Isomerism 11.

Chapter 11 Isomerism

Intext Exercise 1
1. Option (b) has all same 1 hydrogen
o
7.
2. No. of c atom different in (a)
3. (b) option has same functional group but different
arrangement around them.
4. (i) and (iv) are 1o and 2o amine respectively hence 8.
functional isomers.
9.
5.
10. Cl
6.
Cl
Cl Cl
C
C
C C C C

Intext Exercise 2
1. Given in Ans 7. (a) has active methelene group and its enol form is
resonance stabilized.
2. Given in Ans
8. (b) active methelene group and no +m group.
3. Phenol is aromatic hence max enol % in d.
9. (c) has 3 intramolecular hydrogen bonding and
4. (a) has no hydrogen on sp3 in keto form
once aromaticity is over then keto form is more
5. (b) has hydrogen on sp3 carbon. stable then enol form.
6. (d) has hydrogen on sp3 carbon. 10. B, C, D, F, G will show tautomerism.
Intext Exercise 3
1. Ans given
7.
2. Ans given
3. All have different groups on two atoms.

8.
4.
Ans. 4
9. (i) cis (ii) trans (iii) trans
5. (a) (b) (c)
10.
No GI No GI No GI
6. Cumulenes with even No. of double bond do not
show GI.
11.2 Chemistry
Intext Exercise 4
1. Self explainatory
2. Self explainatory 8.
3. Self explainatory
4. Self explainatory
9. I and II are G.I. and II has intramolecular hydrogen
0 × 20 + 80 (- 12)
5. a mix = 100 bonding between
amix = 9.6
10. If you make even No. of changes about a chiral
6. (d) is mirror image of structure given in Q.

7.

Intext Exercise 5
1. Odd No. of changes about both the chiral carbon 4. (d) two chiral atoms without symmetry.
produces enantiomers
5. Odd No. of changes about chiral atom produces
2. 24 = 16. enantiomers.

6. Put lowest priority group on dash line by making

even no. of changes. Move 1 2 3 If clockwise
then R otherwise S.
3.
7. Three chiral atom hence 23 = 8.

Intext Exercise 6
1. Gauche form has intramolecular hydrogen bonding. 6. in (b) dihedral angle is 60o hence minimum torsional
o o strain, CH3—CH3 group are at maximum distance
2. CH3, CH3 has 180 angle after 120 rotation angle
o hence minimum VW strain.
between then is 60 hence gauche form.
7. Energy : Eclipse > partial Eclipse > gauche > anti
3. do yourself.
8. (a) Intramolecular hydrogen bonding and minimum
4. In most stable conformational isomers bulky group
tarsional strain.
should be on equatorial position as it is trans both
group at (e, e). 9. do yourself.
5. Stability : III > II > IV > I 10. Energy level of propane is above ethene
Me3C e e a a eclipsed ethane high energy
CH3 e a e a staggered propane low energy
 Isomerism 11.3
EXERCISE 1
1. length of parent chain changes 17. (d) has no hydrogen.

18.

19. Alcohols do not exhibit Tautomerism.

2.
20. H - C / N C!
diad
= N-H
2 1
21. (d) active methylene group has more enol content.
3. 22. (c) both double bonded carbon has different groups.

23. both vectors cancel out.

C
|
24. C—C—C==C C—C==C—C C - C = C
4. cis/trans
5. Do self.
25. (a) Ph - C - C = C - C different groups on double
| | bonded carbon
H H
6.
26. Self.

27.

7.

8. 28. Self.
29. (a) Shows about 6 member ring

9. C—C—C—C—C—C
(b) (c)
H3C CH3
30. (a) compound has Z conf. about C=C and Z should

31. It has single chiral carbon hence it is optically active.

32. (a) no chiral carbon atom.
10. Self. 33. 2 chiral carbon with symmetricity hence
11. C – C – C – O – C C – C – O – C – C C - C - O - C 2n 1 + 2n/2 1 = 21 + 2o = 3
|
C
12. (b) has 2 degree of unsaturation while other has 1. 34.
13. same as Q. 11.
14. Self.
15. IIIrd pair is functional isomers. 35.
16. (d) as it form aromatic enol form.
11.4 Chemistry
36. (b) — (d), 2 changes hence identical 49. Self
37. (b) — (c), 2 changes hence identical 50. Fact
38. 3 No. of chiral atom with symmetricity hence meso C
compounds are 51. (c) C C C COOH
C
(a) C C C C
C
(b) C C C C
H
39. cis — cis, trans — trans, cis S trans
(d) C C C* COOH
cis R turn hence 4
C
25 × (- 158) + 75 ×158
40. a = 100 =+ 79 o 52. Fact.

