomers of C 6 H 14 is : [IIT-2007]
(A) 3 (B) 4 (C) 5 (D) 6
21. The number of stereoisomers obtained by bromination of trans–2–butene is : [IIT-2007]
(A) 1 (B) 2 (C) 3 (D) 4
22. Statement-I : Molecules that are not superimposable on their mirror images are chiral
Because
Statement-II : All chiral molecules have chiral centres. [IIT-2007]
(A) Statement-1 is True, Statement-2 is True ; Statement-2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
23. The correct statement(s) concerning the structures E, F and G is (are) [IIT-2008]

H3C O OH
H3C H3C CH3
H3C CH3 H3C CH3 H3C OH
(E ) (F ) (G )

(A) E, F and G are resonance structures

(B) E, F and E, G are tautomers
(C) F and G are geometrical isomers
(D) F and G are diastereomers
24. The correct statement(s) about the compound given below is (are) :- [IIT-2008]

Cl H
H3C CH3
Cl H

(A) The compound is optically active

(B) The compound possesses centre of symmetry
(C) The compound possesses plane of symmetry
(D) The compound possesses axis of symmetry
25. The correct statement(s) about the compound H 3C(HO)HC – CH = CH – CH(OH)CH 3 (X) is (are) :
(A) The total number of stereoisomers possible for X is 6 [IIT-2009]
(B) The total number of diastereomers possible for X is 3
(C) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible for
X is 4
(D) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for X is 2
26. The bond energy (in kcal mol –1 ) of a C–C single bond is approximately : [IIT-2010]
(A) 1 (B) 10
(C) 100 (D) 1000
27. In the Newman projection for 2,2–dimethylbutane [IIT-2010]
X
H3C CH3

H H
Y
X and Y can respectively be –
(A) H and H (B) H and C 2 H 5 (C) C 2 H 5 and H (D) CH 3 and CH 3
28. Amongst the given option, the compound(s) in which all the atoms are in one plane in all the possible
conformations (if any), is (are) - [IIT-2011]
H H H
C–C
(A) (B) H – C  C – C (C) H 2 C = C = O (D) H 2 C = C = CH 2
H2C CH2 CH2
29. Which of the given statement(s) about N,O,P and Q with respect to M is (are) correct ? [ I I T - 2 0 1 2 ]
HO HO Cl CH3 CH3
H H
H OH H OH HO H
Cl CH3
HO H HO
Cl OH H
HO H HO H
CH3 Cl CH3 Cl Cl
M N O P Q
(A) M and N are non-mirror image stereoisomers (B) M and O are identical
(C) M and P are enantiomers (D) M and Q are identical
P & Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O, On heating P forms the cyclic
anhydride.
Upon treatment with dilute alkaline KMnO 4, P as well as Q could produce one or more than one from
S, T and U. [JEE ADVANCED-2013]
COOH COOH COOH
H OH H OH HO H
H OH HO H H OH
COOH COOH COOH
(S) (T) (U)
30. Compounds formed from P and Q are respectively
(A) Optically active S and optically active pair (T, U)
(B) Optically inactive S and optically inactive pair (T, U)
(C) Optically active pair (T, U) and optically active S
(D) Optically inactive pair (T, U) and optically inactive S

P RE VIOU S Y EARS QU E STION S ANSWER KEY E XE R CISE -5 (B)

1. (A) 2. (C) 3. (B) 4.(B) 5. (B) 6. (B) 7.(A) 8. (A)

9. (B) 10. (C) 11. (C) 12. (A) 1 3. (A) 14. (D) 1 5. (D) 16. (B)

17. (B) 18. (D) 19. (B) 20. (C) 21. (A) 22. (C) 23. (B, C, D)

24. (A, D) 25. (A, D) 26. (C) 27. (B, D) 28. (B, C) 29. (A, B, C) 30. (B)