41. 53.

54. two chiral atom with symmitricity

42. Same physical property but different optical
two optically active, one optically
property.
inactive
43. (d) because it is always unsymmetric
55. == C > C — C
44. (c) has center of symmetry.
56. (d) as it is aromatic.
57. Fact
45.
58. Intramolecular hydrogen bonding make stable
confermers.
— 2 changes hence same (lowest priority group
should be on | | | | | line) 61. Flagpole

62. Baeyer’s angle strain :

46. cyclopropane>cyclobutane>cyclohexane>cyclopentane
63.
47. Identical substituent on the same side.
48. Mirror image 64.
EXERCISE 2
C C
1. Ans. 4 4. ; ;C C C C
OH

2.
5. ;

C C C
3. C—C—C—N—C, C—C—N—C—C,
C NH2
1o
;
C-C-N-C
 Isomerism 11.5

6. 22.

23.

24. This show GI and it has E

7. Relative position changes hence position isomers 25.

8. do self

9. metamers groups around changes

26.
10. metamers groups around changes
11. Fact. 27.
12. Acidic hydrogen replaced with D
!

!
28.

!
Ph C C C CH2
13. Enol content : 29.

14. Enol content :

30. In case of MP : trans > cis
DM : cis > trans
BP : cis > trans

15.

16. 31. (a) 2 (b) 2 (c) 4 (a) 2

32.
17.

18.

33.
19.

20. Both the double bonded c atoms have same groups

21. (c) 34. hence I and II same

11.6 Chemistry
42. Stability :
35.

43. Fact
36. (b) Same group on opposite side at equal distance
from center. 44. Fact

37. (d) has plane of symmetry and center of symmetry.

Other has no symmetry
45. Minimum torsional strain condition

38. hence enantiomers

46. Minimum v w strain, minimum torsional strain.

39. 47.

40. 48. Fact

49. bulky group should be on equatorial position for
stability
41. Energy :

EXERCISE 3
1.
temperature and light

C
2.
C C C C C C C C C Total 7
C O C O

6 ×13.5 - 4 ×13.5 2 8. 24 = 16
3. a mix = 10 = 10 ×13.5 =+ 2.7 units
2
excess % = 10 ×100 = 20% all are unsymmetrical hence optically active
4. Optically pure compound can separate enontioners

9.
5.

6.
hence 4 fraction 10.

7.
 Isomerism 11.7
11. Intramolecular hydrogen bonding
12. Fact.
24. 27 = 128

13.

25. 23 = 8

26. (d) does not have hydrogen to show tautomerism

14. at 1, 2 position — (a, a) or (e, e) — trans

(a, e) — cis 27. , ,

15. ,
28. For cis trans Nomenclature at least one group
16. (a) plane of symmetry should be common on double bonded carbon atoms.
(b) plane of symmetry 29. (c) two geometrical isomers about partial double
bond
(c) plane of symmetry
(d) No. element of symmetry

17. s-cis s-trans

(d) No. of geometrical isomers = 25 = 35
30. (a) resonating structure
18. Fact.
(d) Functional isomers
19. (a) has center of symmetry,
31. (a) function isomers
(b) does not have any plane of symmetry
(c) position isomers
20. Both structure are diasteromer
32. (II) is optically inactive
21. No element of symmetry due to methyl group.
22. Product should no show geometrical isomerism 33.
otherwise there will be more than two product hence
products are Ph—NH—N==CH2,
34. (a), (b) and (c) show GI about double bond and (d)
will show around single bond.
35. (d) does not show GI.
23. 36. Threo functional group opposite side, erythro
25 = 32. functional group same side
11.8 Chemistry
37. (c) has same group on double bonded carbon atom

(b)

48.

49. (d) no H for tautomerism

38. (a) planar, not chiral
(b) Chiral, resolvable
(c) Chiral, non resolvable (a) (b) (c)
(d) planar, not chiral
Ans (b)
39. Fact. 50.

40.

51. enol context :

(A) has 4 carbon (B) has 3 carbon hence they are not
related

1 2
41.

42. 3 4
about only one carbon hence they are diastereomers.
43. (a) chain isomers (b) position isomers 2>3>4>5>1
(c) position isomers (d) functional isomers 5
44. (a) and (b) are optically active and mirror image 52. (b) no H for tautomerism
to each other in horizontal mirror. (b) and (c) are
(a)
one chiral carbon only.
45. (a), (b) and (d) does not have H for tautomerism (c) (d)

(c)
53. (b) has repulsion betuaen groups hence enol
46. enantiomers have same physical and chemical form more stable.
properties but different reactivity with chiral reagent (d) becomes aromatic in enol form.
and different optical rotation of plane polarized
light.
54.
47.
55. (a) chain isomers (d) functional isomers
 Isomerism 11.9
56. (a) I syn II anti 67. (c) Intramolecular HB and minimum VW strain
68. Fact.

57. (c) 69. (c) maximum VW strain and maximum torsional

strain
70. (d) small groups hence less torsional strain
58. (d) functional isomers
71. (b) has plane of symmetry
59. II dihedral angle 60o hence minimum torsional
72. p form is racemic mixture hence optically inactive
strain and CH3 groups are at maximum distance
due to external compensation.
hence minimum VW strain.

60. (b) 73.

(a) and (d) has plane of symmetry

(c)
74.

61.
75. (i) E (ii) Z (iii) E (iv) E

62. (a) does not have any chiral atom. 76.

63.
77. acetic acid is optically inactive hence zero.
78. 1, 2 cis (a, e) (iii), (viii)
1, 3 cis (e, e), (a, a) (v), (vi), (vii)
1, 4 cis (a, e)

79. a

(p) Same
(Q) enantionmer
64. Asymmetric optically active and free from all (r) enantiomers (s) enantiomer
symmetry elements.
(t) enantiomer
Dissymmetric optically active compound with Cn
8
symmetry elements. 80. x % = 32 × 100 = 25 %

81. [a]mix = 60×150 + 40× - 150 = 20×150 = 30 o

65. 100 100

82. 23 = 8

66. (a) minimum VW strain and tortional strain

11.10 Chemistry
(d) I II confermers
83. cis cis DM : >
tran trans Stability > : hydrogen bonding
cis R trans
cis S trans 89. (a) Structure isomers, GI = 2 for both
hence 4. (b) Structure isomers, GI = 3 for both
84. two chiral carbon with symmetricity hence 3 optical (c) GI, GI = 2 for both
isomers and geometrical isomers about double bond GI
hence 3 × 2 = 6 (four optically active, two meso). 90. * 2+2

2+2
*

85. 25 1 = 31 *

86. Z = 2 R=3 23 = 8
Y=2 W=2
87. do self
88. I II conformers
(a) DM : >
91.
Stability : > : hydrogen bonding and second Z.
(b) Same as (a)
(c) I II Not confermers but diasteromers
DM : >
Stability < : Less VW strain second Z.

1.
S
(2S, 3R) 6. 2×2=4
R

2. (a) Ph—C—C==C—C 7.
cis + trans

3. 8. (a) is chiral. rotates plane of polarised light.

9. Fact.
4. C C C C
10. C C C C ; C C C C
mol wt = 12 × 5 + 4 × 3 = 72 Cl Cl
CH3
5. (a) H Cl
11. H Cl POS is present
CH3
12. I, II have chiral carbon atom.
 Isomerism 11.11

1. Chiral atom is not necessary for chiral molecule 7. (a) can rotate about partial double bond
(b) planar (c) planar
2.
(d)

8. Total 6 optical isomers, 4 OA, 2 OIA

RER RES
RZR RZS
3. (b) has zero dipole moment SES
4. (b) does not have any suitable hydrogen. SZS

5. (a) (b)
9.

(c) (d)
10.
O
11. O O O O O
6. M, Q are diastereomers. * *
* *
about one chiral atom hence diastereomers (1) (2) (1) (2) (1) (3)
HO H OH HO H OH HO H OH

12. Pe Pe Pe
HH HH HH
Pe Pe Pe
HO H OH HO H OH HO H OH
Optically Inactive Optically Active Optically Active
OH OH
HO H OH HO H HO H
Pe Pe
H OH H OH
Pe
HH
Pe
Pe Pe
HO H HO H H HO H H
OH
Optically Inactive Optically Active Optically Active
OH OH
HO H Pe HO H Pe
H OH H OH

Pe Pe
HO H H HO H H

Optically Active Optically Active

13. Two chiral atom but bridge head does not allow other diastereomers to form hence only given structure and its
mirror image. Ans 2

14.
11.12 Chemistry